Electrochemical Surface Science: Molecular Phenomena at Electrode Surfaces

ACS SYMPOSIUM SERIES 378
Electrochemical Surface Science

Molecular Phenomena at Electrode
Surfaces
Manuel P. Soriaga, EDITOR
Developed from a symposium sponsored

by the Division of Colloid and Surface Chemistry
at the 194th Meeting
of the American Chemical Society,
New Orleans, Louisiana,
August 30-September 4, 1987
American Chemical Society, Washington, DC 1988
In Electrochemical Surface Science; Soriaga, M.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
Library of Congress Cataloging-in-Publication Data
Electrochemical surface science.

(ACS symposium series, 0097-6156; 378)
"Developed from a symposium sponsored by the

Division of Colloid and Surface Chemistry at the 194th
Meeting of the American Chemical Society, New Orleans,
Louisiana, August 30-September 4, 1987."
Includes bibliographies and indexes
1. Electrochemistry—Congresses
chemistry—Congresses. 3. Electrodes—Surfaces
Congresses.
I. Soriaga, Manuel P.. 1949- . II. American Chemical

Society. Division of Colloid and Surface Chemistry.
III. American Chemical Society. Meeting (194th: 1987:
v
New Orleans, La.). IV. Series.
QD551.E494 1988 541.3*724 88-26311
ISBN 0-8412-1542-1
Copyright © 1988
American Chemical Society
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1988 ACS Books Advisory Board

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Preface
V E L O P M E N T O F SOPHISTICATED S U R F A C E A N A L Y T I C A L TECHNIQUES
over the past two decades has revived interest in the study of phenomena
that occur at the electrode-solution interface. As a consequence of this
renewed activity, electrochemical surface science is experiencing a rapid
growth in empirical information Th symposiu which thi book
based brought together establishe
the three interrelated disciplines of electrochemistry, surface science, and
metal-cluster chemistry to help provide a better focus on the current
status and future directions of research in electrochemistry. The
symposium was part of the continuing series on Photochemical and
Electrochemical Surface Science sponsored by the Division of Colloid
and Surface Chemistry of the American Chemical Society.
This volume contains 36 chapters, the first of which is an overview
chapter. The eleven following chapters describe the use of ultrahigh
vacuum surface spectroscopic methods in the study of the
electrode-solution interface. The next eight chapters report recent
advances in the adaptation of new experimental techniques, such as
scanning tunneling microscopy, to electrochemical problems. The seven
following chapters discuss critical aspects of in situ vibrational
spectroscopy. The last nine chapters describe various electrode processes
such as the electrochemical reactivity of polymer deposits, C 0 2
methanation, and surface organometallic chemistry. The broad but

balanced range of important topics discussed by experts here should
make this volume invaluable to students and active researchers in
electrochemical surface science.
Acknowledgments
The symposium and this volume have benefited from financial support
provided by the Division of Colloid and Surface Chemistry of the
American Chemical Society, the Petroleum Research Fund, Shell
xi

Development Company, and Texas A & M University. I gratefully
acknowledge the cooperation of the authors in meeting the various
deadlines.
MANUEL P. SORIAGA
Texas A&M University
College Station, TX 77843
June 30, 1988
xii

Chapter 1
Electrochemistry: The Senior but Underused

Area of Surface Science
Manuel P. Soriaga
Department of Chemistry, Texas A&M University, College Station,

TX 77843
Electrochemistry ought to be regarded as a vintage area of
i n t e r f a c i a l science It has long been known that the
application of an externa
s o l i d - s o l u t i o n interfac
adjacent chemical species. Catalytic reactions activated
by control of p o t e n t i a l at the electrode-solution
interface thus serves as an alternative to activation by
control of temperature at gas-solid interfaces. In fact,
on the singular basis of c a t a l y t i c s e l e c t i v i t y , the
electrochemical route towards synthesis and catalysis
should be favored over the thermal approach because the
application of elevated temperatures activates other
reaction pathways. For a two-electron reaction, for
example, a potential change of only half a volt can lead
8
to a 10 -fold increase in reaction rate. Assuming an
activation energy of 75 kJ m o l e -1, this enormous rate
increase can be effected only at temperatures above 600 K.
Such drastic conditions invariably lead to a wide spectrum
of thermal excitations which could result in undesirable
side-reactions such as indiscriminate bond-breaking.
In addition to the universal concern for catalytic
s e l e c t i v i t y , the following reasons could be advanced to
argue why an electrochemical scheme would be preferred
over a thermal approach: (i) There are experimental
parameters (pH, solvent, electrolyte, potential) unique
only to the electrode-solution interface which can be
manipulated to dictate a certain reaction pathway, (ii)
The presence of solvent and supporting electrolyte may
sufficiently passivate the electrode surface to minimize
c a t a l y t i c fragmentation of starting materials. (iii)
Catalyst poisons due to reagent decomposition may form
less readily at ambient temperatures, (iv) The chemical
behavior of surface intermediates formed in e l e c t r o l y t i c
solutions can be closely modelled after analogous well-
characterized molecular or cluster complexes (1-8). (v)
For hydrogenation (or oxidation) reactions, the aqueous
solvent functions as a convenient source of hydrogen (or
0097H5156/88/0378-0001$06.00/0
° 1988 American Chemical Society

2 E L E C T R O C H E M I C A L SURFACE SCIENCE
o x y g e n ) . ( v i ) B e c a u s e e l e c t r o c a t a l y s i s employs a r e d u c i n g
and an oxidizing electrode, there is promise for
implementation of the concept of p a i r e d e l e c t r o s y n t h e s i s
(A) -
It is true that electrochemistry has enjoyed
tremendous successes i n the f i e l d s of chemical analysis
( s e n s o r s ) and e n e r g y c o n v e r s i o n (batteries). It i s also a
fact that the use of electrochemistry has become
w i d e s p r e a d i n modern-day i n o r g a n i c c h e m i s t r y where r e d o x
p o t e n t i a l s o f newly s y n t h e s i z e d m a t e r i a l s are d e t e r m i n e d
a l m o s t as r o u t i n e l y as s p e c t r o s c o p i c and c r y s t a l l o g r a p h i c
d a t a . However, d e s p i t e i t s h i s t o r i c a l s i g n i f i c a n c e and
despite a l l t h e a p p a r e n t advantages enumerated above,
electrochemistry remains relegated to the background
i n s o f a r as l a r g e - s c a l e c a t a l y t i c s y n t h e s i s i s c o n c e r n e d .
T e c h n o l o g i c a l and e n g i n e e r i n g c o m p l e x i t i e s , s u c h as s l o w
mass t r a n s p o r t i n s o l u t i o d th t f electricity
are important f a c t o r
e l e c t r o c h e m i c a l approach
i s the absence of a t o m i c - l e v e l d e s c r i p t i o n s of processes
which occur at the e l e c t r o d e - s o l u t i o n i n t e r f a c e . T h i s l a c k
o f f u n d a m e n t a l i n f o r m a t i o n can be a t t r i b u t e d t o t h e f a c t
that, until these past two decades, conventional
electrochemical methods (10), s u c h as voltammetric,
amperometric, coulometric, impedance, and transient
m e a s u r e m e n t s , were t h e o n l y t o o l s r e a d i l y a v a i l a b l e f o r
the study of e l e c t r o d e processes; these techniques are
severely restricted i n the type of information they
provide since the results obtained from them are
m a n i f e s t a t i o n s of only the macroscopic p r o p e r t i e s of the
electrode-solution interface.
The recognition of the lack of molecular-level
i n f o r m a t i o n on e l e c t r o c a t a l y t i c phenomena and t h e r e s o l v e
t o have t h i s weakness r e c t i f i e d i s now f i r m l y e s t a b l i s h e d
within the • e l e c t r o c h e m i c a l and surface science
c o m m u n i t i e s . T h i s i s e v i d e n c e d by r e c e n t i n t e r n a t i o n a l
conferences and workshops devoted solely to
e l e c t r o c h e m i c a l problems (11-4). I t i s a l s o w e l l - r e a l i z e d
t h a t e l e c t r o c h e m i s t r y cannot advance f u r t h e r u n l e s s the
practitioners in this f i e l d begin t o view electrode-
s o l u t i o n p r o c e s s e s from a m o l e c u l a r - l e v e l p e r s p e c t i v e .
The c e n t r a l i s s u e w h i c h has t o be a d d r e s s e d i n any
c o m p r e h e n s i v e s t u d y o f e l e c t r o d e - s u r f a c e phenomena i s t h e
determination of an unambiguous c o r r e l a t i o n between
interfacial composition, interfacial structure, and
interfacial reactivity. This p r i n c i p a l concern i s of
course i d e n t i c a l to the goal of fundamental s t u d i e s i n
h e t e r o g e n e o u s c a t a l y s i s a t g a s - s o l i d i n t e r f a c e s . However,
e l e c t r o c h e m i c a l s y s t e m s a r e f a r more c o m p l i c a t e d since a
f u l l t r e a t m e n t o f t h e e l e c t r o d e - s o l u t i o n i n t e r f a c e must
i n c o r p o r a t e n o t o n l y t h e compact ( i n n e r ) l a y e r b u t a l s o
the boundary (outer) l a y e r o f the e l e c t r i c a l d o u b l e - l a y e r .
The e f f e c t o f t h e o u t e r l a y e r on e l e c t r o d e r e a c t i o n s has
been n e g l e c t e d i n most s u r f a c e e l e c t r o c h e m i c a l s t u d i e s but
i n c e r t a i n s i t u a t i o n s , s u c h as i n c o n d u c t i n g p o l y m e r s and

1. SORIAGA Electrochemistry 3
b i o l o g i c a l systems, processes w i t h i n t h e boundary l a y e r

can e x e r t n o n - t r i v i a l i n f l u e n c e s .
1
In the surface electrochemist s pursuit of
fundamental s t r u c t u r e - c o m p o s i t i o n - r e a c t i v i t y c o r r e l a t i o n s ,
l e s s o n s c a n be a n d have been l e a r n e d f r o m t h e s u c c e s s e s
a c h i e v e d i n b o t h h e t e r o g e n e o u s a n d homogeneous c a t a l y s i s .
F o r example, e x t e n s i v e work on f u e l c e l l e l e c t r o d e s ( 1 5 -
2A) h a s a c c o m p l i s h e d much t o show t h a t c o n c e p t s d e v e l o p e d
i n t h e s t u d y o f oxygen r e d u c t i o n by P t p a r t i c l e s i n g a s -
s o l i d reactions are applicable t o the electrochemistry of
H2 a n d O2 . T h e e s s e n t i a l i n g r e d i e n t s in experimental
s t r a t e g i e s w h i c h have c o n t r i b u t e d t o t h e m o l e c u l a r - l e v e l
u n d e r s t a n d i n g o f a wide v a r i e t y o f homogeneous c a t a l y t i c
processes i n c l u d e (25-6) : ( i ) t h e u s e o f p u r e a n d w e l l -
characterized starting materials, ( i i ) s t r u c t u r a l and
compositional a n a l y s i s o f homogeneous c a t a l y s t s , ( i i i )
structural and compositional analysis o f important
intermediates, (iv
including the concentratio
(v) quantitative analysis of reaction product
distributions. T h e s e e l e m e n t s , w h i c h h a v e now become
r o u t i n e i n model s t u d i e s o f h e t e r o g e n e o u s c a t a l y s i s a t
g a s - s o l i d i n t e r f a c e s , a r e j u s t b e g i n n i n g t o be a p p r e c i a t e d
in surface electrochemical investigations.
S t u d i e s o f t h e p h y s i c s and c h e m i s t r y a t t h e g a s - s o l i d
interface have e n j o y e d tremendous advances from t h e
systematic a p p l i c a t i o n o f modern s u r f a c e spectroscopic
methods (27.) , s u c h a s l o w - e n e r g y e l e c t r o n d i f f r a c t i o n f o r
surface c r y s t a l l o g r a p h i c determinations, Auger e l e c t r o n
spectroscopy f o r surface elemental analysis, X-ray
photoelectron spectroscopy f o r surface bonding studies,
high-resolution electron-energy loss spectroscopy f o r
s u r f a c e v i b r a t i o n a l i n f o r m a t i o n , and t h e r m a l desorption
mass s p e c t r o m e t r y f o r a d s o r p t i o n e n t h a l p y measurements.
T h e s e p o w e r f u l t e c h n i q u e s have p r o v i d e d r e v e a l i n g g l i m p s e s
of g a s - s o l i d i n t e r f a c i a l processes at t h e atomic l e v e l .
Unfortunately, they c a n n o t be e m p l o y e d t o p r o b e t h e
e l e c t r o d e - e l e c t r o l y t e i n t e r f a c e under r e a c t i o n c o n d i t i o n s
s i n c e s u r f a c e c h a r a c t e r i z a t i o n h a s t o be p e r f o r m e d o u t s i d e
the electrochemical cell. Doubts have been raised
concerning the validity of correlating structural
i n f o r m a t i o n a c q u i r e d i n t h e a b s e n c e o f an e l e c t r o c h e m i c a l
environment with r e a c t i v i t y data o b t a i n e d under p o t e n t i a l
c o n t r o l . To h e l p m o l l i f y t h e s e c o n c e r n s , i t has been
pointed out that fruitful structure-reactivity
c o r r e l a t i o n s have been a c c o m p l i s h e d i n homogeneous systems
(25-6) d e s p i t e t h e f a c t t h a t s t r u c t u r a l d e t e r m i n a t i o n s a r e
done i n t h e s o l i d s t a t e w h i l e t h e r e a c t i v i t y measurements
a r e p e r f o r m e d i n s o l u t i o n . R e s u l t s from r e c e n t s t u d i e s o f
emersed e l e c t r o d e s (12,28-9) h a v e a l s o d i s p e l l e d most o f
t h e e a r l i e r doubts. A r e c e n t workshop o r g a n i z e d by t h e
N a t i o n a l R e s e a r c h C o u n c i l h a s recommended t h a t t h e u s e o f
h i g h - v a c u u m s u r f a c e p h y s i c s methods s h o u l d b e c o n t i n u e d
(12.) . The u t i l i z a t i o n o f such techniques i n surface
electrochemistry was i n i t i a l l y restricted t o only a

h a n d f u l o f l a b o r a t o r i e s ( 3 0 - 2 ) b u t t h e number h a s now
i n c r e a s e d . I t i s p a r t i c u l a r l y encouraging t o note t h a t
s u r f a c e s c i e n c e l a b o r a t o r i e s which p r e v i o u s l y devoted a l l
e f f o r t s t o g a s - s o l i d i n t e r f a c e s now a p p o r t i o n s i g n i f i c a n t
t i m e t o t h e s t u d y e l e c t r o c a t a l y t i c phenomena (33-4).
O p t i c a l s p e c t r o s c o p i c methods n o t r e s t r i c t e d t o h i g h -
vacuum c o n d i t i o n s , s u c h a s i n f r a r e d r e f l e c t i o n - a b s o r p t i o n
s p e c t r o s c o p y (25.) , e l l i p s o m e t r y (2£) , and s u r f a c e - e n h a n c e d
Raman s p e c t r o s c o p y ( 3 7 - 8 ) , a r e a v a i l a b l e f o r e x a m i n i n g
i n t e r m e d i a t e s a t t h e e l e c t r o c h e m i c a l d o u b l e - l a y e r under
r e a c t i o n c o n d i t i o n s . However, none o f t h e s e c a n d e t e r m i n e
the complete structure and composition of the
electrocatalyst-adsorbate interfacial aggregate. The
c a p a b i l i t i e s o f l a s e r [as i n s e c o n d - h a r m o n i c g e n e r a t i o n
( 3 9 - 4 0 ) ] a n d s y n c h r o t r o n r a d i a t i o n [as i n n e a r - e d g e a n d
extended X-ray absorption fine structure (4_L) ] i n
elucidating interfacia
c o n d i t i o n s have r e c e n t l
these areas have bee vigorou
activities i n s u r f a c e e l e c t r o c h e m i c a l s t u d i e s have
i n c l u d e d t h e a d a p t a t i o n o f new t e c h n o l o g i e s , s u c h a s
scanning t u n n e l i n g microscopy (42-3), and t h e r e v i v a l o f
c o n v e n t i o n a l methods, s u c h as M o s s b a u e r s p e c t r o s c o p y (££),
n u c l e a r m a g n e t i c r e s o n a n c e , and X - r a y d i f f r a c t i o n ( 4 5 ) .
In v i e w o f t h e c o m p l e x i t y o f h e t e r o g e n e o u s systems,
none o f t h e above t e c h n i q u e s w i l l be a b l e t o s u p p l y , by
i t s e l f , a complete atomic-level description of surface
phenomena. A m u l t i - t e c h n i q u e a p p r o a c h h a s b e e n p e r c e i v e d
by many a s most a p p r o p r i a t e f o r f u n d a m e n t a l studies i n
e l e c t r o c h e m i c a l s u r f a c e s c i e n c e ( 3 0 - 2 ) . S i n c e none o f t h e
existing electrochemical laboratories are adequately
equipped t o perform a comprehensive experimental study,
c o l l a b o r a t i v e e f f o r t s between r e s e a r c h g r o u p s o f d i f f e r e n t
expertise are burgeoning. E a s i e r access t o n a t i o n a l or
central facilities are also being contemplated f o r
experiments which cannot be p e r f o r m e d elsewhere. The
judicious combination of the available methods i n
conjunction with the appropriate electrochemical
measurements a r e p e r m i t t i n g s t u d i e s o f e l e c t r o c a t a l y s t
s u r f a c e phenomena u n p a r a l l e l e d i n m o l e c u l a r d e t a i l .
I n a n y s c i e n t i f i c e n d e a v o r , mere a c c u m u l a t i o n o f
e m p i r i c a l i n f o r m a t i o n i s n o t enough t o g u a r a n t e e major
advances. Efforts have t o be e x e r t e d t o f o r m u l a t e
f u n d a m e n t a l c o n c e p t s from t h e a v a i l a b l e d a t a . F o r example,
i t i s no l o n g e r s u f f i c i e n t t o d e s c r i b e how an a d s o r b e d
s p e c i e s i s bound t o t h e s u r f a c e s i m p l y i n terms o f i t s
i n t e r f a c i a l o r i e n t a t i o n . I t i s e s s e n t i a l t o p r o c e e d beyond
such phenomenological i l l u s t r a t i o n s a n d a c t u a l l y examine
t h e n a t u r e o f t h e s u r f a c e - a d s o r b a t e c h e m i c a l bond. I t i s
i n t h i s a s p e c t t h a t c o n c e p t s from t h e r e l a t e d a r e a s o f
c o o r d i n a t i o n a n d o r g a n o m e t a l l i c c h e m i s t r y h a v e b e e n most
m e a n i n g f u l . F o r example, i n t h e s o - c a l l e d s u r f a c e - c l u s t e r
analogy (1-4) , b o n d i n g i n chemisorption systems i s
modelled a f t e r bonding i n m o l e c u l a r o r c l u s t e r complexes.
S k e p t i c i s m t o t h e s u r f a c e - c l u s t e r analogy has been r a i s e d

1. SORIAGA Electrochemistry 5
because o f t h e w i d e s p r e a d knowledge t h a t w h i l e metal

c o m p l e x e s c a n be d e s c r i b e d b y d i s c r e t e o r b i t a l s , m e t a l
s u r f a c e s a r e u s u a l l y c h a r a c t e r i z e d by band s t r u c t u r e .
However, what i s n o t known t o a s many i s t h e f a c t t h a t t h e
s u r f a c e b a n d s t r u c t u r e c a n a c t u a l l y be d e c o n v o l u t e d into
components o f g i v e n symmetries w i t h r e s p e c t t o a g i v e n
s i t e ( 3 - 4 ) . I n t h i s manner, t h e s u r f a c e - a d s o r b a t e b o n d c a n
be d e s c r i b e d i n t e r m s o f t h e o v e r l a p o f s y m m e t r y - a d a p t e d
s u r f a c e bands and a d s o r b a t e o r b i t a l s ; t h i s d e s c r i p t i o n i s
e x a c t l y t h e same a s t h a t o f t h e m e t a l - l i g a n d b o n d i n
monometal o r s m a l l c l u s t e r complexes.
With t h e experimental and t h e o r e t i c a l s t r a t e g i e s
a v a i l a b l e today, research i n electrochemical surface
s c i e n c e has been r e v i v e d . There i s g r e a t o p t i m i s m t h a t
much o f t h e m y s t e r i e s s u r r o u n d i n g e l e c t r o c a t a l y s i s w i l l
soon be unravelled i n molecular detail hitherto
unachievable.
Literature Cited
1. Muetteries, E . L . B u l l . Soc. Chim. Belg. 1975, 84, 959.

2. Muetteries, E . L . B u l l . Soc. Chim. Belg. 1976, 85, 451.
3. S a i l l a r d , J . Y . ; Hoffman, R. J . Am. Chem. Soc. 1984,
106, 2006.
4. A l b e r t , M . R . ; Yates, J.T., J r . The S u r f a c e
Scientists's Guide to Organometallic Chemistry;
American Chemical Society: Washington, DC, 1987.
5. Rodriguez, J.F.; Bravo, B . G . ; Mebrahtu, T . ; Soriaga,
M.P. Inorg. Chem. 1987, 26, 2760.
6. Rodriguez, J.F.; Harris, J.E.; Bothwell, M . E . ;
Mebrahtu. T; Soriaga, M.P. Inorg. Chim. Acta. 1988, in
press.
7. Soriaga, M.P.; Binamira-Soriaga, E.; Hubbard, A.T.;
Benziger, J . B . ; Pang, K.-W.P. Inorg. Chem. 1985, 24,
65.
8. Schardt, B . C . ; Stickney, J.L.; Stern, D . A . ; Frank,
D.G.; Katekaru, J.Y.; Rosasco, S.D.; Salaita, G.D.;
Soriaga. M.P.; Hubbard, A . T . Inorg. Chem. 1985, 24,
1419.
9. Baizer, M.M.; Lund, H. Organic Electrochemistry;
Marcel Dekker: New York. 1983.
10. White, R . E . ; Bockris, J.O'M.; Conway. B . E . ; Yeager, E.
Comprehensive Treatise of Electrochemistry; Plenum
Press: NY 1984; Vol 8.
11. Molecular Phenomena at Electrode Surfaces; Symposium
sponsored by the Surface and C o l l o i d Chemistry
D i v i s i o n of the American Chemical Society. New
Orleans, LA, 1987.
12. Characterization of Electrochemical Processes; Special
workshop convened by the National Research Council.
Denver, CO, 1985.
13. Furtak, T.E.; Kliewer, K.L.; Lynch, D.W., Eds; Non-
T r a d i t i o n a l Approaches to the Study of the S o l i d -
Electrolyte Interface. North-Holland: Amsterdam, 1980.

6 ELECTROCHEMICAL SURFACE SCIENCE
14. Hansen, W.N.; Kolb, D . M . ; Lynch, D.W., E d s . ;

Electronic and Molecular Structure of Electrode-
Electrolyte Interfaces. Elsevier: Amsterdam, 1983.
15. Ross, P . N . J. Electrochem. S o c. 1979, 126, 78.
16. Stonehart, P . ; Zucks, P.A. Electrochim. Acta. 17,
2333.
17. Lundquist, J.T.; Stonehart, P. Electrochim. Acta.
1973, 18, 349.
18. Kunz, H.R. Proc. Electrocatal. Fuel C e l l React. 1978,
79, 14.
19. Kunz, H.R.; Gruver, G. J. Electrochem. Soc. 1975, 122,
1279.
20. Stonehart, P.; Kinoshita, K . ; Bett, J.S. In
Electrocatalysis; Breiter, M.W., E d . ; The
Electrochemical Society: Princeton, NJ, 1974.
21. Blurton, K . F . ; Greenberg, P . ; Oswin, H . G . ; Rutt, D.R.
J . Electrochem. Soc
22. Bett, J . S . ; Lundquist
P. Electrochim. Acta. 1979, 18, 343.
23. Bregoli, L.J. Electrochim. Acta. 1978, 23, 489.
24. Peuckert, M . ; Yoneda, T . ; Dalla Betta, R . A . ; Boudart,
M. J . Electrochem. Soc. 1986, 133, 944.
25. Schrauzer, G.N. Transition Metals i n Homogeneous
Catalysis; Marcel Dekker: New York, 1971.
26. Cotton, F . A . ; Wilkinson, G. Advanced Inorganic
Chemistry; Wiley: New York, 1980.
27. Somorjai, G.A. Chemistry in Two Dimensions: Surfaces;
Cornell University Press: Ithaca, NY, 1981.
28. Hansen, W.N. J. Electroanal. Chem. 1983, 150, 133.
29. Stickney, J.L.; Rosasco, S.D.; Salaita, G.N.; Hubbard,
A.T. Langmuir. 1985, 1, 66.
30. Hubbard, A . T . Accts. Chem. Res. 1980, 13, 177.
31. Ross, P.N. In Chemistry and Physics of Solid Surfaces;
Vaneslow, R.; Howe, R., Eds.; Springer-Verlag: NY,
1982.
32. Homa, A . S . ; Yeager, E.; Cahan. B.D. J . Electroanal.
Chem. 1983, 150, 181.
33. Wieckowski, A . ; Rosasco, S.D.; Salaita G . N . ; Hubbard,
A . T . ; Bent, B . ; Zaera, F.; Somorjai, G.A. J. Am. Chem.
Soc. 1985, 107, 21.
34. Stuve, E . M . ; Rogers, J.W., J r . ; I n g e r s o l l , D.;
Goodman, D.W.; Thomas, M.L.; Paffett, M.T. Chem. Phys.
Letters. 1988, in press.
35. Pons, S.; Bewick, A. Langmuir. 1985, 1, 141.
36. Muller. R.H. Adv. Electrochem. Electrochem. E n g r .
1973, 9, 227.
37. Van Duyne, R.P. In Chemistry and Physics of the Solid
Surface; R. Vaneslow, E d . ; CRC: FL, 1981.
38. Gao, P.; Weaver, M.J. J. Phys. Chem. 1986, 90, 4057.
39. Richmond, G.L. Langmuir. 1986, 2, 132.
40. Campbell, D . J . ; Corn, R.M. J. Phys. Chem. 1987, 91,
5668.

1. S O R I A G A Electrochemistry 7
41. Gordon, J.G.; Melroy, O.R.; Borges, G . L . ; Reisner,

D . L . ; Abruña, H . D . ; Chandrasekhar, P . ; A l b a r e l l i ,
M . J . ; Blum, L . J. E l e c t r o a n a l . Chem. 1986, 210, 311.
42. L i n , W.; Fan, F . - R . F ; Bard, A.J. J. Electrochem. Soc.
1987, 134, 1038.
43. Sonnefield, R.; Hansma, P.K. Science. 1986, 232, 211.
44. Scherson, D . A . ; Yao, S.B.; Yeager, E.; Eldridge, J.;
Kordesch, Μ.Ε.; Hoffman, R.W. J. Electroanal. Chem.
1983, 150, 535.
45. Fleischman, M . ; Graves, P . ; Hill, I . ; O l i v e r , Α . ;
Robinson. J . J. Electroanal. Chem. 1983, 150, 33.
R E C E I V E D June 27, 1988

Chapter 2
Molecular Adsorption at Well-Defined

Platinum Surfaces
Voltammetry Assisted by Auger Spectroscopy,
Electron Energy-Loss Spectroscopy,
and Low-Energy Electron Diffraction
Arthur T. Hubbard, Donald A. Stern, Ghaleb N. Salaita,

Douglas G. Frank, Frank Lu, Laarni Laguren-Davidson,
Nikola Batina, and Donald C. Zapien
Department of Chemistry
Reviewed here are surface electrochemical studies of

organic molecules adsorbed at well-defined Pt(111)
electrode surfaces from aqueous solution. Emphasis is
placed upon studies of n i c o t i n i c acid (NA), pyridine
(PYR), and nine related pyridine carboxylic acids.
Packing densities (moles per unit area) adsorbed from
solution at controlled pH and electrode potential, and
measured by means of Auger spectroscopy are discussed.
V i b r a t i o n a l spectra of each adsorbed obtained by use
of electron energy-loss spectroscopy (EELS) are compared
with the IR spectra of the parent compounds. E l e c t r o -
chemical r e a c t i v i t y is studied by use of c y c l i c
voltammetry. Monolayer structures observed by means
of low-energy electron d i f f r a c t i o n (LEED) are described.
Substances studied are as follows: 3-pyridine
carboxylic acid ( n i c o t i n i c acid, NA, "niacin"); pyridine
(PYR); 3-pyridylhydroquinone (3PHQ), synthesized here for
the first time; 4-pyridine carboxylic acid ( i s o n i c o t i n i c
acid, INA); 2-pyridine carboxylic acid ( p i c o l i n i c acid,
PA); 3,4-pyridine dicarboxylic acid (3,4PDA); and the
analogous other pyridine dicarboxylic acids 3,5PDA,
2,3PDA, 2,4PDA and 2,6PDA. Each of the pyridine deriv-
atives is adsorbed at P t (111) i n a t i l t e d v e r t i c a l
orientation; an angle of 70-75° between the p y r i d y l
plane and the P t (111) surface is t y p i c a l . Pt-N bonding
is evidently the predominant mode of surface attachment
of these compounds, although coordination of carboxylate
is an important mode of a d d i t i o n a l surface attachment at
positive potentials. EELS spectra display strong O-H
stretching vibrations near 3550 cm-1 due to carboxylic
acids i n the meta and para-positions, and weak-to-moderate
-1
signals near 3350 cm due to ortho-carboxylates.
0097-6156/88/0378-0008$08.25/0
c
1988 American Chemical Society

2. HUBBARD ET AL. Molecular Adsorption at Weil-Defined Platinum Surfaces 9
N i c o t i n i c acid and related meta-carboxylic acids display

the remarkable c h a r a c t e r i s t i c that coordination of the pen-
dant carboxylic acid moieties to the Pt surface i s con-
t r o l l e d by electrode p o t e n t i a l . Oxidative coordination of
the carboxylate pendant occurs at p o s i t i v e electrode
potentials, r e s u l t i n g i n disappearance of the 0-H
vibration and loss of surface a c i d i t y as judged by
absence of r e a c t i v i t y towards KOH. Carboxylate i n the
4-position of pyridine (as i n INA) i s v i r t u a l l y inde-
pendent of electrode potential, whereas strong coor-
dination of ortho-carboxylates to the Pt surface is
present at most electrode potentials. Adsorbed pyridine
carboxylic acids are stable i n vacuum; when returned to
solution the adsorbed material displays the same chemical
and electrochemical properties as prior to evacuation.
An era of remarkable progress i n the study of s o l i d electrode sur-

faces has begun (1-5)
recent progress, arrange
technique i n v e s t i g a t i o n of e l e c t r o d e s u r f a c e s ; well-defined
e l e c t r o d e s u r f a c e s as a p a r t of e l e c t r o c h e m i c a l research;
evidence f o r the s t a b i l i t y i n vacuum of l a y e r s adsorbed from
solution; Auger spectroscopy as a t o o l f o r q u a n t i t a t i o n and
c h a r a c t e r i z a t i o n of adsorbed l a y e r s ; e l e c t r o n energy-loss
spectroscopy (EELS) f o r investigation of molecular structure and
mode of surface attachment of substances adsorbed at electrode
surfaces; low-energy electron d i f f r a c t i o n (LEED) as a probe of
both s u b s t r a t e s u r f a c e s t r u c t u r e and adsorbed layer long-range
order; and voltammetric experiments i l l u s t r a t i n g the influence of
electrode surface crystallographic structure on the electrochemi-
c a l r e a c t i v i t y of adsorbed molecules.
A substantial added benefit of multi-technique investigations
of electrode surfaces i s that the same experimental tools required
to bring the electrode surface to a well-defined state happen also
to be very p r o f i c i e n t at revealing the various important changes
i n the nature of the surface which occur during subsequent chemi-
c a l or electrochemical treatment or use of the electrode. Also,
the d i a g n o s t i c power of the m u l t i - t e c h n i q u e approach i s par-
t i c u l a r l y advantageous for i n v e s t i g a t i o n of complicated surfaces.
Advances i n technique have brought many complicated surfaces to a
well-defined state (3-6). Although i n p r i n c i p l e there are many
techniques from which to choose, i n practice i t i s advisable to
select techniques which work well together, answer the more impor-
tant questions about the sample, and y i e l d the necessary informa-
t i o n without appreciably a l t e r i n g the sample. For example, when
the objective i s to determine the structure of the all-important
f i r s t atomic/ionic/molecular layer at a s i n g l e - c r y s t a l surface,
LEED i s the method'of c h o i c e ( 7 ) ; X-ray d i f f r a c t i o n , EXAFS,
neutron d i f f r a c t i o n , and atomic/ion scattering, while excellent
f o r certain other purposes, are disadvantageous for t h i s task due
to l e s s e r s e n s i t i v i t y , g e n e r a l i t y and convenience. Auger
spectroscopy i s preferable for measurement of packing density and
elemental composition of surface molecular layers (8), although
XPS (ESCA,9) or SIMS (10) might also be employed. Vibrational
spectra of molecular or atomic layers are obtainable at high sen-

s i t i v i t y and v i r t u a l l y unlimited frequency range by EELS (11). On

the other hand, i n f r a r e d r e f l e c t i o n - a b s o r p t i o n spectroscopy
(IRRAS, 12) o f f e r s higher resolution than EELS i n a few s p e c i a l
cases, such as carbon monoxide, where the signal due to a c e r t a i n
v i b r a t i o n i n a monolayer meets p r a c t i c a l l i m i t s of detection.
Surface regular Raman spectroscopy i s showing signs of usefulness
f o r molecular l a y e r s at smooth s u r f a c e s and promises to allow
d i r e c t comparison between gas-solid and l i q u i d - s o l i d i n t e r f a c i a l
Raman spectra at least i n favorable cases (13). C y c l i c voltam-
metry and chronocoulometry are r e l i a b l e methods for electrochemi-
c a l characterization, along with variations based upon the use of
thin-layer electrodes (14), although numerous a l t e r n a t i v e or more
complicated methods are a v a i l a b l e (15). Examination of a surface
i n the presence of a bulk f l u i d generally requires s a c r i f i c e s i n
sensitivity, resolution, signal-to-noise ratio, interfering
signals, and other aspects. Such s a c r i f i c e s are pointless i f not
repaid by observation of some otherwise-unobservable phenomenon;
repayment i s to be expecte
fully identified. In
of the p r o p e r t i e s of a s u r f a c e to b r i n g i t to a w e l l - d e f i n e d
state, and accordingly there i s no substitute for a balanced ap-
proach to surface characterization based upon Auger, EELS, LEED,
IRRAS, and related measurements. Procedures for preparation and
c h a r a c t e r i z a t i o n of e l e c t r o d e s u r f a c e s are d i s c u s s e d i n more
d e t a i l i n Reference 5 and references cited therein.
Before proceeding to methods and applications of electrode
surface characterization, perhaps we should remind ourselves of
the m o t i v a t i o n s f o r i n v e s t i g a t i n g s u r f a c e s t r u c t u r e and com-
position. Chemical and e l e c t r o c h e m i c a l processes at s u r f a c e s
depend upon surface structure, composition, mode of bonding and
related c h a r a c t e r i s t i c s . P r a c t i c a l p r o p e r t i e s such as s u r f a c e
s t a b i l i t y , e l e c t r i c a l behavior, photochemistry, c o r r o s i o n ,
passivation, h y d r o p h i l i c i t y , adhesion, mechanical d u r a b i l i t y and
l u b r i c i t y , to name a few, often vary strongly with surface atomic
structure and composition. Surfaces shown to be clean by Auger
spectroscopy (or equivalent methods) and shown to have a s p e c i f i c
atomic structure by LEED (or equivalent methods) are termed "well-
defined surfaces". With apologies for stating the obvious, sur-
faces not d i r e c t l y characterized as to surface structure and com-
position are not "well-defined surfaces" even when prepared from
an oriented single c r y s t a l . This i s because surface s c i e n t i s t s
worldwide have observed that s p e c i f i c c r y s t a l planes do not form
automatically, even on the surfaces or oriented s i n g l e - c r y s t a l s .
Instead, contamination, s t r u c t u r a l reconstruction and disorder are
the general r u l e . Only by repeated and persistent experimenta-
t i o n , guided by d i r e c t s u r f a c e c h a r a c t e r i z a t i o n (LEED, Auger,
EELS) i s the surface brought to a clean, ordered, "well-defined"
state.
R e v e r s i b l e e l e c t r o c h e m i c a l r e a c t i v i t y i s present i n the
chemisorbed states of some compounds. C h a r a c t e r i s t i c s shared by
each of these compounds reported to date are as follows:
(a) r e v e r s i b l e e l e c t r o a c t i v i t y i n the unadsorbed state;
(b) attachment to the surface by way of a functional group
other than the electroactive center;

2. HUBBARD E T A L . Molecular Adsorption atWell-Defined Platinum Surfaces 11
(c) and none of the atoms i n the electroactive part of the

molecular a r e i n v o l v e d i n chemical bonding d i r e c t l y with the
surface. Current-potential behavior of two such compounds, 2,5-
dihydroxy-4-methylbenzylmercaptan (DMBM) and ( 3 - p y r i d y l )
hydroquinone (3PHQ), i s i l l u s t r a t e d by Figures 1-A and 1-B, i n
which only an adsorbed layer i s present to participate i n the
electrode reaction. The reactions are:
P r i o r to recording the current-potential curves i n Figure 1-A, the

P t ( l l l ) surface was immersed into 0.7mM DMBM, followed by r i n s i n g
with pure supporting e l e c t r o l y t e (lOmM t r i f l u o r o a c e t i c a c i d ) .
Figure 1-B ( s o l i d curve) shows a similar experiment involving im-
mersion into 0.5mM 3PHQ followed by r i n s i n g with lOmM KF (adjusted
to pH 4 with HF). The dotted curves i n Figures 1-A and 1-B are
obtained by a variation of the above procedures i n which the ad-
sorbed layer of DMBM or 3PHQ i s subjected to one hour i n vacuum
p r i o r to c y c l i c voltammetry. The voltammetric r e s u l t s before and
a f t e r evacuation are v i r t u a l l y i d e n t i c a l , demonstrating that DMBM
and 3PHQ are retained at the P t ( l l l ) surface i n vacuum and are not
removed from t h e s u r f a c e by r i n s i n g with water. Adsorbed
! f
2,2 ,5,5 -tetrahydroxybiphenyl (THBP), a l s o , i s s t a b l e toward
evacuation and r i n s i n g , Figure 1-C. Adsorbed hydroquinone (HQ) i s
t y p i c a l of numerous h o r i z o n t a l l y - o r i e n t e d , adsorbed simple
aromatic compounds i n being stable toward solution and evacuation
(3,4), Figure 1-D.
Auger spectroscopy y i e l d s data f o r molecular l a y e r s from
which r e l a t i v e l y a c c u r a t e and p r e c i s e packing d e n s i t i e s and
elemental analyses are obtained. Two methods are available, a l -
lowing v e r i f i c a t i o n of precision and self-consistency. The f i r s t
of these methods i s based upon measurement of elemental Auger s i g -
nals (IQ, 1^, IQ, etc.), while the other method measures the a t -

» I 1 1 I I
-0.2 0.0 0.2 0.4 0.6
POTENTIAL, VOLT vs. Ag/AgCI
1 1 1 1 1 1 1
I i i 1 i i i 1
-0.1 0.0 0.1 0.2 0.3 0.4
E L E C T R O D E P O T E N T I A L ( V O L T vs. Ag/AgCI)
Figure 1. Cyclic voltammetry of adsorbed molecules at Pt(lll). Sweep rate, 5 mV/s. A. Solid
curve (—): immersion into 0.7 mM DMBM followed by rinsing with 10 mM TFA. Dotted
curve (....): as in solid curve, except 1 h in vacuum prior to voltammetry. B. Solid curve (—):
immersion into 0.5 mM 3PHQ, followed by rinsing with 1 mM HF. Dotted curve (....): as in
solid curve, except 1 h in vacuum prior to voltammetry. Continued on next page.

2. HUBBARD ET AL. Molecular Adsorption at Well-Defined Platinum Surfaces 13
c\J
£
o
<
AFTER
BEFORE^ / UHV
CO UHV
-z.
UJ
Q START,
\
UJ
rr
O
1/xA/cnV
i:
0.0 0.2 0.4 0.6
POTENTIAL, VOLT vs. Ag/AgCI
1 1 1 1 1 1 1
: d
C\J
E AFTER J "
/ UHV | _
< - OH BEFORE-*
>-
H OH /
CO
START
LJ
Q
LJ
(Z
01 : V ~ 6/i A/cm J
(J
1 1 1 1 1 1 1
0.0 0.2 0 . 4 0.6 0.8 1.0 1.2
POTENTIAL, VOLT vs. A g / A g C I
Figure 1. Continued. C. Solid curve (—): immersion into 2 mM THBP followed by rinsing
with 10 mM TFA. Dotted curve (....): as in solid curve, except 1 h in vacuum prior to
voltammetry. (Reproduced with permission from ref. 3. Copyright 1984 Elsevier.) D. Solid
curve (—): immersion into 0.03 mM HQ followed by rinsing with 10 mM TFA. Dotted curve
(....): as in solid curve, except 1 h in vacuum prior to voltammetry.

tenuation of substrate Auger signal by the adsorbed layer. Pack-

i n g d e n s i t y measurements by these methods are i n e x c e l l e n t
agreement. For example, molecular packing d e n s i t y of 3PHQ a t
2
P t ( l l l ) (-0.1V, pH4, 0.5mM) i s 0.28 nmol/cra based upon I /Ip£, c
0.27 nmol/cnr based upon Ip /Ip°> or 0.27 nmol/cm based upon t
coulometric electrochemical data (16).

Shown i n Figure 2-A are the experimental Auger signal r a t i o s
IQ/IPJ (carbon signal, 272eV/clean surface Pt signal, 161eV), and
I p A p ° (Pt s i g n a l , 161eV, from coated surface/clean surface)
t
graphed versus n i c o t i n i c acid (NA) concentration ( C ^ ) at P t ( l l l ) .

Note that Iq/I^ increases with Cma due to increases i n T ^ , while
Ip^/IpJ. decreases accordingly. Molecular packing densities ob-
tained from such data using Equations 3 and 4 are shown i n Figure
2 2
2-B ( B = 0.377 cm /nmol; f=0.70; and K= 0.16 cm /nmol) for
c
r = I / I ) / 6 B ( 1 / 3 + 2 f
( C Pt t C /3)l ( )
T = (1-I /I °)/(9K) p t p (4)
adsorption of NA at -0.2V (vs. Ag/AgCI reference). Packing den-

s i t i e s of NA at +0.3V are shown i n Fieure 2-C. The saturation NA
packing density i s near 0.38 nmol/cm (43.7 A/molecule), which
f a l l s between the theoretical packing densities of 0.290 nmol/cm^
(57.2A/molecule) f o r a horizontal orientation, and 0.579 nmol/cm
(28.7A/molecule) f o r the N-attached v e r t i c a l orientation, based
upon c o v a l e n t and van der Waals r a d i i (17). T h i s i s one of
several types of evidence pointing to a f i l l e d - v e r t i c a l orienta-
t i o n of adsorbed NA i n which the pyridine ring forms an angle of
75° with the P t ( l l l ) surface. A model i l l u s t r a t i n g the method of
c a l c u l a t i o n of t h i s angle i s shown i n Figure 3. Pyridine and a l l
of the pyridine carboxylic acids studied to date are oriented near
v e r t i c a l l y at P t ( l l l ) with most or a l l of the angles of t i l t i n
the range from 70 to 76°. A brief l i s t i n g of data w i l l be given
i n Reference 16. Underlying causes of t h i s recurring orientation
w i l l be discussed below a f t e r consideration of further types of
evidence. The precision, simplicity and self-consistency of NA
packing density data based upon Auger spectroscopy i s characteris-
t i c of data obtained for a wide variety of adsorbed compounds.
Auger measurements of t h i s type are a highly recommended s t a r t i n g
point f o r studies of molecular substances at electrode surfaces.
(See Table I.)
A s t r i k i n g feature of the EELS spectra of NA adsorbed from
a c i d i c solutions (HF/KF) at negative potentials i s the pressure of
a strong 0-H stretching band at 3566 cm , Figure 4-A. This band
vanishes when the NA layer i s rinsed with base, Figure 4-C, and
also when adsorption i s carried out at positive potentials, Figure
4-B. The EELS spectra are e s s e n t i a l l y the envelope of the gas-
phase or s o l i d IR spectra (lower curves i n Figures 4-A through 4-
C). Assignments of the EELS s p e c t r a of analogy with the IR
spectra are given i n Table I I . The intensity of the 0-H peak
varies smoothly from maximum to minimum as the electrode potential
during adsorption i s varied from negative to positive, Figure 5-A.
This variation of 0-H signal i s not due to variation i n packing

2. HUBBARD E T A L . Molecular Adsorption at Well-Defined Platinum Surfaces 15
LOG CNAGTOI/L)
B -
o (O) FROM I /I*
c }
0.5
o
(O)FR0M I p / I p t
E
3 0.4
cn
CO 0.3
C0 H
2
LJ
Q 02
CD N
52 0.1 pH3.3, -0.2V,Pt(lll)
-5 -4 -3
LOG C (M)
Figure 2. Auger signal ratios and packing densities of NA adsorbed at Pt(lll). Experimental
conditions: adsorption from 10 mM KF adjusted to pH 7 with HF, followed by rinsing with 1
mM HF (pH 3.3); temperature, 23±1 ° C; electron beam at normal incidence, 100 nA, 2000
eV. A. Auger signal ratios: (I(/Ip) and (I /I ) for NA adsorbed at -0.2 V vs. Ag/AgCI
t pt pt
reference. B. Packing density of NA adsorbed at -0.2 V. Continued on next page.

W
0.6
(0) FROM I /I*
E
c
c f
o
o 05 (0) FROM I p t /Ip f
tz
CO
0.3
UJ C0 H
Q 2
0.2
O 0.1
0.0 _L
-5 -4 -3 -2' -I
LOG C
Figure 2. Continued. C. Packing density of NA adsorbed at +0.3 V.
|4 3.28 4#-2.03-»| I+L20-J09 |^-2.42 - * | l . 2 5 | 1.25 H ' 4 0

*!
h 5 3 1
H 8.46 •)
MOLECULAR AREA, X « 8.46 2

(7.33cos 74% 3 . 4 s i n 7 4 ° )
Figure 3. Model illustrating the method of calculation of angle from packing density data.

ENERGY LOSS (cm-1)

Figure 4. Vibrational spectra of NA. Experimental conditions: adsorption from 1 mM NA in
10 mM KF, pH 3 (A and B) or pH 7 (C), followed by rinsing with 2 mM HF (A and B, pH 3)
or 0.1 mM KOH (pH 10 for C); EELS incidence and detection angle 62° from the surface
-1
normal; beam energy, 4 eV; beam current about 120 pA; EELS resolution, 10 meV (80 cm )
-1
F.W.H.M.; IR resolution, 4 cm . A. Upper curve: EELS spectrum of NA adsorbed at
Pt(lll) [pH 3; electrode potential, -0.3 V]. Lower curve in A and B: mid-IR spectrum of NA
vapor (18). Continued on next page.

ENERGY LOSS (cm-1)

Figure 4. Continued. B. Upper curve: EELS spectrum of NA adsorbed at Pt(lll). [pH 3;
electrode potential, +0.6 V], Continued on next page.

2. HUBBARD E T A L . Molecular Adsorption at Weil-Defined Platinum Surfaces 19
ENERGY LOSS Ccm-1)

Figure 4. Continued. C. Upper curve: EELS spectrum of K NA" adsorbed at Pt(lll). [pH 10;
+
electrode potential, -0.3 V].

T r -i r
O 1-2 0.6
fee
A 8
K 1.0 h 0.5 3
CD
0 8 0.4 O
6 m
CO CO
X 0.6 0.3
—I
O
X -<
0.4 0.2
o
CO
_l 0.2 0.1
UJ 3
LJ
0.0 0.0
-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
POTENTIAL, VOLTS vs. Ag/AgCI
o
E
>
CO
z
UJ
o
o
2
O
2
-0.4 -0.2 0.0 0.2 0.4 0.6

ELECTRODE POTENTIAL (volt vs. Ag/AgCI)
Figure 5. OH-CH signal ratio (EELS) and packing density (Auger) of NA adsorbed at
1 1
Pt(lll) vs. electrode potential. A. Ratio of EELS O-H (3566 cm" ) to C-H (3068 cm" )
+
peak height. B. Packing density of K ions. Experimental conditions: (A) adsorption from 1
mM NA in 10 mM KF at pH 7, followed by rinsing in 2 mM HF (pH 3); (B) adsorption from
1 mM NA in 10 mM KF at pH 3, followed by rinsing with 0.1 mM KOH (pH 10). EELS
conditions as in Figure 4; Auger conditions as in Figure 2.

2. HUBBARD E T A L . Molecular Adsorption at Well-Defined Platinum Surf aces 21
Table I. Packing Density, r(namomol/cnr)
Ring-to-Surface Angle, Jd (degree)
Electrode r r
Potential from from from
Compound Volt W t I /Ip?
P t
Coulometry 0
3PHQ -0.1 0.28 0.27 0.27 74°

PYR -0.1 0.46 0.45 71°
NA -0.2 0.36 0.36 75°
INA -0.3 0.42 0.35 71°
PA -0.3 0.28 0.29 76°
BA 0.4 0.32 0.35 0°
3,5PDA 0.4 0.31 0.29 74°
3,4PDA 0.4
2,3PDA 0.4
2,4PDA 0.4 0.30 0.27 ca 65°
2,5PDA 0.4 0.35 0.29 76°
2,6PDA 0.4 0.31 0.27 75°
Experimental conditions: ImM adsorbate i n lOmM KF (pH3), followed

by r i n s i n g with 2mM HF (pH3).
3,5 PDA 3,4PDA 2,6PDA 2,3 PDA 2.4POA

Table II - Assignments of EELS Bands of Adsorbed

N i c o t i n i c Acid and Pyridine
pH/ Peak Primary

Electrode Frequency Symmetry
Compound Potential cm Species Description
f
NA 3/-0.2 3566 C: A
s 0-H stretch
3068 A* C-H stretch
f
1748 A C=0 stretch
1
1566 A CC stretch
f
1368 A CC, CN stretch
1
1132 A ,A" C-0 stretch; C-H,
0-H bend
f
784 A ,A" 0C0, C-H bend
stretch
NA 3/+0.6 3071 C : A*
g C-H stretch
1
1733 A C=0 stretch
T
1592 A CC stretch
1388 A\A" CC,CN stretch,
C-H bend
1
1192 A C-H bend
1
1117 A C-0 stretch
1
1007 A ,A" ring, C-H bend
824 A" 0C0, r i n g bend
673 A" 0C0, ring bend
!
463 A",A ring bend; Pt-N
stretch
f
203 A Pt-0 stretch
PYR 3/-0.1 3055 C : A ,B

2 V C-H stretch
1 2
A B C C
1537 i» 2 stretch
A B cc C N
1471 i» ? > stretch
1250 B-^ C-H bend
1134 A ;B C-H bend; X-sens.
1 2
1000 A ,A ,B ring; C-H bend;

1 2 2
X-sens.
719 B ring, C-H bend
1
B A r i n b e n d Pt
416 1? 1 8 J ~N
stretch

2. HUBBARD E T A L . Molecular Adsorption at Weil-Defined Platinum Surfaces 23
density, Figures 4 and 5. The disappearance of the 0-H v i b r a t i o n

with increasing positive potential i s due to coordinate covalent
bonding of the carboxylic acid moiety with the Pt surface, Equa-
t i o n 5.
At negative potentials i n a l k a l i n e solutions, adsorbed NA retains

+
K ions, as demonstrated by Auger spectroscopy, Figure 5-B. This
+ +
retention of K ions i s due to i n t e r a c t i o n of K with the pendant
carboxylate moiety and greatly exceeds the amounts expected simply
from d i f f u s e double-layer interactions. Potential-dependence of
+
K retention i s e s s e n t i a l l y absent f o r compounds i n c a p a b l e of
p o t e n t i a l - d e p e n d e n t c a r b o x y l a t e pendancy ( p y r i d i n e , p i c o l i n i c
acid, i s o n i c o t i n i c acid and 2,6-pyridine dicarboxylic a c i d ) .
Shown i n Figure 6-A are EELS spectra of the entire series of
pyridine carboxylic acids and diacids adsorbed at P t ( l l l ) from
a c i d i c solutions at negative electrode p o t e n t i a l . Under these
conditions a l l of the meta and para pyridine carboxylic acids and
diacids exhibit prominent 0-H vibrations (OH/CH peak r a t i o near
unity). In c o n t r a s t , at p o s i t i v e p o t e n t i a l s only the para-
carboxylic acids display pronounced 0-H vibrations, Figure 6-B.
A l l of the 0-H vibrations are absent under a l k a l i n e conditions,
Figure 6-C. This s i t u a t i o n i s i l l u s t r a t e d by the reactions of ad-
sorbed 3,4-pyridine dicarboxylic acid:

ENERGY LOSS (cm-1)

Figure 6. EELS spectra of pyridine carboxylic acids adsorbed at Pt(lll). Experimental
conditions: (A and B) adsorption from 1 mM NA in 10 mM KF at pH 3, followed by rinsing
with 2 mM HF (pH 3); (C) adsorption from 10 mM KF (pH 3), followed by rinsing with 0.1
mM KOH (pH 10); other conditions as in Figure 4. A. Adsorption at -0.2 V vs. Ag/AgCI
(pH 3). Continued on next page.

ENERGY LOSS Ccm-1)

Figure 6. Continued B. Adsorption at +0.6 V (pH 3). Continued on next page.

ELECTROCHEMICAL SURFACE SCIENCE
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
i M' i ' i i ' i ' ' ' i ' * ' i ' i
0 1000 2000 3000 4000
ENERGY LOSS Ccm-i)

Figure 6. Continued. C. Adsorption at -0.2 V (pH 10).

C0 H 2 Q
0.6 V
/ / / / / / / / / /
C0 H
2
-0.3 V 0.6 V (6)
C0 H
2
C0 K
2
C0 H2 2 KOH C0 K
2
-0.3 V
/ / / / \ / / / /
In summary, para c a r b o x y l i c a c i d groups remain a c t i v e at a l l

potentials i n the useful range, while meta carboxylates are com-
plexed with the Pt surface at p o s i t i v e potentials unless sheltered
from the surface by ortho-substituents. Ortho-carboxylates are
complexed to the Pt surface over most or a l l of the useful poten-
t i a l ranges.
LEED patterns of pyridine adsorbed at P t ( l l l ) are shown i n
Figure 7-A. Best c l a r i t y of the pattern occurs when the PYR con-
centration i s lmM. Measurement of the lengths and d i r e c t i o n s of
LEED vectors i n Figure 7-A, followed by conversion of the LEED
vectors to r e a l space by means of standard formulas, reveals that
the structure i s approximately (3.3x4.7) with an included angle of
77°. D i g i t a l simulation of the LEED pattern demonstrates that the
best f i t between theory and experiment occurs when the model
structure i s Pt(lll)(3.324x4. 738, 77.1°)R34.0°-PYR. In matrix
notation t h i s i s :
a
l a
2 1.684 2.145
b-, b 9 -4.255 5.106
The simulated LEED pattern i s shown i n Figure 7-B. Comparison of

the simulated LEED pattern with the observed LEED pattern (lower
camera shutter speed) i s shown i n Figure 7-C. As can be seen,
t h e r e i s good a g r e e m e n t . T h i s PYR l a y e r s t r u c t u r e i s
incommensurate; that i s , the mesh vectors of the layer are not
exact multiples of the substrate mesh. The nearest commensurate
structure would have been (2/3x/21, 79°)R30°, Figure 7-D. A l -
though t h i s commensurate a l t e r n a t i v e i s numerically quite s i m i l a r

Figure 7. L E E D pattern and structure of pyridine at P t ( l l l ) . A . L E E D pattern of P Y R

adsorbed at P t ( l l l ) , 51 eV. Continued on next page.

HUBBARD ET AL. Molecular Adsorption at Well-Defined Platinum Surfaces
Figure 7. Continued. B. Diagram of the LEED pattern in A. Continued on next page.

Figure 7. Continued. C. Comparison of calculated and observed LEED patterns. Continued on

next page.

2. HUBBARD E T A L . Molecular Adsorption atWell-Defined Platinum Surj'aces

Figure 7. Continued. E. Diagram of calculated LEED pattern corresponding to nearest

commensurate structure, (2^/3x^/21, 79.1 ° )R30 °. Continued on next page.

2. HUBBARD ETAL. Molecular Adsorption at Well-Defined Platinum Surf aces 33
Figure 7. Continued F. Structure of the PYR adsorbed layer: Pt(lll)(3.324 x 4.738,

77°)R34°-PYR.
I 1.684 2.145 1
In matrix notation: | -4.255 5.106 |
2
The PYR packing density in this structure is 0.421 nmol/cm .

i i | i i i i \i i i i i i i i i |i i i i i i i »»| • »' 1
l '
6kHz
ENERGY LOSS (cm-1)

Figure 8. Vibrational spectra of pyridine. Upper curve: EELS spectrum of PYR adsorbed at
Pt(lll) (pH 3); lower curve: mid-IR spectrum of liquid PYR (18). Experimental conditions:
adsorption at -0.1 V from 1 mM PYR in 10 mM KF (pH 3), followed by rinsing with 2 mM
HF (pH 3); other conditions as in Figure 4.

to the proposed incommensurate structure, i t would have resulted

i n a very d i f f e r e n t LEED p a t t e r n , F i g u r e 7-E (3.464x4.583,
79°)R30° or:
2 2
-4 5
Auger spectra f o r PYR indicate that the packing density at the
s a t u r a t i o n l i m i t i s 0.45 nmol/cm^ based upon (Ig/Ip°) or 0.46
A
nmol/cm from (Ip^/Ip^)- s t r i k i n g c h a r a c t e r i s t i c of the PYR
isotherms (16) i s the v i r t u a l constancy of packing density over
f i v e order of magnitude i n PYR concentration (10 M to neat PYR,
12M). These data point to a t i l t e d structure with a ring-to-
surface angle, J0=71°, Figure 7-F. Based upon three PYR molecules
per uniJ: c e l l , the packing density f o r t h i s structure i s 0.421
nmol/cm , i n good agreement with experiments. The r i g i d constancy
of PYR packing density and the incommensuracy of the PYR adsorbed
layer are indications that the 71° angle of adsorbed PYR r e s u l t s
from a b a l a n c i n g of f o r c e s between sigma-donor bonding of the
nitrogen atom to P t ( l l l
the aromatic r i n g . Mor
resulted i n energy setbacks due to decreased aromatic character
and decreased nitrogen sigma-donation.
An EELS spectrum of PYR adsorbed a t P t ( l l l ) from aqueous
solution i s shown i n Figure 8. Also shown i s the mid-IR spectrum
of l i q u i d PYR (18). The EELS spectrum of adsorbed PYR i s essen-
t i a l l y the envelope of the IR spectrum of l i q u i d PYR, with the ex-
1
ception of a peak at 416 cm" attributable at least i n part to
the Pt-N bond. Assignments of the EELS peaks based upon accepted
IR assignments (19) are given i n Table 2. There i s also a close
correspondence between the EELS spectrum of PYR adsorbed from
aqueous solution and the EELS spectra reported f o r PYR adsorbed at
Pt s i n g l e - c r y s t a l surfaces from vacuum (20).
References:
1. Hubbard, A.T. Accounts of Chemical Research 1980, 13, 177.
2. Hubbard, A.T. J . Vac. S c i . Technol. 1980, 17, 49.
3. Hubbard, A.T.; Stickney, J.L.; Soriaga, M.P.; Chia, V.K.F.;
Rosasco, S.D.; Schardt, B.C.; Solomun, T.; Song, D.; White,
J.H.; Wieckowski, A. J . Electroanal. Chem. 1984, 168, 43.
4. Hubbard, A.T. Chemical Reviews 1988, in press.
5. Hubbard, A.T. in "Comprehensive Chemical Kinetics", Bambord,
C.H., Tipper, D.F.H., Compton, R.G., eds., Vol. 28, Chapter 1,
(Elsevier, Amsterdam, 1988).
6. Somorjai, G.A. "Chemistry i n Two Dimensions: Surfaces",
(Cornell University Press, Ithaca, NY, 1981).
7. (a) Duke, C.B. Adv. Chem. Phys 1974, 27, 215;
(b) Estrup, P.J. i n "Characterization of Metal and Polymer
Surfaces", L.H. Lee, ed., (Academic Press, NY, 1977),
Vol. 1, pp 187ff;
(c) Somorjai, G.A.; F a r r e l l , H.H. Adv. Chem. Phys. 1971, 20,
215.
8. (a) Chang, C . C . Surface S c i . 1971, 25, 53;
(b) Hawkins, D. J . , "Auger Electron Spectroscopy, A B i b l i o -
graphy, 1927-1975" (Plenum, NY, 1977);
(c) Somorjai, G.A.; Szalkowski, F.J. Adv. High Temp. Chem.
1971, 4, 137;

(d) Taylor, New Jersey, in "Techniques of Metal Research", R.

F. Bunshah, ed. (Wiley-Interscience, NY, 1971), Vol. 7,
pp 117ff;
(e) Thompson, M.; Baker, M. D.; Christie, Α.; Tyson, J.F.
"Auger Electron Spectroscopy" (Wiley, NY, 1985).
9. (a) Betteridge, D. "Photoelectron Spectroscopy: Chemical and
Analytical Aspects" (pergamon, NY, 1972);
(b) Carlson, T.A. "Photoelectron and Auger Spectroscopy",
(Plenum, NY, 1975);
(c) Delgas, W.N.; Hughes, T.R.; Fadley, C.S. Catalysis Revs.
1970 4, 179;
(d) Herglotz, H.K.; Suchan, H.L. Adv. Coll. Interf. Sci.
1975, 5, 79.
10. Hoenig, R.E. Adv. Mass Spectrom. 1974, 6, 337.
11. (a) Sexton, B.A. Applied Phys. 1981, 126, 1;
(b) Kesmodel, L.L. J. Vacs. Sci. Technol. 1983, A1, 1456.
12. Golden, W.G., in "Fourier Transform Infrared Spectroscopy"
Ferraro, J.R. and
Orlando, Florida, 1985)
13. Campion, A. Chem. Phys. Lett. 1987, 135, 501.
14. Hubbard, A.T. Critical Revs. Analytical Chem. 1973, 3, 201.
15. Delahay, P., "Double and Electrode Kinetics" (Wiley, NY,
1965).
16. Stern, D.A.; Laguren-Davidson, L.; Frank, D.G.; Gui, J.Y.;
Lin,C.H.; Lu, F.; Salaita, G.N.; Walton, Ν.; Zapien, D.C.;
Hubbard, A.T. J. Amer.Chem.Soc.
17. Pauling, L.C. "The Nature of the Chemical Bond" (Cornell Univ.
Press, Ithaca, NY, 1960), 3rd edition.
18. (a) Pouchert, C.J."The Aldrich Library of FTIR Spectra"
(Aldrich Chemical Co., Inc., Milwaukee, Wis., 1985).
(b) "The Interpretation of Vapor Phase Spectra" (Sadtler
Research Labs., Philadelphia, 1984), Volume 2.
19. Green, J.H.S.; Dynaston, W.; Paisley, H.M. Spectrochim.
Acta 1963, 9, 549.
20. (a) Grassian, V.H.; Muetterties, E.L. J. Phys. Chem. 1986,
90, 5600;
(b) Surman, M.; Bare, S.R.; Hoffman, P.; King, D.A.
Surface Sci. 1987, 179, 243.
R E C E I V E D June 29, 1988

Chapter 3
Long-Range Structural Effects

in the Anomalous Voltammetry
of Platinum(111)
Philip N. Ross, Jr.
Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory,

University of California, Berkeley, CA 94720
The history of the
is reviewed and an experimenta
t i o n between the anomalous behavior and the conditions
of measurement (e.g., surface preparation, electrolyte
composition) i s presented. The behavior i s anomalous
in the sense that features appear in the voltammetry of
well-ordered Pt(111) surfaces that had never before
been observed on any other type of Pt surface, and
these features are not easily understood in terms of
current theory of electrode processes. A number of
possible interpretations for the anomalous features are
discussed. A new model for the processes i s presented
which is based on the observation of long-period i c e -
- l i k e structures in the low temperature states of water
on metals, including Pt(111). It is shown that this
model can account for the extreme structure s e n s i t i v i t y
of the anomalous behavior, and shows that the most
probable explanation of the anomalous behavior i s based
on capacitive processes involving ordered phases in the
double-layer, i.e., no new chemistry i s required.
P r i o r to the p u b l i c a t i o n i n 1980 of C l a v i l i e r ' s h i s t o r i c paper (1)
reporting anomalous voltammetry of Pt(111), there had been a number
of studies of the voltammetry of single c r y s t a l Pt electrodes, with
some using modern methods of surface analysis ( e . g . , LEED or RHEED)
for characterization of the structure of the c r y s t a l p r i o r to immer-
sion i n e l e c t r o l y t e (2-6), and a l l were i n q u a l i t a t i v e agreement
with the seminal work ( i n 1965) on Pt s i n g l e c r y s t a l s by W i l l (7).
By today's standards of surface preparation, W i l l ' s procedures for
surface preparation were crude, the surface structures were not
characterized by use of surface a n a l y t i c a l instrumentation (which
was neither widely a v a i l a b l e nor w e l l developed at that time), and
he employed extensive potentiodynamic c y c l i n g through the "oxide"
formation p o t e n t i a l region p r i o r to reporting the quasi-steady state
voltammetry curve, i . e . , the potentiodynamic I-V curve. The studies
employing surface a n a l y t i c a l methods made a decade or more l a t e r were
0097-6156/88/0378-0037$06.00A)
• 1988 American Chemical Society

generally regarded as v a l i d a t i n g the major conclusions of W i l l ' s

study: 1) that the r e l a t i v e bond strength of hydrogen on the low
index surfaces of Pt are (100) > (110) > (111); 2) that the m u l t i p l e
features i n the voltammetry curve f o r p o l y c r y s t a l l i n e Pt i n acid
e l e c t r o l y t e are associated with adsorption on s i t e s having the d i f -
ferent l o c a l geometries of the (100), (110) and (111) planes. How-
ever, with respect to the q u a n t i t a t i v e d e t a i l s of the r e s u l t s , there
were major discrepancies between d i f f e r e n t groups, p a r t i c u l a r l y with
respect to the charge under the I-V curve i n the hydrogen adsorption
p o t e n t i a l region from P t ( l l l ) surfaces, and to the e f f e c t of poten-
t i a l c y c l i n g ( l i k e that employed by W i l l ) on the amount of t h i s
charge and on the d e t a i l e d shape of the I-V curve (8). I t was c l e a r ,
at least to t h i s author (2,6), that the discrepancies i n the r e s u l t s
between d i f f e r e n t groups using UHV methods were caused by the i n t e r -
active e f f e c t between impurities and transformations to the surface
structure caused by the p o t e n t i a l c y c l i n g used to clean the surface
of i m p u r i t i e s . The use of oxygen atmospheres during t r a n s f e r of the
c r y s t a l from UHV to the
e f f e c t , and produced I-
to p o t e n t i a l c y c l i n g (9). With the p u b l i c a t i o n of these r e s u l t s ,
the problem of understanding the m u l t i p l e states of adsorbed on Pt
electrodes appeared to be f u l l y resolved, with W i l l ' s o r i g i n a l s i t e -
geometry i n t e r p r e t a t i o n upheld and further refined.
There was no precedent i n the published or even unpublished
h i s t o r y of studies with Pt electrodes (single c r y s t a l or otherwise)
for the type of I-V curve reported by C l a v i l i e r (1) f o r P t ( l l l ) , and
his observations might have been dismissed f o r a time had they not
been defended so strongly by Parsons (10). Motivated by subsequent
communications with Parsons' on the i n t e g r i t y of C l a v i l i e r ' s r e s u l t s ,
we accelerated the pace of modifications we were making to the UHV-
electrochemistry apparatus i n my laboratory, converting the c e l l to
a t h i n - l a y e r type (11) with the hope of reducing the e f f e c t of e l e c -
t r o l y t e impurities on the voltammetry. With the use of t h i s c e l l ,
we were able to produce the f i r s t corroboration of the C l a v i l i e r
type voltammetry with a P t ( l l l ) c r y s t a l prepared i n UHV and charac-
t e r i z e d by LEED as a highly ordered ( l l l ) - l X l surface (12). This
voltammetry i s reproduced i n Figure l a . The s e n s i t i v i t y of t h i s I-V
curve to the atomic scale " f l a t n e s s " of the surface i s i l l u s t r a t e d
by the comparison with the curve l b , which i s the same c r y s t a l i o n -
bombarded but not annealed. I f the annealed surface i s cycled
potentiodynamically through "oxide" formation, the shape of the I-V
curve changes r a p i d l y , and i s transformed into one resembling Figure
l b , and many others reported previously f o r "cycled" (111) e l e c -
trodes (4-7,9). The features which occur i n the scans f o r the
annealed (111) surface i n the p o t e n t i a l range 600-850 mV are the
anomalous features f i r s t reported by C l a v i l i e r . They are anomalous
i n the sense that they had never been reported before with any Pt
electrode, s i n g l e c r y s t a l or p o l y c r y s t a l l i n e , and they occur i n a
p o t e n t i a l region which form thermodynamic considerations (12) i n d i -
cates they are u n l i k e l y to be e i t h e r adsorbed hydrogen or adsorbed
oxygen.
To obtain these s t a r t l i n g new r e s u l t s with Pt s i n g l e c r y s t a l s ,
C l a v i l i e r employed a novel surface preparation technique that did
not require a complex and expensive UHV system, but did require
considerable s k i l l and experience. C l a v i l i e r ' s o r i g i n a l papers

3. ROSS Anomalous Voltammetry ofPt(lll) 39
Figure 1. a) C y c l i c voltammetry curve recorded from a UHV pre-

pared, well-annealed P t ( l l l ) c r y s t a l i n d i l u t e HF e l e c t r o l y t e .
C r y s t a l was immersed under p o t e n t i a l control at 0.6 V (RHE) and
swept cathodically to the l i m i t i n g p o t e n t i a l ; b) same experiment
performed with the same c r y s t a l but not annealed a f t e r
ion bombardment.

should be referred to with regards to the d e t a i l s of the method, as

I s h a l l not discuss i t further here, and only r e f e r to i t subse-
quently as the "bead method.*' Because the bead method does not r e -
quire UHV systems, i t can be practiced by a wider number of i n t e r -
ested electrochemists, and t h i s has proven to be (and w i l l continue
to be) a s i g n i f i c a n t f a c t o r i n the development of an understanding
of the anomalous voltammetry, i . e . , what species/processes are
involved. A number of laboratories around the world were soon able
to use the bead method to reproduce, i n v i r t u a l l y every d e t a i l ,
C l a v i l i e r ' s o r i g i n a l voltammetry, and have proceeded to use the
method i n studies of the chemistry of the anomalous features. The
p a r t i c u l a r r e s u l t s with the bead method that I s h a l l r e f e r to i n
t h i s review are from studies of the e f f e c t of anion type and concen-
t r a t i o n (13-16) and of the e f f e c t of atomic scale roughness (observed
using step-terrace surface structures) on the p o t e n t i a l region and
i n t e g r a l charge of the anomalous features (17,18).
In contrast to the successful implementation of the bead method
i n studying the anomalou
with UHV-electrochemical system
Subsequent work from our apparatus following corroboration of
C l a v i l i e r ' s r e s u l t s concentrated on the e f f e c t of p o t e n t i a l c y c l i n g
through "oxide" formation p o t e n t i a l on the surface structure (19),
and l a t e r on the e f f e c t of pH and type of anion (Wagner, F.T.; Ross,
P.N., J . E l e c t r o a n a l . Chem.. i n press) on the anomalous features.
Using the system i n Yeager's laboratory, Hanson (20) was able to r e -
produced C l a v i l i e r ' s voltammetry not only f o r the (111) surface, but
also the (100) and (110) surfaces as w e l l . In s p i t e of the r e l a -
t i v e l y small number of contributions to the l i t e r a t u r e that have come
from the UHV-electrochemical systems, they have made and e s s e n t i a l
v a l i d a t i o n of the bead method of surface preparation, and have v e r i -
f i e d the structure s e n s i t i v i t y of the anomalous features inferred
from purely electrochemical observations.
Possible Interpretations of the Anomalous Features
Table I gives a summary of the observational data base which I s h a l l

use here f o r a discussion of possible i n t e r p r e t a t i o n s f o r the anom-
alous voltammetry. The discussion here i s of necessity b r i e f , and
only summarizes the d e t a i l e d discussion presented i n our recent
paper (Wagner, F.T.; Ross, P.N., J . E l e c t r o a n a l . Chem.. i n press).
The anomalous features are observed on well-ordered (111) surfaces
i n a v a r i e t y of e l e c t r o l y t e s over a wide range of pH (0-11), but the
p o t e n t i a l s at which the features appear and the d e t a i l e d shapes of
the I-V curves vary considerably. S p e c i f i c a l l y , the p o t e n t i a l region
(versus RHE) i n which the features appear changes with anion concen-
t r a t i o n i n sulphate and c h l o r i d e e l e c t r o l y t e s , but not i n f l u o r i d e ,
perchlorate, bicarbonate or hydroxide e l e c t r o l y t e . In s u l f a t e e l e c -
t r o l y t e , at constant anion concentration the region s h i f t s (versus
RHE) with varying pH, while i n f l u o r i d e , perchlorate, bicarbonate and
hydroxide e l e c t r o l y t e i t does not. The use of UHV surface a n a l y t i c a l
techniques has established to a reasonable (but not d e f i n i t i v e )
extent that adventitious impurities are not involved i n the anomalous
process, i . e . , the only species p a r t i c i p a t i n g i n the chemistry are
protons/hydroxyIs, water and the anions of the solute. On the basis
of the pH and anion concentration dependencies, I agree with the

Table I. Summary of observations of the anomalous features
o Appearance of anomalous features on P t ( l l l ) requires c r i t i c a l

degree of long-range order, e.g., p e r f e c t l y ordered domains 12-25A
o P o t e n t i a l region depends on the type of anion, and anion

concentration and pH as follows:
In s u l f a t e constan
and/or chloride
no s h i f t vs. SCE at constant with
varying pH
no s h i f t with increasing at
In perchlorate constant pH
f l u o r i d e , carbonate
and/or hydroxide 59 mV/pH vs. SCE at constant C^_ with
varying pH
o In s u l f a t e and/or c h l o r i d e , there i s a conservation of charge

integrated under the p o t e n t i a l region f o r "normal hydrogen" and
2
the anomalous features with Q ~ 280 yC/cm . Roughening causes
the normal hydrogen charge to increase with a commensurate
decrease i n charge f o r anomalous features.
o In f l u o r i d e , perchlorate and/or hydroxide, there i s no simple

conservation of charge between the normal hydrogen region and the
anomalous features. Roughening causes r e d i s t r i b u t i o n of charge
both anodic and cathodic to anomalous features.

i n t e r p r e t a t i o n put forward by Kolb and co-workers (15) that the anom-

alous features on P t ( l l l ) i n s u l f a t e and chloride acid solutions are
associated with processes of s p e c i f i c adsorption of these anions.
The i d e n t i t y of the species and processes involved i n the anomalous
features observed on P t ( l l l ) i n s u l f a t e and chloride acid solutions
are associated with processes of s p e c i f i c adsorption on these anions.
The i d e n t i t y of the species and processes involved i n the anomalous
features observed i n perchlorate, f l u o r i d e , bicarbonate and hydroxide
e l e c t r o l y t e remains more uncertain than i n the cases of the s u l f a t e
and c h l o r i d e e l e c t r o l y t e s . P r i m a r i l y by the process of e l i m i n a t i o n ,
i . e . , hydrogen adsorption and s p e c i f i c adsorption of anions appear
highly u n l i k e l y , the process i n a c i d i c f l u o r i d e and perchlorate
e l e c t r o l y t e s i s most probably related to water d i s s o c i a t i o n , and the
species are most probably surface intermediates of t h i s process,
i . e . , oxygen-like. I n basic e l e c t r o l y t e s , i t appears l i k e l y , by
d i r e c t analogy with the process i n s u l f a t e e l e c t r o l y t e s , that
s p e c i f i c adsorption of hydroxyl anion i s the process there The
s p e c i f i c a l l y adsorbed hydroxyl
state molecular configuratio
from d i f f e r e n t i n i t i a l states. I t i s not c l e a r how these hydroxyl/
oxygen-like species d i f f e r from the place-exchanged OH formed on the
surface at higher p o t e n t i a l s (21). I t i s even more d i f f i c u l t to
explain why the molecular configuration of any of these species would
be unique to the (111) surface, nor why roughening the (111) surface
should cause the process to disappear e n t i r e l y . In the discussion
which f o l l o w s , a model i s presented which attempts to resolve these
d i f f i c u l t i e s w i t h i n the framework of c l a s s i c a l double-layer theory
but using new concepts i n ordered structures f o r the double-layer at
Pt(lll).
Understanding S e n s i t i v i t y to Long-Range Surface Order
I know of no other examples i n the surface science l i t e r a t u r e i n

which the adsorption of a small molecule (small i n t h i s case r e f e r -
r i n g to the values of molecular/ionic r a d i i of the adsorbate r e l a -
t i v e to the s i z e of p e r f e c t l y f l a t regions on the metal surface)
depends c r i t i c a l l y on the existence of large regions of perfect sur-
face structure. There are some examples of such s e n s i t i v i t y i n the
adsorption of aromatic molecules, where the "lying-down" configura-
t i o n , which requires attachment to m u l t i p l e points on the surface,
depends c r i t i c a l l y on the existence of f l a t domains of s i z e greater
than the molecule i t s e l f (see f o r example the discussion by Hubbard
i n h i s chapter i n Chemical Reviews, "Electrochemistry at Well-
Characterized Surfaces," The American Chemical Society, Washington,
D.C., i n press). Because these aromatic molecules provided the
p r i n c i p a l precedent f o r such s t r u c t u r a l e f f e c t s , we spent a great
deal of time i n my laboratory, perhaps 2-3 man years of e f f o r t , pur-
suing the "impurity hypothesis" based on an adventitious organic
impurity. When t h i s hypothesis was found wanting from our studies,
we turned to concepts of ordered networks i n the double-layer. Fred
Wagner, who worked with me on these studies of the anomalies on
P t ( l l l ) , has pursued the concept of ordered networks i n h i s own
studies, as he reports i n another paper i n t h i s conference. In the
discussion which f o l l o w s , I present a conceptual model f o r the
double-layer at the P t ( l l l ) surface which uses what has been learned

3. ROSS Anomalous Voltammetry of Pt (111) 43
about hydrogen bonding i n adsorbed water layers from studies of

water adsorption on metal surfaces at low temperature (<150 K) and
extends the one-dimensional c l a s s i c a l models (22) into a three-
dimensional model. This model i s then used to formulate a mechanism
to explain how sulphate anion adsorption would be s e n s i t i v e to the
symmetry of the surface, e.g., ( I l l ) vs. (100) or (110), and a c r i t -
i c a l l e v e l of atomic roughness i n the surface, e.g., the steps and
step-terrace structures.
Fortunately, the large, but diverse l i t e r a t u r e on the adsorption
of water on metals has been c o l l e c t e d i n a comprehensive manner i n
the recent review by T h i e l and Madey (23). As shown i n t h e i r review,
i t i s now w e l l established that water forms ordered s u p e r l a t t i c e
structures at low temperatures (e.g., 100°K) on a number of metal
surfaces having hexagonal symmetry, i . e . , f c c ( l l l ) and hcp(OOl),
including and e s p e c i a l l y P t ( l l l ) . The s u p e r l a t t i c e structures have
(/3 x /3) R-30° symmetry indicated by LEED, and models have been
derived showing that such symmetr i expected f o long-period i c e
l i k e structures. The mos
water superlattices was b
Ru(001), the hexagonal surface f o r the hep metal. They supplemented
t h e i r LEED analysis with ESDIAD (electron stimulated desorption-ion
angular d i s t r i b u t i o n ) , which provided d i r e c t i n d i c a t i o n of the
o r i e n t a t i o n of water molecules on the surface, and applied the
Bernal-Fowler-Pauling symmetry rules f o r hydrogen bonding i n bulk
ice to derive the surface hydrogen bonded network shown i n Figure 2.
In the f i r s t water layer of t h i s b i l a y e r structure, every other water
molecule forms a bond to the surface v i a the oxygen lone p a i r and
two hydrogen-bonds to the oxygen lone p a i r s of the water molecules
i n the hydrating part of the b i l a y e r (the puckered p o s i t i o n s ) . Water
b i l a y e r s not d i r e c t l y bound to the Ru surface were not strongly bound
into a regular structure, i . e . , the structure i s highly ordered only
i n the f i r s t b i l a y e r . There i s a close match (within 1.5%) between
the Ru and i c e l a t t i c e parameters, but T h i e l and Madey show that t h i s
e p i t a x i a l r e l a t i o n i s not e s s e n t i a l i n forming the i c e - l i k e structure
on other metal surfaces, with hexagonal symmetry provided the metal
l a t t i c e parameter f a l l s w i t h i n c e r t a i n l i m i t s . The i c e - l i k e s t r u c -
tures have not been observed on fcc(100), (110) or ( l l l ) - s t e p p e d
surfaces of any metal, even those that form such structures on the
(111) surfaces. T h i e l and Madey argue that the absence of i c e - l i k e
structures on these surface i s not due to the lack of appropriate
e p i t a x i a l r e l a t i o n s , but to the magnitude of the bond energy of water
on the d i f f e r e n t i a l surfaces (and at imperfections) i n r e l a t i o n to
the strength of the hydrogen bond. On numerous f c c ( l l l ) surfaces,
the metal-water bond energy i s equal to twice the OH—0 hydrogen bond
energy (21 kJ per mole of hydrogen bonds), so that the breaking of
the i c e symmetry to form an a d d i t i o n a l metal-water bond (e.g., lower-
ing the water molecules from hydrogen-bonded s i t e s to chemisorption
s i t e s ) does not r e s u l t i n a net lowering of the surface energy. On
the more open fee surfaces such as (100) or (110), or on "rough"
surfaces, the metal-water bond energy i s reported to be s i g n i f i c a n t l y
higher, by 10-20 k J per mole, so that the i c e symmetry i s not favored
over a structure having a greater number of water molecules bonded
to chemisorption s i t e s on the metal surface.
There i s no a - p r i o r i r e l a t i o n s h i p between these i c e - l i k e
structures formed on fee(111) metal surfaces at low temperature and

second l |
layer
Side View Adsorbed Ice l h
t
(001]
tetc.
Sixth Layer
Third Bilayer
Fifth Layer
Fourth Layer
Second Bilayer
Third Layer
Second Layer
First Bilayer
First Layer
Figure 2. Model f o r long-period i c e - l i k e structures on fee (111)

or hep (001) surfaces proposed by Doering and Madey (24): a)
view perpendicular to f c c ( l l l ) surface; b) view p a r a l l e l to (111)
plane.

3. ROSS Anomalous Voltammetry of Pt(lll) 45
the structure of water i n the double-layer at the same metal surfaces

i n aqueous s o l u t i o n . One can, however, construct such a r e l a t i o n s h i p
s t a r t i n g from the c l a s s i c a l model of Bockris and Matthews (25) f o r
the i n t e r a c t i o n of the hydronium ion with the Pt surface and the
c l a s s i c a l model (26.) of tetrahedral ( i c e - l i k e ) coordination of water
about the hydronium ion, and apply (just) the general p r i n c i p l e s of
surface bonding elucidated by T h i e l and Madey that give r i s e to long
period i c e - l i k e structures, i . e . , i c e - l i k e structures w i l l occur when
the hydrogen bonding forces acting p a r a l l e l to the surface balance
the s p e c i f i c metal-water/hydronium i n t e r a c t i o n acting perpendicular
to the surface. Let us use these p r i n c i p l e s and c l a s s i c a l models to
construct a p i c t u r e of the process of s p e c i f i c adsorption of (bi)
sulphate ions on P t ( l l l ) that would explain: 1) why the s p e c i f i c
adsorption of (bi) sulphate ion would produce the anomalous features;
2) why the adsorption does not occur to the same extent (or with the
same d e t a i l e d chemistry) on a Pt(100) or (110) surface, nor on a
"rough" (111) surface.
To use the general force-balanc
assumptions about the r e l a t i v
various molecules involved: 1) on the atomically f l a t P t ( l l l ) sur-
+
face, the Pt9P30 bond i s somewhat stronger than the PtdÔ) bond
(there i s some evidence f o r t h i s i n the recent EELS study by Wagner
and Moylan (2jO; 2) the Pt-HSO^j bond energy i s intermediate between
+ +
that f o r Pt-H 0 and P t - H 0 ; 3) the Pt-H 0 and the P t - H 0 bonds are
2 3 2 3
somewhat structure s e n s i t i v e , with H2O (H30 ) bonding s l i g h t l y more

+
strongly at steps and (100) or (110) surfaces; 4) the Pt-HS04 bond i s

strongly structure s e n s i t i v e , with the anion bond much more strongly
at steps and at (100) and (110) surfaces. Following the c l a s s i c a l
model of Bockris and Matthews (22), at the p o t e n t i a l at the minimum
i n the voltammetry curve between the charge f o r "normal" adsorbed
t n e
hydrogen and the charge from the anomalous features (0 i )» m n
inner Helmholtz layer i s formed by H3O " hydrated (according to the

4
Boering-Madey argument f o r the hydrogen bonding i n water) into a

long-period i c e - l i k e b i l a y e r , as depicted i n Figure 3. The incorpo-
r a t i o n of H3O " into a Doering-Madey type i c e - l i k e structure i s pre-
4
v i o u s l y suggested by Wagner and Moylan (27_) i n t h e i r study of the

coadsorption of water and HF on P t ( l l l ) at low temperature. The
o r i e n t a t i o n of H3O " i n such structures i s consistent with the
4
enhanced symmetric/asymmetric bend i n t e n s i t y r a t i o seen i n EELS

v i b r a t i o n spectra. Chemical i n t u i t i o n and charge compensation sug-
gest the anions form the outer Helmholtz layer by occupying the high
symmetry s i t e s i n the pure H2O b i l a y e r , as shown i n Figure 4. Note
that the anions only p a r t i a l l y charge compensate the hydronium ions,
so that one could r e f e r to t h i s structure i n c l a s s i c a l terms as
"super-equivalent" hydronium ion adsorption. The structure of
successive layers forming the d i f f u s e double-layer would l o g i c a l l y
become progressively less ordered, since the anion layer (the OHP)
becomes the ordering template, but the anions are only weakly
hydrated and the ordering force i s d i s s i p a t e d . There i s ample prec-
edent f o r the formation of charge compensated b i l a y e r s on P t ( l l l ) i n
t h i s p o t e n t i a l region indicated i n the studies by Hubbard and co-
workers (28-30). As the p o t e n t i a l i s made anodic to t h i s p o t e n t i a l
(0 £ ), protons are driven out of the IHP and the anions are drawn
m n
towards the metal surface due to the (+) p o t e n t i a l f i e l d from the Pt

surface. The hump i n the I-V curve corresponds to the change i n

Figure 3. Model f o r a hydronium ion inner layer on the P t ( l l l )

surface derived from the long-period i c e - l i k e structures of water
on metals at low temperature.

3. R O S S Anomalous Voltammetry ofPt(lll) 47
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r—I r—I 4J
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PU w
C Φ Ο
D -P CD
δ
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capacitance of the inner-layer due to t h i s deprotonation. According

to the s t r u c t u r a l model of Figure 5, the charge under t h i s hump could
2
be as high as 1/3 e~ per Pt atom (or about 85 uC/cm ) depending on
+
the i n t e r a c t i o n of the proton on H30 with the Fermi sea of the metal
at 0 in» In the l i m i t of strong i n t e r a c t i o n , t h i s model corresponds
TO
to the o r i g i n a l C l a v i l i e r i n t e r p r e t a t i o n of the hump as "hydrogen

desorption." As the p o t e n t i a l i s made cathodic to 0 i , protons are
m n
discharged and adsorb onto the Pt surface i n the c l a s s i c a l manner

(22). However, since c l a s s i c a l electrochemical " p i c t u r e s " of the
interface did not depict the structure p a r a l l e l to the surface, i t
was not widely appreciated that at any instant i n time one-third of
the surface atoms are not coordinated to a water molecule, i . e . ,
even i f one does not invoke the i c e - l i k e structure f o r water i n the
double-layer, the water molecules cannot be more densely packed i n
the plane of the surface than i n t h i s structure. Thus, i f the bond-
ing of hydrogen to the surface i s affected by i n t e r a c t i o n with water
molecules i n the double-layer then i t i s e a s i l y seen from Figure 3
that there are three d i f f e r e n
P t ( l l l ) , one having no d i r e c
i s not merely c o i n c i d e n t a l , therefore, that a s i g n i f i c a n t f r a c t i o n
of the hydrogen on the P t ( l l l ) surface has exactly the same heat of
adsorption i n s o l u t i o n as i n vacuum (9). Returning again to the
capacitive hump anodic to 0 i , the deprotonation of the inner-
T O n
layer i s followed, at more anodic p o t e n t i a l s , by displacement of

water from the inner-layer as w e l l and the "contact adsorption" of
the (bi)sulphate anion. As shown i n Figure 5, the model structure
indicates that the sharp spike i n the anomalous feature i s the
contact adsorption of the anion with the Pt surface, 1 anion being
adsorbed f o r every 9 Pt atoms, into a (11D-3 x 3 ordered anionic
superlattice.
I cannot emphasize too strongly an important aspect of the model
presented here: there are no processes occurring i n the anomalous
features that do not occur on a l l Pt surfaces!! What i s d i f f e r e n t
about the well-ordered (111) surface from a l l other Pt surface
morphologies i s that these processes occur i n a much narrower poten-
t i a l region. The narrowing of the p o t e n t i a l region where these
processes occur i s due to the ordered structure of the double-layer
at the well-ordered (111) surface, a structure which does not occur
on other surface morphologies, as w i l l be discussed i n greater d e t a i l
below. As the s t r u c t u r a l model presented here i n d i c a t e s , the anom-
alous processes are a l l phase t r a n s i t i o n s , and the capacitive current
observed i n the I-V curve corresponds to the change i n the concentra-
t i o n of i o n i c charge i n the inner layer, from 5.4 x 10*^ hydronium
2 2
ions per cm to 0.2 x 1 0 ^ (bi)sulphate anions per cm . It is dif-
f i c u l t to make the model q u a n t i t a t i v e at t h i s stage, because the
absolute values of the capacitance and the capacitive currents
depends on more precise knowledge of the degree of i n t e r a c t i o n of
these ions with the electron sea of the Pt surface. Back-of-the-
envelope type c a l c u l a t i o n s suggest the model produces capacitance
and capacitive currents consist with experiment. Consider the change
i n i o n i c concentrations c i t e d above, and assume the change i n " e f f e c -
2
t i v e charge" i n the inner-layer i s 50 uC/cm (the maximum possible
2
value i s 115 uC/cm ). On a p o l y c r y s t a l l i n e Pt surface, these same
capacitive processes occur i n the normal "double-layer p o t e n t i a l
region, from 0.3 V to 0.8 V (RHE). Then, we can approximate the

Figure 5. Model showing deprotonation of the inner layer i n the

p o t e n t i a l region between 0 i and 0<ji . Protons are trans-
m n p
ferred to outside the OHP by the conventional Grotthus mechanism.

2
capacitance as C = dq/dV = 50/0.5 = 100 uF/cm , and the charac-
2
t e r i s t i c current at 0.1 V/s as 10 uA/cm . These are t y p i c a l of
the capacitance and current i n the double-layer region observed with
p o l y c r y s t a l l i n e Pt. On the well-ordered (111) surface, these same
capacitive processes occur over a much narrower p o t e n t i a l , about
2 2
100 mV, so C = 50/0.1 = 500 uC/cm and i = 50 uA/cm at 0.1
V/s. Note these estimated capacitive currents are, r e s p e c t i v e l y ,
c h a r a c t e r i s t i c of the current f o r the sputtered (111) surface
(Figure l b ) and f o r the anomalous features on the annealed (111)
surface.
The discussion of anion adsorption from d i l u t e suphuric acid has
used the term (bi)sulphate to r e f e r to the anion. The ambiguity i s
i n t e n t i o n a l . The l o c a l pH i n the IHP i s much lower than i n the bulk
and the predominant anion species i n the OHP may then be sulphase,
rather than the bisulphate anion, which i s the predominant anion i n
the bulk. I t i s , however, not obvious which of these species i s
adsorbing, and thus the ambiguous designation
Why are the anomalou
(111) surface, and not t
l e v e l of roughness? The answer to t h i s question, i n terms of the
model presented here, was alluded to above, but i s worth discussing
i n f u r t h e r d e t a i l . The key to the structure s e n s i t i v i t y , indeed to
the e n t i r e phenomenon i t s e l f , i s the formation of the ordered
hydronium i c e - l i k e network i n the double-layer. The formation of
t h i s network requires that a d e l i c a t e balance be achieved between
r e l a t i v e l y weak bond forces, as a r t i c u l a t e d so elegantly i n the d i s -
cussion of water on metals by T h i e l and Madey. The hydrogen bonds
are very d i r e c t i o n a l and very s e n s i t i v e to bond length. The points
of attachment of network to the metal atoms must therefore have hex-
agonal symmetry, a condition which cannot be met on the (100)-1 x 1
(the unreconstructed) surface. As T h i e l and Madey have shown, i t i s
possible to construct a i c e - l i k e network on an unreconstructed
fcc(110) surface l i k e Ag(110), but the Pt(110) surface i s recon-
structed to a 2 x 1 "missing row" (31) structure which i s stable
even i n acid e l e c t r o l y t e (9). The missing row structure i s a
sawtooth-type s t r u c t u r e , and the v e r t i c a l a r t i c u l a t i o n of the sur-
face makes i t impossible to form the hydrogen-bonded network. In
the case of step-terrace structures (17,18), where the anomalous
features are seen to depend on a c r i t i c a l length of the (111) t e r -
races, apparently there i s a c r i t i c a l ensemble s i z e to form not only
the hydronium network inner-layer but the f u l l ordered double-layer.
Note i n Figures 4-5 that a complete (bi)sulphate 3 x 3 u n i t c e l l
requires a p e r f e c t l y f l a t Pt domain s i x atoms on a s i d e , which i s
consistent with the experimental observation of 5 or more as the
c r i t i c a l terrace length.
Let us now extend the long-period hydronium i c e - l i k e model f o r
the IHP on P t ( l l l ) to explain the observations i n e l e c t r o l y t e s other
than sulphate. In acid c h l o r i d e , both the observations and the
model carry-over d i r e c t l y from the case of sulphate. In f l u o r i d e ,
perchlorate, bicarbonate and hydroxide, i n which the anomalous
features s h i f t considerably i n both p o t e n t i a l and appearance (espe-
c i a l l y i n the basic media) from sulphate, another model i s needed.
Both (bi)sulphate and chloride are large weakly hydrated anions, and
i n the double-layer model of Figures 4-5, they i n t e r a c t strongly with
both the hydronium ions and the Pt surface. The contact adsorption

of these anions screens the net (+) image charge on the metal surface
from the water molecules i n the OHP, so that much higher f i e l d s
(anodic p o t e n t i a l ) are required to cause water d i s s o c i a t i o n and "OH'*
formation on the surface. Fluoride e s p e c i a l l y i s a small strongly
hydrated anion, which does not i n t e r a c t strongly e i t h e r with hydron-
ium ion or the metal surface, and does not screen the p o t e n t i a l f i e l d
of the metal atoms from the water i n double-layer. To account f o r
these fundamental differences i n p h y s i c a l properties, i t i s necessary
to construct a double-layer model which r e t a i n s c e r t a i n basic e l e -
ments of Figures 4-5, but i s very d i f f e r e n t i n e s s e n t i a l features.
Because the f l u o r i d e ion has weak charge compensating properties, the
"super-equivalent" hydronium ion layer cannot form the IHP. Instead,
I suggest formation of a Doering-Madey long-period i c e - l i k e layer
with hydronium ions a l t e r n a t e l y i n the f i r s t and second b i l a y e r s and
i n s e r t i o n of f l u o r i d e ions into the more dense 2X2 packing p o s i t i o n s
i n the second b i l a y e r . The l a t t e r achieves a nearly charge compen-
anc
sated double-layer at 0 in» * *-he view of t h i s structure p a r a l l e l
to the surface would loo
double-layer model. Thus
f l u o r i d e ion has two e f f e c t s on the double-layer structure: a) i t
reduces the i n t e r a c t i o n of hydronium ion with the Pt surface because
t h i s i n t e r a c t i o n i s i n t r i n s i c a l l y a cooperative i n t e r a c t i o n ; b) the
p o t e n t i a l f i e l d from the metal i s r e l a t i v e l y unscreened by the
anions. The consequence of these e f f e c t s are to eliminate the phase
t r a n s i t i o n s i n the IHL at 0 i due to deprotonation and anion
m n
adsorption, and instead cause phase t r a n s i t i o n s at higher p o t e n t i a l

associated with d i s s o c i a t i o n of the water molecules i n the IHL to
form ordered OH structures. As before with sulphate, I argue that
no electrode processes take place on P t ( l l l ) i n f l u o r i d e e l e c t r o l y t e
that do not also occur on other Pt surfaces i n the same e l e c t r o l y t e .
The c r u c i a l difference between these processes on P t ( l l l ) and on
other Pt surfaces i s again the squeezing of the p o t e n t i a l region i n
which these processes take place due to the ordered structures, i . e . ,
t r a n s i t i o n s from one ordered phase to another i n a narrow range of
p o t e n t i a l ( I r e s i s t the temptation to give these t r a n s i t i o n s an
order, e.g. f i r s t order phase t r a n s i t i o n , u n t i l more i s known about
them). P o t e n t i a l c y c l i n g experiments (Wagner, F.T.; Ross, P.N., J .
Electroanal. Chem., i n press) that progressively roughen the surface
2
c l e a r l y show that of the 80-90 yC/cm under the anomalous features
at 0.6-0.8 V, about 25% of that charge reappears i n the "normal"
hydrogen region, while the remaining charge i s spread a n o d i c a l l y
into the "oxide" formation p o t e n t i a l region. This r e d i s t r i b u t i o n of
charge with loss of surface order i s consistent with the model.
Roughening breaks the long-period i c e - l i k e structure of the double-
layer, which changes the a s s o c i a t i o n between water and adsorbed
hydrogen producing a r e d i s t r i b u t i o n of charge among the three d i f -
ferent states of hydrogen on the (111) surface, and some increase i n
t o t a l charge due d i r e c t l y to the increase i n the roughness. The "OH"
formation process, which could be termed a UPD state of oxygen, moves
towards the oxygen Nernst p o t e n t i a l due to a lowered free energy of
formation on the disordered versus the ordered surface. The process
i s also no longer a t r a n s i t i o n between ordered phases, and the charge
becomes smeared out i n p o t e n t i a l .

The Path to D e f i n i t i v e Models of the Anomalous Processes
The path of discovery i n the great period of atomic physics from ca.
1920-1940 has become a model f o r the process of i n t e l l e c t u a l d i s -
covery which s o c i a l s c i e n t i s t s term "the s c i e n t i f i c method." B r i e f l y
stated, the inquiry begins with the observation of anomalous behav-
i o r , e.g., the Stark e f f e c t , so termed because the observations are
t o t a l l y new and the r e s u l t s inexplicable i n terms of current theory.
Others t r y to duplicate the observations, with u s u a l l y contradictory
r e s u l t s , and a period of controversy ensues u n t i l eventually a con-
sensus emerges defining the nature of the phenomena. Hypothetical
models are presented which attempt to explain the new behavior, and
t h e o r i s t s and experimentalists alternate i n disproving one hypothesis
and bringing f o r t h a new one, u n t i l eventually a model evolves that
explains a l l observations. The purpose of t h i s t a l k has been to put
the study of the anomalous electrochemical behavior of P t ( l l l ) into
that same type of i n t e l l e c t u a l framework Following a period of
controversy concerning th
emerged a consensus concernin
anomalous behavior, which was summarized here i n Table I . We are
now a t the stage of inquiry where hypothetical models are needed to
i n i t i a t e the next stage i n the process of discovery. I have
attempted to present such a model here. I hope that t h i s model w i l l
stimulate t h e o r i s t s to use i t as a basis f o r c a l c u l a t i o n s of free
energies of formation of the ordered phases and the corresponding
capacitances. These c a l c u l a t i o n s should give r i s e to new and more
refined models, and guide experiments designed to t e s t the new
theory. The key to a c t i v a t i n g t h i s t r a d i t i o n a l cycle of theory and
experiment i s entry of t h e o r i s t s , who have so f a r remained on the
s i d e l i n e s while the experimentalists sort out the v a l i d observations.
Acknowledgments
The author acknowledges the steady support over the l a s t decade f o r

studies on s i n g l e c r y s t a l electrochemistry from the Department of
Energy, Assistant Secretary f o r Conservation and Renewable Energy,
O f f i c e of Energy Storage and D i s t r i b u t i o n , under Contract No.
DE-AC03-76SF00098.
L i t e r a t u r e Cited
1. C l a v i l i e r , J . J . Electroanal. Chem. 1980, 107, 205; 1980, 107,

211.
2. Ross, P. N. J . Electroanal. Chem. 1977, 76, 139.
3. Yeager, E . ; O'Grady, W.; Woo, M . ; Hagans, P. J . Electrochem.
Soc. 1978, 125, 348.
4. Hubbard, A . ; Ishikawa, R.; Kutakaru, J . J . Electroanal. Chem.
1978, 86, 271.
5. Yamamoto, K . ; Kolb, D. M . ; Kotz, R.; Lehmpfuhl, G. J .
Electroanal. Chem. 1979, 96, 233.
6. Ross, P. N. J . Electrochem. Soc. 1979, 126, 67.
7. W i l l , F. J . Electrochem. Soc. 1965, 112, 451.
8. Yeager, E. J . Electrochem. Soc. 1980, 128, 160C.
9. Ross, P. N. Surf. S c i . 1981, 102, 463.
10. Parsons, R. J . Electrochem. Soc. 1980, 127, 126C.

3. ROSS Anomalous Voltammetry of Pt(lll) 53
11. Ross, P. N . , Jr.; Wagner, F. T. In Advances in

Electrochemistry and Electrochemical Engineering; Gerischer,
H.; Tobias, C. W., Eds.; Wiley: New York, 1985; Vol. 13.
12. Wagner, F. T.; Ross, P. N . , Jr. J . Electroanal. Chem. 1983,
150, 141.
13. C l a v i l i e r , J.; Faure, R.; Guinet, G.; Durand, R. J .
14. Markovic, M . ; Hanson, M.; McDougall, G.; Yeager, E. J .
15. Al-Jaaf-Golze, K . ; Kolb, D.; Scherson, D. J . Electroanal.
Chem. 1986, 200, 353.
16. C l a v i l i e r , J.; Chauvineau, J . J . Electroanal. Chem. 1984, 178,
343.
17. Love, B . ; Seto, K . ; Lipkowski, J . J . Electroanal. Chem. 1986,
199, 219.
18. C l a v i l i e r , J.; Armand, D.; Sun, S.; Petit, M. J . Electroanal.
Chem. 1986, 205, 267
19. Wagner, F. T.; Ross
20. Hanson, M. Ph.D. Thesis
Cleveland, OH, 1985.
21. Wagner, F. T.; Ross, P. N . , Jr. Appl. Surf. Sci. 1985, 24, 87.
22. Bockris, J.; Devanathan, M . ; Mueller, K. Proc. Roy. Soc.
(London), 1963, A274, p. 55.
23. Thiel, P.; Madey, T. Surf. Sci. Rept. 1987, 7; 211.
24. Doering, D.; Madey, T. Surf. S c i . , 1982, 123, 305.
25. Bockris, J.; Matthews, D. Proc. Roy. Soc. (London), 1966, 292,
p. 479.
26. Wicke, E . ; Eigen, M.; Ackermann, T. Zeit. Phys. Chem. (Neue
Folge) 1957, 1, 1195.
27. Wagner, F . ; Moylan, T. Surf. S c i . 1987, 182, 125.
28. Salaita, G.; Stern, D.; Lu, F . ; Baltruschat, H . ; Schardt, B . ;
Stickney, J.; Soriage, M . ; Frank, D.; Hubbard, A. Langmuir
1986, 2, 828.
29. Lu, F . ; Salaita, G.; Baltruschat, H . ; Hubbard, A. J .
30. Stern, D.; Baltruschat, H . ; Martinez, M.; Stickney, J.; Song,
D.; Lewis, S.; Frank, D.; Hubbard, A. J . Electroanal. Chem.
1987, 217, 101.
31. Ducros, R.; M e r r i l l , R. Surf. Sci. 1977, 55 227.
R E C E I V E D May 17, 1988

Chapter 4
Gas-Phase Adsorption Model Studies

of Electrode Surfaces
1 2
J. K. Sass and K. Bange
1
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-1000
Berlin 33, Federal Republic of Germany
2
Schott Glaswerke, Postfach 130367, D-6200 Wiesbaden 13, Federal
Republi f German
Model adsorptio
v a c u u m (UHV.), a i m e d at s i m u l a t i n g t h e inter-
facial r e g i o n b e t w e e n a m e t a l a n d a n e l e c t r o l y t e ,
are d e s c r i b e d . It is s h o w n t h a t by m e a s u r i n g t h e
w o r k f u n c t i o n c h a n g e , i n d u c e d by such a s y n t h e t i c
a d s o r b a t e layer, a m e a n i n g f u l c o m p a r i s o n t o in
situ e l e c t r o c h e m i c a l d a t a may be a c h i e v e d . T h e
a g r e e m e n t w h i c h has b e e n o b t a i n e d , by such
c o m p a r i s o n , f o r t h e specific a d s o r p t i o n o f t h e t w o
h a l i d e s b r o m i d e a n d c h l o r i d e o n A g { 1 1 0 } is
argued to provide definite evidence for the
relevance of e l e c t r o c h e m i c a l surface science
studies. O t h e r recent i n v e s t i g a t i o n s o f i n t e r e s t i n g
coadsorption systems with electrochemical
s i g n i f i c a n c e , in particular t h o s e w h e r e non
-specific a d s o r p t i o n b e h a v i o u r w o u l d be e x p e c t e d ,
are briefly r e v i e w e d .
Encouraging p r o g r e s s in observing and understanding molecular

p h e n o m e n a at s o l i d - e l e c t r o l y t e interfaces has b e e n m a d e in r e c e n t years.
S i g n i f i c a n t c o n t r i b u t i o n s t o this a d v a n c e m e n t h a v e c o m e f r o m the
application of experimental procedures which were d e v e l o p e d for the
s t u d y o f g a s - s o l i d i n t e r a c t i o n s in u l t r a h i g h v a c u u m / 1 / . T h e s e surface science
t e c h n i q u e s are attractive b e c a u s e t h e y p r o v i d e a w i d e r a n g e o f m i c r o s c o p i c
i n f o r m a t i o n a b o u t solid surfaces a n d a d s o r b a t e layers. T h e d r a w b a c k is, o f
c o u r s e , t h a t t h e y c a n n o t be used directly at e l e c t r o c h e m i c a l interfaces a n d
t h a t a certain m e a s u r e o f a m b i g u i t y is t h e r e f o r e i n h e r e n t in such s t u d i e s .
Considerable effort had to be invested, for example, before
c o n t a m i n a t i o n levels d u r i n g t r a n s f e r o f a s a m p l e f r o m a n e l e c t r o c h e m i c a l
cell t o a v a c u u m c h a m b e r c o u l d b e a d e q u a t e l y assessed a n d c o n t r o l l e d 121.
W i t h this p r o v i s i o n , e l e c t r o d e m o d i f i c a t i o n s by e l e c t r o c h e m i c a l processes
c a n b e s t u d i e d in m u c h g r e a t e r d e t a i l t h a n is possible in situ a n d m a n y
i n t e r e s t i n g results h a v e b e e n o b t a i n e d by such e x p e r i m e n t s . Intrinsic
l i m i t a t i o n s o f this transfer m e t h o d arise, h o w e v e r , w i t h loosely b o u n d
0097-6156/88/0378-0054$06.00/0

4. SASS AND BANGE Gas-Phase Adsorption Model Studies 55
species, f o r e x a m p l e s o l v e n t m o l e c u l e s , w h i c h may d e s o r b a f t e r r e m o v a l o f
t h e s a m p l e f r o m s o l u t i o n since t h e transfer is typically carried o u t at o r n e a r
room temperature.
T h e e x p e r i m e n t a l a p p r o a c h discussed in this article is, in c o n t r a s t ,
particularly a m e n a b l e t o i n v e s t i g a t i n g s o l v e n t c o n t r i b u t i o n s t o the
i n t e r f a c i a l p r o p e r t i e s 131. Species, w h i c h electrolyte s o l u t i o n s are c o m p o s e d
o f , are d o s e d in c o n t r o l l e d a m o u n t s f r o m t h e gas p h a s e , in u l t r a h i g h
v a c u u m , o n t o c l e a n m e t a l substrates. Sticking is e n s u r e d , w h e r e necessary,
by c o o l i n g t h e s a m p l e t o sufficiently l o w t e m p e r a t u r e . A g a i n s u r f a c e -
sensitive t e c h n i q u e s can be u s e d , to c h a r a c t e r i z e m i c r o s c o p i c a l l y t h e
i n t e r a c t i o n o f s o l v e n t m o l e c u l e s a n d ionic species w i t h t h e solid s u r f a c e .
E v e n w i t h o u t f u r t h e r c o n s i d e r a t i o n such i n f o r m a t i o n is certainly m o s t
v a l u a b l e . T h e u l t i m a t e g o a l in these studies, h o w e v e r , is t o actually m i m i c
structural e l e m e n t s o f t h e interfacial r e g i o n a n d t o be a b l e t o assess t h e
e x t e n t t o w h i c h this may b e a c h i e v e d .
A key e l e m e n t in c o n s i d e r i n g t h e p r o p e r t i e s o f t h e interfacial electric
d o u b l e layer is t h e d i s t i n c t i o n b e t w e e n specific a n d n o n - s p e c i f i c a d s o r p t i o n .
W i t h r e g a r d t o t h e feasibilit
this d i s t i n c t i o n is also ver
e l e c t r o d e s u r f a c e , such as t h e h a l i d e s for e x a m p l e , may b e d o s e d s e p e r a t e l y
a n d , b e c a u s e o f e l e c t r o n i c e q u i l i b r a t i o n , n o t necessarily in i o n i c f o r m . U p o n
s u b s e q u e n t d o s i n g o f s o l v e n t m o l e c u l e s o n l y lateral m o t i o n s o f t h e t w o
a d s o r b a t e s are r e q u i r e d f o r a m i n i m i z a t i o n o f t h e e n e r g y . In c o n t r a s t , t h e
p r e p a r a t i o n o f a fully s o l v a t e d ion o n a m e t a l surface in U H V is clearly a
m o r e d e m a n d i n g task. A l t h o u g h s o l v a t e d ions may be g e n e r a t e d in t h e g a s
p h a s e t h e r e w o u l d p r o b a b l y be insufficient intensity in a c o l l i m a t e d b e a m
s u i t a b l e f o r U H V studies. In s e q u e n t i a l d o s i n g of b o t h species, o n t h e o t h e r
h a n d , p r o h i b i t i v e l y large a c t i v a t i o n barriers f o r s o l v e n t e n c l o s u r e o f t h e i o n
m a y p r e v e n t t h e s i m u l a t i o n . O n l y in o n e o f several c o a d s o r p t i o n studies o f
alkalis a n d w a t e r , for e x a m p l e , w a s t h e r e any e v i d e n c e f o r a c o m p l e t e
h y d r a t i o n shell a r o u n d an alkali ion IS/. T h e m a j o r d i f f e r e n c e in t h e
e x p e r i m e n t a l c o n d i t i o n s of this study w a s t h a t instead o f s u b m o n o l a y e r
alkali d e p o s i t s multilayers o f p o t a s s i u m a n d w a t e r r e a c t e d t o f o r m b u l k
p o t a s s i u m h y d r o x i d e w h i c h t o s o m e e x t e n t w a s d i s s o c i a t e d a n d h y d r a t e d by
a d d i t i o n a l w a t e r . In t h e o n l y o t h e r r e p o r t , r e l e v a n t t o n o n - s p e c i f i c
a d s o r p t i o n , vibrational spectroscopy indicated the f o r m a t i o n of hydrated
p r o t o n s f r o m t h e i n t e r a c t i o n o f h y d r o g e n f l u o r i d e a n d w a t e r /6/. In b o t h o f
t h e s e studies e q u a l a m o u n t s o f cations a n d a n i o n s w e r e a p p a r e n t l y
p r e s e n t , h o w e v e r , a n d it is n o t yet clear h o w a n excess o f h y d r a t e d ions
might be g e n e r a t e d .
For this r e a s o n , t h e e m p h a s i s in this article is d i r e c t e d m o r e t o w a r d s t h e
s i m u l a t i o n o f specific a d s o r p t i o n a n d , in particular, t h e r e c e n t e n c o u r a g i n g
comparison of electrochemical and UHV data for the interaction of
b r o m i n e a n d c h l o r i n e w i t h A g { 1 1 0 } 11, 87. A brief o u t l i n e o f t h e c o n c l u s i o n s
e m e r g i n g f r o m a l k a l i - w a t e r c o a d s o r p t i o n e x p e r i m e n t s is g i v e n t o illustrate
basic m o d e s o f i o n - s o l v e n t i n t e r a c t i o n o n m e t a l surfaces a n d t o discuss
f u t u r e d i r e c t i o n s o f this research.
Concepts and Procedures
T h e c o n s e c u t i v e stages o f a typical g a s - p h a s e - a d s o r p t i o n e x p e r i m e n t , in
w h i c h t h e s i m u l a t i o n of an e l e c t r o c h e m i c a l i n t e r f a c e is t h e a i m , are
s c h e m a t i c a l l y illustrated in F i g u r e 1. T h e d e p i c t e d s e q u e n c e illustrates in
p a r t i c u l a r t h e case w h e n specific a d s o r p t i o n o f a n i o n is e x p e c t e d f r o m

e l e c t r o c h e m i c a l d a t a . In t h e first step (Figure 1a) d o s i n g o f just t h e i o n i c

species is p e r f o r m e d a n d its c o v e r a g e is d e t e r m i n e d . T h e next step i n v o l v e s
p o p u l a t i n g nearest n e i g h b o u r sites of t h e a d s o r b e d ions w i t h s o l v e n t
m o l e c u l e s (Figure 1b). F r o m t h e o r e t i c a l a n d e x p e r i m e n t a l w o r k r e l a t e d t o
h e t e r o g e n e o u s catalysis o n e expects that s o l v e n t m o l e c u l e s e x p e r i e n c e
s t r o n g p e r t u r b a t i o n s at t h o s e sites, a n d such a n effect has i n d e e d b e e n
o b s e r v e d f o r surface interactions b e t w e e n p o l a r m o l e c u l e s a n d i o n i c
species / 3 / W i t h a d d i t i o n a l s o l v e n t a d s o r p t i o n a stage may t h e n be r e a c h e d
w h e r e a p p r o x i m a t e l y t h e first a d s o r b a t e layer is c o m p l e t e d (Figure 1c). T h i s
s i t u a t i o n is o f particular interest f o r a c o m p a r i s o n w i t h e l e c t r o c h e m i c a l
d a t a b e c a u s e it represents w h a t is c o m m o n l y c o n s i d e r e d t h e i n n e r layer in
d o u b l e layer m o d e l s o f specific a d s o r p t i o n . T h e d e p o s i t i o n o f fully s o l v a t e d
ions o n t o p o f this first layer, to s i m u l a t e t h e o u t e r o r d i f f u s e layer o f t h e
i n t e r f a c e (Figure 1e), is n o t yet possible, as w a s p o i n t e d o u t earlier. B u t at
least t h e p r e s e n c e o f a n a d j a c e n t c o n d e n s e d b u l k p h a s e can b e s i m u l a t e d
by t h e a d d i t i o n o f a f e w multilayers of s o l v e n t in t h e final step o f t h e
e x p e r i m e n t (Figure 1d).
C o m p a r i n g F i g u r e 1d w i t
important features of th
r e p r o d u c e d yet by t h e s i m u l a t i o n : t h e a b o v e m e n t i o n e d i o n i c excess c h a r g e
in t h e d i f f u s e layer a n d t h e bulk electrolyte ions w i t h t h e i r s c r e e n i n g
p r o p e r t i e s . F o r t u n a t e l y , t h e c o n d i t i o n of z e r o d i f f u s e layer c h a r g e c a n o f t e n
be e x t r a c t e d f r o m e l e c t r o c h e m i c a l d a t a such t h a t t h e a b s e n c e o f t h e d i f f u s e
layer d o e s n o t seriously d e p r e c i a t e t h e p u r p o s e o f t h e U H V e x p e r i m e n t .
Similarly, it may be e x p e c t e d t h a t t h e structural p r o p e r t i e s o f t h e i n n e r
layer, f o r a certain c o m p o s i t i o n , d o n o t d e p e n d o n t h e electrolyte
c o n c e n t r a t i o n in t h e b u l k s o l u t i o n p h a s e .
D e s p i t e t h e s e a r g u m e n t s a n d t h e c o n c e p t u a l attractiveness o f t h e
p r o c e d u r e w h i c h is s k e t c h e d in F i g . 1 c o n v i n c i n g e v i d e n c e f o r t h e r e l e v a n c e
o f a p a r t i c u l a r gas p h a s e a d s o r p t i o n e x p e r i m e n t can o n l y b e o b t a i n e d by
direct comparison to electrochemical data T h e electrode potential a n d the
w o r k f u n c t i o n c h a n g e are t w o m e a s u r a b l e q u a n t i t i e s w h i c h are particularly
u s e f u l f o r such a c o m p a r i s o n . In b o t h m e a s u r e m e n t s t h e v a r i a t i o n o f t h e
electrostatic p o t e n t i a l across t h e interface can be o b t a i n e d a n d c o m p a r e d
by p r o p e r l y r e f e r e n c i n g these t w o values 11L T o g e t h e r w i t h t h e i o n i c excess
c h a r g e in t h e d o u b l e layer, w h i c h in t h e U H V e x p e r i m e n t w o u l d b e
e x p r e s s e d in t e r m s o f c o v e r a g e o f t h e i o n i c species, t h e m a c r o s c o p i c
electrical p r o p e r t i e s o f t h e interfacial c a p a c i t o r can t h u s b e c h a r a c t e r i z e d in
both environments.
Such a c o m p a r i s o n has f o r m e d t h e basis, f o r e x a m p l e , f o r t h e assertion
t h a t t h e d o u b l e layer can be e m e r s e d essentially intact f r o m s o l u t i o n /67. A
c o m m o n a m b i g u i t y , a l t h o u g h f o r d i f f e r e n t reasons, in b o t h e m e r s i o n a n d
U H V m o d e l e x p e r i m e n t s is t h e d i f f e r e n c e in t h e a m o u n t o f s o l v e n t p r e s e n t
e i t h e r at t h e e m e r s e d or s y n t h e s i z e d i n t e r f a c e , c o m p a r e d t o t h e in-situ
s i t u a t i o n . In t h e U H V t h e t o t a l a m o u n t o f s o l v e n t a d s o r b e d , a n d its
d i s t r i b u t i o n i n t o t h e first a n d s u b s e q u e n t layers, can in m a n y instances
directly b e d e t e r m i n e d , b u t this i n f o r m a t i o n is difficult to o b t a i n a n d n o t
yet a v a i l a b l e f o r t h e e m e r s e d a n d t h e real i n t e r f a c e . T o g a t h e r such missing
pieces in t h e interfacial p u z z l e is t h e m o t i v a t i o n f o r t h e w o r k d e s c r i b e d in
this p a p e r . O n e i m p o r t a n t p r e r e q u i s i t e for any m o d e l o f t h e d o u b l e layer is,
f o r e x a m p l e , t h e density o f s o l v e n t m o l e c u l e s in t h e i n n e r layer as a
f u n c t i o n o f t h e c h a r g e o n t h e interfacial c a p a c i t o r .

4. SASSAND BANGE Gas-Phase Adsorption Model Studies 57
_ ~ _ ~ ~ -Solvated _
F i g u r e 1. A s c h e m a t i c r e p r e s e n t a t i o n of the synthesis o f the

e l e c t r o c h e m i c a l d o u b l e layer in U H V : a) a d s o r p t i o n o f specifically
a d s o r b e d ions w i t h o u t s o l v e n t ; b) a d d i t i o n o f h y d r a t i o n w a t e r ; c)
c o m p l e t i o n o f t h e i n n e r layer; d) a d d i t i o n o f s o l v e n t multilayers, e)
m o d e l f o r t h e d o u b l e layer at a n e l e c t r o d e surface in s o l u t i o n .

Coadsorption of Bromine and Water on Aqf 110)
Br/Aq (110)
In p r e p a r a t i o n f o r t h e c o a d s o r p t i o n e x p e r i m e n t s it is i m p o r t a n t t o study t h e
n a t u r e o f t h e i n t e r a c t i o n o f t h e ionic species, by itself, w i t h t h e m e t a l
s u r f a c e . A s e l e c t r o n e g a t i v e species, t h e h a l o g e n s are w e l l k n o w n t o attract
c h a r g e f r o m t h e m e t a l substrate a n d to f o r m a d i p o l e layer w h i c h increases
t h e w o r k f u n c t i o n . Since t h e h a l o g e n s are typically e x p o s e d t o t h e m e t a l
s u r f a c e in m o l e c u l a r f o r m in a surface science e x p e r i m e n t a n d t h e s t i c k i n g
c o e f f i c i e n t varies w i t h a d s o r b a t e c o v e r a g e t h e n e e d f o r c o v e r a g e
c a l i b r a t i o n arises. F i g . 2 s u m m a r i z e s w o r k f u n c t i o n m e a s u r e m e n t s a n d L E E D
results w h i c h w e h a v e used f o r this p u r p o s e /9A T h e p (2x1) a n d c (4 x 2)
L E E D p a t t e r n s , w h i c h a p p e a r in t h e c o v e r a g e r a n g e s i n d i c a t e d in F i g . 2,
c o r r e l a t e very w e l l w i t h t h e c o n c e p t o f a linear increase o f t h e w o r k
f u n c t i o n 4>: A t a b o u t t w o thirds o f t h e m a x i m u m w o r k f u n c t i o n c h a n g e , t h e
p(2x1) L E E D p a t t e r n , w h i c h is first seen at - 0.25 m o n o l a y e r s , d i s a p p e a r s
a n d , at a slightly h i g h e r
obtain a saturation coverag
l i n e a r r e l a t i o n s h i p b e t w e e n w o r k f u n c t i o n a n d Br c o v e r a g e .
H2O/Br/Aqf110)
T h e key issue in s i m u l a t i o n e x p e r i m e n t s , a n d t h e most d i f f i c u l t t o a d d r e s s , is

t h e t r a n s f e r a b i l i t y o f t h e c o n c l u s i o n s d r a w n f r o m t h e results o b t a i n e d in
v a c u u m . In this section w e shall t h e r e f o r e e x a m i n e in s o m e d e t a i l a recently
p r o p o s e d p r o c e d u r e / 9 / w h i c h permits o n e t o directly c o m p a r e p r o p e r t i e s o f
t h e s y n t h e t i c interfacial layers p r e p a r e d in v a c u u m a n d t h o s e p r e s e n t at in
situ e l e c t r o c h e m i c a l interfaces. For reasons o f space l i m i t a t i o n s it will n o t
be possible to review h o w some of the information presented subsequently
m a y b e o b t a i n e d by s t a n d a r d surface science m e t h o d s / 1 / .
As p o i n t e d o u t a b o v e t h e c o m p a r i s o n b e t w e e n b o t h sets o f results relies
u p o n t h e physical e q u i v a l e n c e o f t h e t w o m e a s u r e a b l e q u a n t i t i e s w o r k
f u n c t i o n (surface science) a n d e l e c t r o d e p o t e n t i a l (electrochemistry) 111.
T h i s e q u i v a l e n c e has b e e n r e a l i z e d in electrochemistry s o m e t i m e a g o a n d
has b e e n e x p l o i t e d t o a n a l y z e m e a s u r e d values o f t h e p o t e n t i a l o f z e r o
c h a r g e 111 a n d o f w o r k f u n c t i o n c h a n g e s u p o n e m e r s i o n o f e l e c t r o d e s at
f i x e d p o t e n t i a l /8/. In t h e s i m u l a t i o n e x p e r i m e n t s t h e a p p r o a c h is q u i t e
similar in t h a t o n e p r e p a r e s a w e l l - d e f i n e d c o m p o s i t i o n o f t h e s y n t h e t i c
e l e c t r o c h e m i c a l a d s o r b a t e layer a n d t h e n o b t a i n s t h e electrostatic
p o t e n t i a l d r o p across it by a w o r k f u n c t i o n m e a s u r e m e n t .
In t h e p r e v i o u s section t h e p r o c e d u r e f o r d e t e r m i n i n g t h e b r o m i n e
c o v e r a g e has b e e n d e s c r i b e d O b t a i n i n g t h e a b s o l u t e w a t e r c o v e r a g e a f t e r
a p a r t i c u l a r d o s i n g e v e n t f r e q u e n t l y requires m o r e s u b t l e c o n s i d e r a t i o n s , in
p a r t i c u l a r w h e n t h e r e is n o t e m p e r a t u r e d i s t i n c t i o n in t h e r m a l d e s o r p t i o n
s p e c t r o s c o p y (TDS) b e t w e e n H2O m o l e c u l e s directly b o u n d t o t h e A g {110}
s u r f a c e a n d t h o s e residing in s u b s e q u e n t multilayers /10/. By e x p l o i t i n g t h e
k n o w n s t o i c h i o m e t r y of t h e hydroxyl f o r m a t i o n a n d recombination
processes o n A g { 1 1 0 } f r o m t h e r e a c t i o n o f a d s o r b e d o x y g e n a n d H2O / 1 1 / it
is, h o w e v e r , possible t o c o p e w i t h this p r o b l e m , such t h a t t h e relative w a t e r
c o v e r a g e s , w h i c h m a y be o b t a i n e d by T D S , can be c o n v e r t e d into a b s o l u t e
c o v e r a g e s o f H2O.
As a n a d d i t i o n a l b o n u s , t h e a p p l i c a t i o n of T D S also p r o v i d e s i n f o r m a t i o n
o n t h e a m o u n t s o f w a t e r p r e s e n t in d i f f e r e n t local e n v i r o n m e n t s o f t h e
c o m p o s i t e d o u b l e layer, since w a t e r b o u n d t o b r o m i n e d e s o r b s at a h i g h e r

4. SASSANDBANGE Gas-Phase Adsorption Model Studies 59
t e m p e r a t u r e t h a n t h a t residing at still u n m o d i f i e d areas o f t h e s u b s t r a t e

s u r f a c e /12/. W i t h a p p r o p r i a t e analysis o f w o r k f u n c t i o n d a t a , o b t a i n e d at
d i f f e r e n t b r o m i n e c o v e r a g e s as a f u n c t i o n o f w a t e r c o v e r a g e , it is t h e r e f o r e
p o s s i b l e t o i d e n t i f y t h e particular c o n t r i b u t i o n o f surface h y d r a t i o n w a t e r
a n d f r e e w a t e r in t h e i n n e r layer t o t h e electrostatic p o t e n t i a l d r o p at t h e
i n t e r f a c e /9/.
In F i g u r e 3 t h e results o f such d a t a analysis are s h o w n . A t b r o m i n e
c o v e r a g e s b e l o w ~~ 0.25, t w o w a t e r m o l e c u l e s are b o u n d t o t h e specifically
a d s o r b e d h a l i d e i o n a n d t h e o r i e n t a t i o n o f this surface h y d r a t i o n w a t e r (cf.
F i g u r e 1) is s e e n t o be such t h a t t h e n o r m a l c o m p o n e n t s o f t h e p e r m a n e n t
d i p o l e m o m e n t , w i t h smaller c o n t r i b u t i o n s f r o m c h a r g e t r a n s f e r a n d t h e
e l e c t r o n i c p o l a r i z a b i l i t y /13/, essentially c o m p e n s a t e t h e d i p o l e layer o f
o p p o s i t e polarity i n d u c e d by t h e ionic h a l o g e n a d s o r b a t e (see curve b in
F i g u r e 3). O f c o u r s e , it must be r e a l i z e d t h a t this e f f e c t o f t h e t w o
a d s o r b a t e s c o u n t e r b a l a n c i n g e a c h o t h e r ' s d i p o l e layer is a p u r e c o i n c i d e n c e
and t h a t t h e i m p o r t a n t c o n c l u s i o n to be d r a w n f r o m this result is t h e
invariability o f t h e effective d i p o l e m o m e n t o f t h e c o m p o s i t e b r o m i d e -
plus-hydration-water comple
t h a t this result is o f a m o r
t h e i n n e r layer w o u l d h a v e b e e n i d e n t i f i e d by t h e U H V s i m u l a t i o n
experiments.
F o l l o w i n g t h e c o n c e p t u a l o u t l i n e of t h e d o u b l e layer s i m u l a t i o n in U H V ,
s k e t c h e d in F i g u r e 1, curve c in F i g u r e 3 s h o w s t h e w o r k f u n c t i o n c h a n g e
d u e t o t h e a d s o r b e d b r o m i d e , t h e surface h y d r a t i o n shell a n d also t h e
w a t e r o c c u p y i n g areas o f t h e A g { 1 1 0 } surface w h e r e t h e i n f l u e n c e o f t h e
b r o m i d e , w h i c h is o n l y s h o r t - r a n g e , c a n n o t exert itself (cf. F i g u r e 1c). T h e
s h a p e o f this curve is n o t difficult to i n t e r p r e t w h e n w e recall t h a t t h e
h y d r a t e d surface b r o m i d e d o e s n o t c o n t r i b u t e t o t h e w o r k f u n c t i o n c h a n g e
a n d t h a t t h e " f r e e " w a t e r is less tightly b o u n d t h a n t h e h y d r a t i o n w a t e r .
Since t h e r e is o n l y limited space a v a i l a b l e in t h e first layer, i.e. t h e i n n e r
layer in p h e n o m e n o l o g i c a l m o d e l s f o r a n i o n specific a d s o r p t i o n /14/, t h e
f r e e w a t e r is g r a d u a l l y d i s p l a y e d f r o m this i n n e r layer a n d t h e w o r k
f u n c t i o n rises b e c a u s e o f t h e c o n c o m i t a n t loss o f t h e f r e e H2O m o l e c u l e s
w h i c h w h e n p r e s e n t i n d u c e a w o r k f u n c t i o n d e c r e a s e /1 SI.
A s o m e w h a t c u r i o u s effect arises w h e n a d d i t i o n a l w a t e r is d o s e d o n t o p
o f this s y n t h e t i c i n n e r layer, in t h a t t h e w o r k f u n c t i o n is o b s e r v e d t o e x h i b i t
s u b s t a n t i a l f u r t h e r decreases. This implies t h a t t h e w a t e r m o l e c u l e s in t h e
m u l t i l a y e r s a b o v e t h e i n n e r layer assume s o m e m e a s u r e o f p r e f e r e n t i a l
o r i e n t a t i o n , i n d u c e d by t h e p r e s e n c e o f t h e a d s o r b e d b r o m i d e in t h e first
layer. This result is p r o b a b l y c o n n e c t e d to structure m a k i n g a n d structure
b r e a k i n g , o r h y d r o p h o b i c a n d h y d r o p h i l i c , p r o p e r t i e s o f soild surfaces, b u t
will n o t be discussed in d e t a i l h e r e .
As p o i n t e d o u t a b o v e , t h e d a t a p r e s e n t e d in F i g . 3c c o r r e s p o n d t o t h e
s i m u l a t i o n o f t h e i n n e r layer in h a l i d e specific a d s o r p t i o n , f o r t h e case o f
z e r o d i f f u s e layer c h a r g e . F r o m d i f f e r e n t i a l capacity m e a s u r e m e n t s
e q u i v a l e n t i n f o r m a t i o n , i.e. t h e electrostatic p o t e n t i a l d r o p across t h e i n n e r
layer as a f u n c t i o n o f h a l i d e c o v e r a g e , can be o b t a i n e d a n d used t o o b t a i n
v a l u e s f o r z e r o d i f f u s e layer c h a r g e . In F i g u r e 4 t h e full line is a
r e p r e s e n t a t i o n o f such d a t a f o r b r o m i d e specific a d s o r p t i o n o n a A g {110}
e l e c t r o d e /16/. T h e a g r e e m e n t b e t w e e n t h e s e m e a s u r e m e n t s a n d t h e
c o r r e s p o n d i n g w o r k f u n c t i o n d a t a t a k e n in U H V is surprisingly g o o d , w h e n
r e c a l l i n g t h a t t h e y w e r e o b t a i n e d at very d i f f e r e n t t e m p e r a t u r e s o f - 100 K
a n d — 300 K. A l s o s h o w n in F i g u r e 4 is a similar c o m p a r i s o n , b a s e d o n r e c e n t
d a t a /17/, f o r c h l o r i d e specific a d s o r p t i o n o n A g { l 10}. A g a i n a g r e e m e n t is
o b t a i n e d , a l b e i t o v e r a smaller c o v e r a g e r a n g e , b e t w e e n t h e results f o r t h e
s y n t h e t i c i n n e r layer a n d t h e o n e in s o l u t i o n .

Bromine Coverage 0 B r
>
0.25 0.5 0.75
-1250
<
0 1 2 3
Figure 2 . 1 , c h a n g e in w o r k f u n c t i o n (<$>) o f a n A g { 1 1 0 } surface w i t h

b r o m i n e exposure. Absolute coverages were determined from the
o b s e r v e d L E E D patterns.
F i g u r e 3. W o r k f u n c t i o n c h a n g e f o r a) b r o m i n e o n A g { 1 1 0 } ; b)
b r o m i n e a n d h y d r a t i o n w a t e r ; c) b r o m i n e a n d w a t e r t o c o m p l e t e t h e
i n n e r layer; d) b r o m i n e a n d multilayers o f w a t e r .

4. SASS AND BANGE Gas-Phase Adsorption Model Studies 61
It is also o f interest t h a t t h e p o t e n t i a l d r o p across t h e i n n e r layers are

very similar f o r t h e t w o h a l i d e s , a l t h o u g h c h l o r i d e a l o n e i n d u c e s a l i m i t i n g
w o r k f u n c t i o n increase of - 1500 m V w h i c h is 300 m V larger t h a n t h a t f o r
b r o m i d e a l o n e (cf. F i g u r e 2). This may be d u e to t h e fact t h a t in a s t r o n g e r
d i p o l e f i e l d ( h a l i d e plus s c r e e n i n g c h a r g e ) t h e surface h y d r a t i o n w a t e r is
m o r e s t r o n g l y r e o r i e n t e d w i t h its p e r m a n e n t d i p o l e in a n a n t i p a r a l l e l
configuration .
The good agreement between electrochemical a n d UHV data,
d o c u m e n t e d in F i g u r e 4, is a very i m p o r t a n t result, b e c a u s e it p r o v e s f o r t h e
first t i m e t h a t t h e m i c r o s c o p i c i n f o r m a t i o n w h i c h o n e o b t a i n s w i t h s u r f a c e
science t e c h n i q u e s in t h e s i m u l a t i o n studies is i n d e e d very r e l e v a n t t o
interfacial electrochemistry. A s an example of such microscopic
i n f o r m a t i o n , F i g u r e 5 s h o w s a structural m o d e l o f t h e i n n e r layer f o r
b r o m i d e specific a d s o r p t i o n at a h a l i d e c o v e r a g e o f — 0.25 o n A g { 1 1 0 } w h i c h
has b e e n d e d u c e d f r o m t h e r m a l d e s o r p t i o n a n d l o w e n e r g y e l e c t r o n
d i f f r a c t i o n m e a s u r e m e n t s /12/. Q u a l i t a t i v e l y similar m o d e l s h a v e b e e n
o b t a i n e d f o r H 0 / Br / Cu(110) /1S7 a n d also f o r H 0 / CI / A g { 1 1 0 } .
2 2
Simulation of Non-Specific Adsorption in Vacuum
A l k a l i ions in a q u e o u s s o l u t i o n are p r o b a b l y t h e most typical a n d m o s t

widely studied representatives of non-specific adsorption. The
e l e c t r o c h e m i c a l t e r m o f n o n - s p e c i f i c a d s o r p t i o n is used t o d e n o t e t h e
survival o f at least t h e primary h y d r a t i o n shell w h e n a n i o n is i n t e r a c t i n g
w i t h a solid e l e c t r o d e . A s p o i n t e d o u t previously, t h e g e n e r a t i o n o f such
h y d r a t e d ions at t h e gas-solid interface w o u l d be o f g r e a t v a l u e b e c a u s e it
w o u l d p r o v i d e a n o p p o r t u n i t y t o s i m u l a t e t h e c h a r g i n g o f t h e interfacial
c a p a c i t o r at t h e o u t e r H e l m h o l t z p l a n e or p e r h a p s e v e n in t h e d i f f u s e layer.
A l t h o u g h q u i t e a f e w studies o f t h e c o a d s o r p t i o n o f w a t e r a n d alkalis
o n m e t a l surfaces in U H V . h a v e b e e n r e p o r t e d / 1 9 - 2 1 / t h e possibility o f
c o m p l e t e h y d r a t i o n o f t h e alkali a d s o r b a t e has n o t b e e n c o n s i d e r e d in m o s t
cases. T h e r e a s o n is p r o b a b l y t h a t , as yet, all t h e e x p e r i m e n t a l e v i d e n c e
s u g g e s t s t h a t t h e alkali ions are "specifically" a d s o r b e d in such g a s - p h a s e
s i m u l a t i o n e x p e r i m e n t s , e v e n w h e n an excess of w a t e r (several multilayers)
is m a d e a v a i l a b l e . This result is n o t yet u n d e r s t o o d , a l t h o u g h o n e s h o u l d
a g a i n k e e p in m i n d t h a t t h e s i m u l a t i o n e x p e r i m e n t s are typically
p e r f o r m e d 150 K b e l o w r o o m t e m p e r a t u r e .
D e s p i t e this a p p a r e n t n o n - e l e c t r o c h e m i c a l b e h a v i o u r o f a d s o r b e d
alkalis, in t h e p r e s e n c e o f c o a d s o r b e d w a t e r , such i n v e s t i g a t i o n s are
d e f i n i t e l y o f g r e a t v a l u e to t h e u n d e r s t a n d i n g o f t h e physical p h e n o m e n a
in t h e d o u b l e layer, at t h e m i c r o s c o p i c level. For e x a m p l e , by w o r k f u n c t i o n
m e a s u r e m e n t s in c o n j u n c t i o n w i t h c o v e r a g e d e t e r m i n a t i o n s o f t h e t w o
c o a d s o r b a t e s o n e can o b t a i n t h e initial d i p o l e m o m e n t o f w a t e r m o l e c u l e s
i n t e r a c t i n g w i t h d i f f e r e n t alkalis. Figure 6 s h o w s a c o m p i l a t i o n o f a v a i l a b l e
d a t a p l o t t e d a g a i n s t alkali i o n radius it is interesting t h a t t h e n a t u r a l
o r i e n t a t i o n of w a t e r , w i t h t h e o x y g e n t o w a r d s t h e m e t a l surface /13/, is
g r a d u a l l y reversed w h e n t h e ionic radius increases. For c e s i u m t h e
p e r p e n d i c u l a r a l i g n m e n t of t h e H2O m o l e c u l a r axis by t h e a l k a l i - s u r f a c e - i o n
plus s c r e e n i n g - c h a r g e d i p o l a r f i e l d a p p e a r s to be substantially larger t h a n
for t h e o p p o s i t e o r i e n t a t i o n o n t h e clean surface. Further e x p e r i m e n t s a r e ,
h o w e v e r , necessary to e l u c i d a t e m o r e clearly t h e i n t e r a c t i o n m e c h a n i s m f o r
this i m p o r t a n t c o a d s o r p t i o n system. T h e interesting recent results
c o n c e r n i n g t h e g e n e r a t i o n of h y d r a t e d p r o t o n s o n m e t a l surfaces in U H V .
/6/, m e n t i o n e d a b o v e , p r o v i d e e n c o u r a g e m e n t f o r f u r t h e r a t t e m p t s t o

F i g u r e 4 . C o m p a r i s o n o f U H V a n d in situ e l e c t r o c h e m i c a l d a t a . S o l i d
a n d d o t t e d lines c o r r e s p o n d t o t h e p o t e n t i a l d r o p across t h e i n n e r
layer f o r t h e Br/H20 a n d CI / H2O systems at a A g { 1 1 0 } e l e c t r o d e . Full
circles c o r r e s p o n d t o t h e c h a n g e in w o r k f u n c t i o n o f a A g { 1 1 0 } s u r f a c e
w i t h Br a n d w a t e r t o c o m p l e t e t h e i n n e r layer (taken f r o m f i g u r e 3 c).
O p e n t r i a n g l e s c o r r e s p o n d t o similar w o r k f u n c t i o n d a t a f o r t h e CI /
H2O system o n A g { 1 1 0 } .
F i g u r e 5. P r o p o s e d structure f o r Br / H2O a d s o r p t i o n o n A g { 1 1 0 }
w h i c h is c o m p a t i b l e w i t h L E E D , A $ a n d T D S m e a s u r e m e n t s / 1 2 / .

4. SASSANDBANGE Gas-Phase Adsorption Model Studies 63
Schematic Orientation
• of Water Molecules
0.01 H O/Cs/Ag(110)
_ 9
Alkali ~ 2
•
- H 0/K/Pt(111)
2
A l k a l i Ion R a d i u s (A)
0.5 1.0 1.5
•
H O/Na/Ag(110)
2
• Na ^
H O/Li/Ag(110)
2
mmmmmm.
\H O/Ag(110)
2
F i g u r e 6. Initial d i p o l e m o m e n t s a n d the p r o p o s e d o r i e n t a t i o n s f o r
s u r f a c e h y d r a t i o n w a t e r o n clean a n d alkali c o v e r e d A g { 1 1 0 } . In
a d d i t i o n t o o u r results f o r A g { 1 1 0 } , d a t a f o r H 0 / K /Pt{111}, t a k e n
2
f r o m r e f e r e n c e 13,are also i n c l u d e d .

p r o d o u c e h y d r a t e d alkali ions o n m e t a l surfaces by a d s o r p t i o n f r o m t h e g a s

phase.
Acknowledgments
O n e o f us (J.K.S.) w o u l d like t o t h a n k M . D o c h e r t y , P. C l a r k e a n d B.
S c h l e r e t h f o r s u p p o r t in t h e p r e p a r a t i o n o f this m a n u s c r i p t . T h e g e n e r o u s
h e l p o f D. Lackey is g r a t e f u l l y a c k n o w l e d g e d . This w o r k w a s s u p p o r t e d in
p a r t by D e u t s c h e F o r s c h u n g s g e m e i n s c h a f t t h r o u g h SFB 6.
References
1. See f o r e x a m p l e : D.A. K i n g a n d D.P. W o o d r u f f (Eds.), T h e C h e m i c a l

Physics o f S o l i d Surfaces a n d H e t e r o g e n e o u s Catalysis, Elsevier,
A m s t e r d a m , 1981-1988.
2. F . T . W a g n e r a n d P.N
3. J.K. Sass, V a c u u m 33
4. J.K. Sass, K. K r e t z s c h m a r a n d S. H o l l o w a y , V a c u u m 31, 483 (1981).
5. H.P. B o n z e l , G . Pirug a n d A . W i n k l e r , C h e m . Phys. Lett. 133, 116
(1985).
6. F . T . W a g n e r a n d T . E . M o y l a n , Surface Sci. 182, 1 2 5 ( 1 9 8 7 ) .
7. S. T r a s a t t i , i n : H. G e r i s c h e r a n d C . W . T o b i a s (Eds.), A d v a n c e s in
E l e c t r o c h e m i s t r y a n d E l e c t r o c h e m i c a l E n g e n e e r i n g , V o l . 10, W i l e y ,
N e w Y o r k , 1977, p. 213.
8. D . M . K o l b a n d W . N . H a n s e n , Surface Sci. 7 9 , 205 (1979)
9. K. B a n g e , B. S t r a e h l e r , J.K. Sass a n d R. Parsons, J. E l e c t r o a n a l . C h e m .
229, 8 7 ( 1 9 8 7 ) .
10. P.A. T h i e l a n d T . E . M a d e y , Surf. Sci. R e p o r t s 7, 211 (1987)
11. K. B a n g e , J.K. Sass, T . E . M a d e y , E . M . Stuve, S u r f a c e Sci., 183, 334,
(1987).
12. K. B a n g e , T . E . M a d e y a n d J.K: Sass, Surface Sci. 162, 272 (1985)
13. G . P i r u g , H.P. B o n z e l , J . E . M ü ller, Phys. Rev. Lett., 58(20), 2 1 3 8 ,
(1987).
14. R. Parsons, T r a n s . F a r a d a y Soc. 64, 1638 (1955).
15. R. D ö h l - O e l z e , Thesis, T e c h n i s c h e U n i v e r s i t ä t B e r l i n , 1986.
16. G . V a l e t t a a n d R. Parsons, J. E l e c t r o a n a l . C h e m . 123, 141 (1981).
17. B. S t r a e h l e r , J.K. Sass, K. B a n g e a n d R. Parsons, Phys. Rev. Lett.,
submitted for publication.
18. K. B a n g e , R. D ö hl, D.E. G r i d e r a n d J.K. Sass, V a c u u m , 33, 757 (1983).
19. M . K i s k i n o v a , G . Pirug a n d H.P. B o n z e l , Surface Sci., 150, 319 (1985).
20. P . A . T h i e l , J . H r b e k , R.A. d e P a o l a a n d F . M . H o f f m a n n , C h e m . Phys.
L e t t ., 108, 25 (1984).
21. C . B e n n d o r f , C . N ö b l a n d T . E . M a d e y , S u r f a c e Sci. 138, 292 (1984).
R E C E I V E D August 24, 1988

Chapter 5
Modeling the Aqueous—Metal Interface

in Ultrahigh Vacuum
via Cryogenic Coadsorption
Frederick T. Wagner and Thomas E. Moylan
Physical Chemistry Department, General Motors Research Laboratories,

Warren, MI 48090-9055
Three stages in th
faces in ultrahig
tal examples of each stage, verified with a variety of
surface spectroscopies, are given. The first stage is
the adsorption of water alone, or water and a neutral
probe molecule, on a well-defined metal surface. Hyd-
rophilic coadsorption of CO and water on Rh(111) is
contrasted with hydrophobic coadsorption on Pt(111),
demonstrating that weakly-bound water can modify the
adsorption of even strongly-bound, neutral species.
The second stage of modeling is the introduction of
solvated ionic species into the model double layer.
+
Coadsorption of HF and water yields adsorbed H O ions; 3
the solvation stoichiometries of ions in the f i r s t

monolayer and in subsequent layers are determined. The
third stage of modeling is establishment of potential
control in UHV. Hydrogen coadsorption is used to def-
lect the effective potential of the water monolayer
below the potential of zero charge. The unique ways in
which UHV models can contribute to an improved molec-
ular-scale understanding of electrochemical interfaces
are discussed.
U l t r a h i g h vacuum s u r f a c e s p e c t r o s c o p i e s can p r o v i d e f a r g r e a t e r
b r e a d t h and depth o f i n f o r m a t i o n about s u r f a c e p r o p e r t i e s than c a n
y e t be a c h i e v e d u s i n g i n s i t u s p e c t r o s c o p i e s a t t h e aqueous/metal
i n t e r f a c e . A p p l i c a t i o n o f t h e vacuum t e c h n i q u e s t o e l e c t r o c h e m i c a l
i n t e r f a c e s i s t h u s d e s i r a b l e , b u t has been plagued by q u e s t i o n s o f
t h e r e l e v a n c e o f t h e emersed, evacuated s u r f a c e s examined t o t h e r e a l
e l e c t r o c h e m i c a l i n t e r f a c e s . T h i s concern i s a c c e n t u a t e d by s u r f a c e
s c i e n t i s t s ' o b s e r v a t i o n s t h a t i n UHV no m o l e c u l a r water remains on
w e l l - d e f i n e d s u r f a c e s a t room t e m p e r a t u r e and above (1). Emersion
and e v a c u a t i o n a t room t e m p e r a t u r e may o r may n o t produce s i g n i f i c a n t
changes i n e l e c t r o c h e m i c a l i n t e r f a c e s ! depending on whether o r n o t
water p l a y s a major r o l e i n t h e s u r f a c e c h e m i s t r y .
0097-6156/88/0378-0065$06.00/0
© 1988 American Chemical Society

B u l k water can be k e p t on s u r f a c e s i n UHV by m a i n t a i n i n g a

s u r f a c e t e m p e r a t u r e below 160 K. A wide range o f s p e c t r o s c o p i e s
i n d i c a t e t h a t water l a y e r s formed a t t h e s e t e m p e r a t u r e s , even f o r
submonolayer c o v e r a g e s , a r e e x t e n s i v e l y hydrogen-bonded and t h u s
r e p r e s e n t an a s s o c i a t e d , condensed phase r a t h e r t h a n a c o l l e c t i o n o f
i s o l a t e d adsorbed water m o l e c u l e s ( 1 ) . We can t h e r e f o r e hope t o
s t u d y f u l l y h y d r a t e d s p e c i e s i n UHV on l i q u i d n i t r o g e n c o o l e d s u r -
f a c e s . The r e l e v a n c e o f such low-temperature i n t e r f a c e s t o normal
aqueous s o l u t i o n s i s a t t e s t e d t o by f r o z e n e l e c t r o l y t e e x p e r i m e n t s
( 2 ) , i n which e l e c t r o c h e m i s t r y q u i t e s i m i l a r t o normal, room-tempera-
t u r e aqueous b e h a v i o r has been observed down t o around 150 K. To t h e
a u t h o r s ' knowledge no one has y e t succeeded, i n a U H V - e l e c t r o c h e m i c a l
t r a n s f e r e x p e r i m e n t , a t c o o l i n g a sample d u r i n g emersion t o m a i n t a i n
a l a y e r o f b u l k water on t h e s u r f a c e a f t e r e v a c u a t i o n , though s e v e r a l
groups a r e now equipped f o r t h e a t t e m p t . However, an a l t e r n a t e ap-
proach a l l o w i n g UHV s t u d i e s o f aqueous i n t e r f a c e s i s a v a i l a b l e and
forms t h e s u b j e c t o f t h i s paper T h i s approach i s t o grow from t h e
vapor phase and w i t h o u t
environment, models o f
r e l e v a n t s p e c i e s . There a r e t h r e e major s t e p s t o such m o d e l i n g : (1)
a d s o r p t i o n o f water a l o n e , o r water p l u s a n e u t r a l probe m o l e c u l e ,
(2) a d d i t i o n o f s o l v a t e d i o n i c s p e c i e s t o t h e UHV i n t e r f a c e , and (3)
e s t a b l i s h m e n t o f c o n t r o l over t h e e f f e c t i v e e l e c t r o c h e m i c a l p o t e n t i a l
of t h e UHV i n t e r f a c e . T h i s c h a p t e r w i l l d e s c r i b e , and p r o v i d e an
e x p e r i m e n t a l i l l u s t r a t i o n o f , each o f t h e s e s t e p s .
Experimental
A l l e x p e r i m e n t s were performed i n a s t a i n l e s s s t e e l u l t r a h i g h vacuum

chamber equipped f o r t e m p e r a t u r e programmed d e s o r p t i o n (TPD), h i g h
r e s o l u t i o n e l e c t r o n energy l o s s s p e c t r o s c o p y (HREELS), Auger e l e c t r o n
s p e c t r o s c o p y (AES), and low energy e l e c t r o n d i f f r a c t i o n (LEED) ( 3 - 5 ) .
Gases were impinged o n t o t h e Rh and P t s i n g l e c r y s t a l samples, c o o l e d
t o 100 K w i t h l i q u i d n i t r o g e n , t h r o u g h c a p i I l a r y argay d o s e r s which
a l l o w e d background p r e s s u r e s i n t h e 10" T o r r (10" Pa) range t o be
m a i n t a i n e d d u r i n g d o s i n g . Water was a d m i t t e d i n t o t h e chamber from
the vapor above a freeze-pump-thaw c y c l e d sample o f t h e pure l i q u i d
h e l d i n a g l a s s ampoule. Anhydrous HF, condensed from a commercial
anhydrous c y l i n d e r ( p r e s s u r i z e d w i t h He) i n t o a s t a i n l e s s s t e e l t u b e ,
was a l s o freeze-pump-thaw c y c l e d t o remove v o l a t i l e i m p u r i t i e s .
S t e p 1 - Water p l u s a n e u t r a l probe m o l e c u l e , CO
The f i r s t s t e p i n t h e UHV modeling o f aqueous/metal i n t e r f a c e s i s t h e

a d s o r p t i o n o f water a l o n e , o r water w i t h a n e u t r a l probe m o l e c u l e , on
the metal o f i n t e r e s t . T h i s s t e p s e t s up t h e hydrogen-bonded, h i g h
d i e l e c t r i c c o n s t a n t medium which c o u l d do much t o d i s t i n g u i s h
a q u e o u s - s o l i d from g a s - s o l i d i n t e r f a c e s by p r o v i d i n g an environment
amenable t o i o n i c s p e c i e s . E x t e n s i v e UHV s t u d i e s o f water on a v a r i -
ety o f s u r f a c e s ( a b l y reviewed i n Ref. 1) have shown water t o be
weakly a d s o r b e d , w i t h H 0-metal and HoQ-rLO i n t e r a c t i o n s summing t o
2
10-12 k c a l / m o l e . S i n c e water i s weakly bound compared t o many neu-

t r a l m o l e c u l e s such a s CO, one might e x p e c t t h e p r e s e n c e o r absence
of water t o have l i t t l e e f f e c t on t h e a d s o r p t i o n c h e m i s t r y o f such
s t r o n g l y bound n e u t r a l s . W h i l e f o r CO on P t ( l l l ) t h e e x p e c t a t i o n o f

5. WAGNER AND M O Y L A N Aqueous-Metal Interface in Ultrahigh Vacuum 67
s m a l l water e f f e c t s i s borne o u t , on R h ( l l l ) a t t r a c t i v e CO-water

i n t e r a c t i o n s s i g n i f i c a n t l y modify t h e a d s o r p t i o n c h e m i s t r y , s u g g e s t -
ing p o s s i b l e r a m i f i c a t i o n s f o r e l e c t r o c a t a l y s i s ( 5 ) .
TPD o f CO p l u s water on R h ( l l l ) and P t ( l l l ) . F i g u r e 1 shows how

i n c r e a s i n g predoses o f CO on R h ( l l l ) c o n t i n u o u s l y s h i f t t h e t h e r m a l
d e s o r p t i o n o f 1/2 monolayer o f DgO t o h i g h e r t e m p e r a t u r e s , i n d i c a t i n g
net a t t r a c t i v e i n t e r a c t i o n s between water and CO on t h i s s u r f a c e .
F i g u r e 2 g i v e s t h e r e s u l t s o f t h e analogous e x p e r i m e n t s on P t ( l l l ) ;
on t h i s s u r f a c e even t h e lowest CO p r e e x p o s u r e s s h i f t water de-
s o r p t i o n t o lower t e m p e r a t u r e s , i n d i c a t i n g n e t r e p u l s i v e i n t e r a c t i o n s
between water and CO. On both s u r f a c e s t h o o n l y d e s o r b i n g s p e c i e s
were water and CO; t h u s no e v i d e n c e f o r an i r r e v e r s i b l e water gas
s h i f t r e a c t i o n was seen. The lack o f and/or desorption, taken
in t h e c o n t e x t o f t h e known thermal b e h a v i o r o f f u n c t i o n a l g r o u p s ,
a l s o a r g u e s a g a i n s t s u r f a c e r e a c t i o n t o form adsorbed s p e c i e s such as
f o r m y l , f o r m a t e , o r c a r b o n a t e i n t h e t e m p e r a t u r e range below which
water d e s o r b s (TS210 K )
HREELS o f CO p l u s water on R h ( l l l ) . More s p e c i f i c i n f o r m a t i o n about

the a c t u a l s p e c i e s p r e s e n t a f t e r c o a d s o r p t i o n i s p r o v i d e d by h i g h
r e s o l u t i o n e l e c t r o n energy l o s s s p e c t r o s c o p y (HREELS), which y i e l d s
v i b r a t i o n a l d a t a r o u g h l y analogous t o t h o s e o b t a i n e d by s u r f a c e i n -
f r a r e d s p e c t r o s c o p y . F i g u r e 3 shows R h ( l l l ) v i b r a t i o n a l s p e c t r a f o r
o n e - h a l f monolayer o f D~0 w i t h i n c r e a s i n g CO p r e d o s e s ( 5 ) . The DgO-
a l o n e spectrum ( F i g u r e 3a) i s c h a r a c t e r i z e d by a l i b r a t i o n a l ( h i n -
d e r e d r o t a t i o n a l ) mode a t 580 cm" , the.D-O-D s c i s s o r i n g mode a t 1190
cm" , and 0-D s t r e t c h e s around 2480 cm" ( 4 ) . On R h ( l l l ) Jow c o v e r -
ages o f CO a l o n e g i v e a s i n g l e C-0 s t r e t c h a t 2020-2070 cm" ascribed
t o CO bound a t o p a s i n g l e Rh atom. For h i g h e r c o v e r a g e s o f CO a l o n e
a second^peak, a s c r i b e d t o CO i n a t w o - f o l d b r i d g e s i t e , grows i n a t
1830 cm , b u t i t s h e i g h t never exceeds 70% o f t h a t o f t h e a t o p CO
pealj. I n t h e p r e s e n c e o f water s m a l l CO c o v e r a g e s y i e l d n o t t h e 2020
cm a t o p peak_jeen i n t h e absence of w a t e r , b u t r a t h e r a new peak
around 1620 cm" . Even a t h i g h CO c o v e r a g e , t h e CO+D2O spectrum i s
d i s t i n c t from t h e C O j a l o n e spectrum, as w i t h water p r e s e n t t h e i n t e n -
s i t y o f t h e 1830 cm" ( b r i d g e d ) peak exceeds t h a t o f t h e 2040 cm
(atc-p) peak, and a s h o u l d e r on t h e low-frequency s i d e o f t h e 1830
cm peak i n d i c a t e s t h a t some o f t h e CO i s s t i l l i n t h e form which
produced t h e 1620 cm" peak a t low.CO c o v e r a g e .
We b e l i e v e t h a t t h e ~1620 cm" peak a r i s e s from CO bound i n a
t h r e e - f o l d h o l l o w s i t e , by a n a l o g y t o rhodium c l u s t e r compounds
1
y i e J d i n g a CO s t r e t c h a t 1600-1685 cm" (6-7) and t o t h e 1655-1700
cm" CO s t r e t c h o b s e r v e d f o r CO+benzene/Rh(lll) ( 8 ) , where LEED
i n t e n s i t y a n a l y s i s has p l a c e d t h e CO i n t h e t h r e e - f o l d h o l l o w . A
HREELS peak around 1620 cm" c o u l d a l s o a r i s e from r e a c t i o n o f CO and
water t o produce f o r m a t e , f o r m y l , o r c a r b o n a t e , a l l o f which s h o u l d
have v i b r a t i o n a l modes i n t h i s f r e q u e n c y range. However, none o f t h e
o t h e r modes e x p e c t e d f o r such s p e c i e s were o b s e r v e d , and t h e l a c k o f
Hg o r COg d e s o r p t i o n p r o d u c t s a l s o argue a g a i n s t t h e p r e s e n c e o f such
s p e c i e s . XPS d a t a a r e a l s o c o n s i s t e n t w i t h a w a t e r - i n d u c e d s h i f t i n
CO b i n d i n g s i t e . A d d i t i o n o f water t o low c o v e r a g e s o f CO on R h ( l l l )
s h i f t s t h e XPS 0 I s s i g n a l due t o CO from 531.7 t o 530.0 eV b i n d i n g
energy, as e x p e c t e d f o r a s h i f t from an a t o p t o a m u l t i p l y - b o u n d s i t e
(9). Thus, w a t e r , though weakly bound t o R h ( l l l ) , s h i f t s t h e much

i i r
Rh(111)
x L CO + 1 L D 0
2
F i g u r e 1. DgO TPD from R h ( l l l ) o f v a r y i n g e x p o s u r e s o f CO f o l -

lowed by 1 L DoO. (Reproduced w i t h p e r m i s s i o n from Ref. 5. Copy-
r i g h t 1988 E l s e v i e r . )
150 200 250

T (K)
F i g u r e 2. HgO TPD from P t ( l l l ) o f v a r y i n g e x p o s u r e s o f CO f o l -

lowed by 1 L FLO. (Reproduced w i t h p e r m i s s i o n from R e f . 5. Copy-
r i g h t 1988 E l s e v i e r . )

5. WAGNER AND MOYLAN Aqueous-Metal Interface in Ultrahigh Vacuum 69
F i g u r e 3. R h ( l l l ) HREELS s p e c t r a of a.) 1 L D J ) , b. - f . ) v a r y i n g
exposures o f CO f o l l o w e d by 1 L D 0. 2 (Reproduced w i t h p e r m i s s i o n
from Ref. 5. C o p y r i g h t 1988 E l s e v i e r . )

more s t r o n g l y - b o u n d CO m o l e c u l e t o a s i t e not p o p u l a t e d i n t h e
absence of water.
C o a d s o r p t i o n on R h ( l l l ) a l s o m o d i f i e s t h e HREELS f e a t u r e s due t o
water. -As shown i n F i g u r e 3, a s u b s t a n t i a l s h a r p e n i n g and s h i f t t o
610 cm o f t h e pure D 0 band a t 580 cm"
2 (due t o t h e superimposed
D 0 l i b r a t i o n and Rh-0 s t r e t c h ) c o r r e l a t e s w i t h t h e growth of t h e
2
~I650 cm" CO mode. The f a c t t h a t t h e v i b r a t i o n a l s p e c t r a of b o t h

s p e c i e s a r e m o d i f i e d by c o a d s o r p t i o n s u g g e s t s a d s o r p t i o n o f water and
CO onto a d j a c e n t s i t e s , a form o f h y d r o p h i l i c c o a d s o r p t i o n .
H 0 + C 0 / R h ( l l l ) produced f e a t u r e s analogous t o t h o s e shown f o r
2
D 0 + C 0 / R h ( l l l ) . A p a r t i a l s u p e r p o s i t i o n o f t h e d o w n s h i f t e d CO
2
s t r e t c h and t h e H-O-H s c i s s o r mode a t 1620 cm" makes t h e e f f e c t l e s s

w e l l - r e s o l v e d f o r HgO than f o r DÔ, but we i n f a c t observed t h e CO
d o w n s h i f t f i r s t w i t n HgO.
HREELS of CO p l u s water on P t ( l l l ) . F i g u r e 4 shows HREELS s p e c t r a

f o r CO and a h a l f monolayer of water on P t ( l l l ) The w a t e r - a l o n e
spectrum ( F i g u r e 4 a ) , e x h i b i t
and OH s t r e t c h a t _ J 4 4 0 cm
1020, and 1950 cm" p r e v i o u s l y a s c r i b e d t o a m i n o r i t y water s p e c i e s
(4). On P t ( l l l ) metal c o a d s o r p t i o n produces not t h e s i n g l e low f r e -
quency t h r e e - f o l d peak seen f o r t h e s e CO and w a t e r . c o v e r a g e s on
R h ( l l l ) , b u t r a t h e r two peaks a t 2080 and 1830 cm" , c o r r e s p o n d i n g t o
the a t o p and t w o - f o l d CO s p e c i e s seen on both s u r f a c e s f o r h i g h e r
c o v e r a g e s of CO a lone. I n c r e a s i n g water a d d i t i o n s t o a c o n s t a n t low
coverage o f CO on P t ( l l l ) d e c r e a s e t h e a t o p / b r i d g e peak h e i g h t r a t i o
i n t h e same way t h a t i n c r e a s i n g t h e coverage o f CO a l o n e would do.
On P t ( l l l ) t h e HREELS f e a t u r e s due t o water a r e unchanged by t h e
presence o f CO. These o b s e r v a t i o n s i n d i c a t e t h a t water and CO adsorb
onto s e p a r a t e p a t c h e s on t h e s u r f a c e , i n a form o f hydrophobic coad-
s o r p t i o n . Water condenses i n t o hydrogen-bonded i s l a n d s , as i n d i c a t e d
by t h e low 0-H s t r e t c h i n g f r e q u e n c y . CO s p r e a d s t o c o v e r t h e r e s t o f
s u r f a c e , g i v i n g a phase s i m i l a r t o t h a t f o r CO a l o n e , b u t w i t h a
coverage n o r m a l i z e d t o t h e w a t e r - f r e e , not t o t a l , s u r f a c e a r e a . CO-
CO r e p u l s i o n s , which have been w e l l documented on P t ( l l l ) ( 1 0 ) ,
produce a s u r f a c e p r e s s u r e w i t h i n t h e CO p a t c h e s which b e a r s upon t h e
edges o f t h e water i s l a n d s . I t i s t h i s l a t e r a l p r e s s u r e which causes
water t o desorb from P t ( l l l ) a t lower t e m p e r a t u r e s i n t h e p r e s e n c e o f
coadsorbed CO.
H y d r o p h i I i c v e r s u s hydrophobic c o a d s o r p t i o n . The c o n t r a s t between

the h y d r o p h i l i c and hydrophobic c o a d s o r p t i o n seen on R h ( l l l ) and
P t ( l l l ) , i f c o n f i r m e d under normal e l e c t r o c h e m i c a l c o n d i t i o n s , might
be o f e l e c t r o c a t a l y t i c importance. On R h ( l l l ) , where n e t a t t r a c t i v e
C0-H 0 i n t e r a c t i o n s produce a mixed phase i n which CO i s d i s p l a c e d t o
2
a t h r e e - f o l d b i n d i n g s i t e which i s not o c c u p i e d i n t h e absence o f

w a t e r , CO and water appear t o occupy a d j a c e n t b i n d i n g s i t e s . Such
thorough m i x i n g o f t h e oxygen s o u r c e (water) and t h e i n t e r m e d i a t e [or
p o i s o n ] (CO) s h o u l d improve e l e c t r o o x i d a t i o n r a t e s f o r C 0 H f u e l s
x
(11). On P t ( l l l ) , where n e t r e p u l s i o n s cause c o n d e n s a t i o n ^ ? CO and

water i n t o s e p a r a t e p a t c h e s , r e a c t i o n between t h e adsorbed s p e c i e s
c o u l d o c c u r o n l y a t t h e b o u n d a r i e s between p a t c h e s , and one would
expect slower k i n e t i c s .
The d i f f e r e n t c o a d s o r p t i o n c h e m i s t r i e s on t h e s e two s t r u c t u r a l l y
and c h e m i c a l l y s i m i l a r s u r f a c e s i l l u s t r a t e t h e importance of t h e

T 1 1 1 1 1 1 i i r
Pt(111)
0.25 L C O + 1 L H 0 2
2110
400 1200 2000 2800 3600

-1
cm
F i g u r e 4. P t ( l l l ) HREELS s p e c t r a f o r a.) 1 L HÔ a t 90 K (does
not change upon a n n e a l i n g ) ; 0.25 L CO f o l l o w e d By 1 L HÔ: b.) a t
90 K, c.) a f t e r f l a s h t o 148 K ( n o t h i n g d e s o r b e d ) , d.) a f t e r f l a s h
t o 323 K (water desorbed). (Reproduced w i t h p e r m i s s i o n from Ref.
5. C o p y r i g h t 1988 Elsevier.)

s u b t l e b a l a n c e o f t h e many d i f f e r e n t l a t e r a l i n t e r a c t i o n s p r e s e n t i n
muIticomponent a d s o r p t i o n systems. Both t r u e l a t e r a l i n t e r a c t i o n s
and t h e s i t e - t o - s i t e v a r i a t i o n s i n m e t a I - a d s o r b a t e i n t e r a c t i o n
s t r e n g t h s w i l l i n f l u e n c e t h e c o a d s o r p t i o n geometry. The v a l e n c e
e l e c t r o n s i n P t have more d - c h a r a c t e r , and a r e t h e r e f o r e more l o c a l -
i z e d , t h a n t h o s e i n Rh. One would then e x p e c t a g r e a t e r s i t e - t o - s i t e
v a r i a t i o n i n m e t a I - a d s o r b a t e i n t e r a c t i o n s on P t than on Rh, a s has
been noted f o r NO a d s o r p t i o n ( 1 2 ) . Moving CO and rUO o f f o f t h e i r
optimum one-component b i n d i n g s i t e s t o o p t i m i z e CO-RgO i n t e r a c t i o n s
would t h u s e x a c t a g r e a t e r m e t a I - a d s o r b a t e f r e e energy p e n a l t y on P t
than on Rh. There i s a l s o some e v i d e n c e t h a t t h e s t r e n g t h o f w a t e r -
water i n t e r a c t i o n s i s d i f f e r e n t on t h e s e two s u r f a c e s ( 4 ) .
Thus, a l t h o u g h water i s weakly bound on s u r f a c e s , i t s p r e s e n c e
can, b u t need b u t n o t i n a l l c a s e s , a l t e r t h e b a l a n c e o f f o r c e s which
d e t e r m i n e s t h e a d s o r p t i o n s t a t e o f much more s t r o n g l y bound s p e c i e s .
F u r t h e r work i s needed t o d e t e r m i n e whether t h e R h ( l l l ) o r t h e
P t ( l l l ) c a s e i s more t y p i c a l and a l s o t o d e t e r m i n e t h e e x t e n t t o
which t h e c r y o g e n i c c o a d s o r p t i o
r e a l aqueous environments
ing i n f o r m a t i o n from UHV gas-phase a d s o r p t i o n s t u d i e s t o h e l p i n t e r -
p r e t h i s r e s u l t s s h o u l d be aware t h a t t h e presence o f water can a l t e r
a d s o r p t i o n c h e m i s t r y even f o r s t r o n g l y - b o u n d n e u t r a l m o l e c u l e s which
are n o t good hydrogen-bond donors o r a c c e p t o r s . And t h e UHV s u r f a c e
s c i e n t i s t hoping t o p r o v i d e g a s - a d s o r p t i o n d a t a r e l e v a n t t o e l e c t r o -
c h e m i s t r y s h o u l d c o n s i d e r d o i n g water c o a d s o r p t i o n e x p e r i m e n t s t o
check f o r s u r p r i s i n g e f f e c t s such as t h o s e demonstrated here f o r
Rh(lll).
S t e p 2 - A d d i t i o n o f i o n i c s p e c i e s t o t h e UHV model: HF + HÔ
A l l e l e c t r o c h e m i c a l t e c h n i q u e s measure charge t r a n s f e r r e d a c r o s s an
i n t e r f a c e . S i n c e charge i s t h e measurable q u a n t i t y , i t i s n o t s u r -
p r i s i n g t h a t e l e c t r o c h e m i c a l t h e o r y has been founded on an e l e c t r o -
s t a t i c b a s i s , w i t h c h e m i c a l e f f e c t s added as a p e r t u r b a t i o n . I n t h e
e l e c t r o s t a t i c l i m i t i o n s a r e t r e a t e d as f u l l y charged s p e c i e s w i t h
some l e v e l o f s o l v a t i o n . I f we a r e t o use UHV models t o t e s t t h e o -
r i e s o f t h e d o u b l e l a y e r , we must be a b l e t o s t u d y i n UHV t h e weakly-
a d s o r b i n g systems where t h e s e i d e a l " e l e c t r o s t a t i c " i o n s c o u l d be
p r e s e n t and where we would e x p e c t t h e e f f e c t s o f water t o be most
dominant. To t h i s end, and t o a l l o w a p p l i c a t i o n o f UHV s p e c t r o s c o p i c
methods t o t h e pH e f f e c t s which c o n t r o l s o much o f aqueous i n t e r -
f a c i a l c h e m i s t r y , we have s t u d i e d t h e c o a d s o r p t i o n o f water and anhy-
drous HF on P t ( l l l ) i n UHV ( 3 ) . S u r f a c e s p e c t r o s c o p i e s have a l l o w e d
us t o f o l l o w t h e i o n i z a t i o n o f t h e a c i d and t o d e t e r m i n e t h e e x t e n t
of s o l v a t i o n both i n t h e l a y e r a d j a c e n t t o t h e metal and i n subse-
quent l a y e r s .
TPD o f HF a l o n e , and o f HF p l u s w a t e r , on P t ( l l l ) . Anhydrous HF, i n

which hydrogen bonding i s e x t e n s i v e , s h a r e s many p r o p e r t i e s w i t h
w a t e r , i n c l u d i n g a broad t e m p e r a t u r e range o f s t a b i l i t y o f t h e l i q u i d
and t h e h i g h d i e l e c t r i c c o n s t a n t o f t h e l i q u i d . T h i s p a r a l l e l i s m o f
behavior extends t o t h e i n t e r a c t i o n s with t h e P t ( l l l ) s u r f a c e . Like
w a t e r , HF i s m o l e c u l a r l y adsorbed on P t ( l l l ) . Each s u b s t a n c e , a d -
s o r b e d a l o n e , g i v e s a s i n g l e d e s o r p t i o n peak f o r c o v e r a g e s up t o t h e
monolayer and a second d e s o r p t i o n peak a t lower t e m p e r a t u r e f o r

subsequent l a y e r s . However, HF d e s o r b s a t 50 K lower t e m p e r a t u r e s

(130 and 126 K f o r t h e monolayer and m u l t i l a y e r , r e s p e c t i v e l y , v e r s u s
179 and 168 K f o r w a t e r ) , p r o b a b l y due t o t h e fewer hydrogen bonds
per m o l e c u l e formed by HF.
C o a d s o r p t i o n o f HF and water has no e f f e c t on t h e water de-
s o r p t i o n peaks, but s t a b i l i z e s p a r t o r a l l of t h e HF t o h i g h e r
t e m p e r a t u r e s , as shown by F i g u r e 5. As long as a t l e a s t 5 m o l e c u l e s
of water per HF m o l e c u l e a r e added t o t h e s u r f a c e (up t o monolayer
c o v e r a g e , o r 8 HÔ/HF f o r subsequent l a y e r s ) no HF d e s o r b s u n t i l
water s t a r t s t o l e a v e t h e s u r f a c e around 170 K, p e a k i n g a t 180 K. As
long as a t l e a s t 1 m o l e c u l e of water i s i n i t i a l l y p r e s e n t per HF, no
HF d e s o r p t i o n w i l l o c c u r u n t i l 150 K, p e a k i n g a t 162 K. I f more HF
t h a n HoO m o l e c u l e s a r e p r e s e n t i n i t i a l l y , some HF w i l l desorb i n a
peak a t 136 K, near t h e t e m p e r a t u r e a t which HF a l o n e d e s o r b s . Coad-
s o r p t i o n t h u s can y i e l d HF d e s o r p t i o n a t t h r e e peaks, one not s t a b i -
l i z e d v s . HF a l o n e , one s t a b i l i z e d by 30 K, and one s t a b i l i z e d by 50
K, i . e . , t o t h e water d e s o r p t i o n t e m p e r a t u r e
HREELS o f t h e HÔ + HF system

I i z i n g HF on t h e s u r f a c e i s made c l e a r by t h e HREELS s p e c t r a o f F i g -
ure 6. As t h e c o n c e n t r a t i o n of HF i n t h e water l a y e r i s i n c r e a s e d a
new peak around 1150 cm" (and s e v e r a l s m a l l e r peaks) f i r s t i n c r e a s e s
and t h e n , as t h e HF/HÔ r a t i o exceeds 1, d e c r e a s e s i n i n t e n s i t y . By
a n a l o g y t o v i b r a t i o n a l s p e c t r a o f a c i d h y d r a t e s of known s t r u c t u r e
(13-16), t h i s p e a k i s i d e n t i f i e d as t h e symmetric bending mode o f t h e
+
p y r a m i d a l H»0 i o n . We have observed t h e same peak upon c o a d s o r p t i o n

of water ana o t h e r , s t r o n g e r , m i n e r a l a c i d s . The r e a c t i o n
+
H02 + HF — > H 0
3 + F"
can proceed f u r t h e r t o t h e r i g h t i n t h e s e c r y o g e n i c e x p e r i m e n t s t h a n
in room t e m p e r a t u r e aqueous s o l u t i o n because t h e low t e m p e r a t u r e
d e c r e a s e s t h e importance of t h e u n f a v o r a b l e e n t r o p y o f s o l v a t i o n of
the f l u o r i d e i o n ( 1 7 ) .
S o l v a t i o n s t o i c h i o m t t r i e s . HREELS i s s e n s i t i v e t o i n t e r n a l modes o f
ion c o r e s , but d e t a i l s of s o l v a t i o n would produce a t most secondary
e f f e c t s on t h e v i b r a t i o n a l s p e c t r a . However, t h e i d e n t i f i c a t i o n o f
the i o n i z a t i o n r e a c t i o n , c o u p l e d w i t h t h e TPD d a t a o u t l i n e d above,
a l l o w us t o q u a n t i f y t h e s o l v a t i o n . The HF d e s o r p t i o n peak c o i n c i -
dent w i t h t h e water peak a t 180 K, seen f o r m o l e c u l a r r a t i o s o f
HrtO/HF^ i n t h e monolayer and >8 i n subsequent l a y e r s , c o r r e s p o n d s t o
trie r e c o m b i n a t i o n o f HÔ* and F" i o n s which had been f u l l y s o l v a t e d .
Screened by s o l v a t i n g water m o l e c u l e s , t h e s e i o n s cannot combine t o
form HF u n t i l t h e s o l v a t i o n water d e s o r b s . The f i g u r e o f 8 f o r l a y -
e r s subsequent t o t h e monolayer agrees w i t h t h e sum o f t h e p r i m a r y
s o l v a t i o n numbers measured i n room t e m p e r a t u r e aqueous s o l u t i o n f o r
the H [4] and F [4*1] i o n s ( 1 8 ) . T h i s agreement, i n c o m b i n a t i o n
w i t h t h e f r o z e n e l e c t r o l y t e work of Stimining's group ( 2 ) , g i v e s hope
t h a t t h e c r y o g e n i c aqueous environment a c c e s s i b l e i n UHV may be r e l e -
v a n t t o s t a n d a r d e l e c t r o c h e m i s t r y . The l e s s e r number of s o l v a t i o n
w a t e r s seen i n t h e f i r s t monolayer s u g g e s t s t h a t even t h e s e c l a s s i -
c a l l y " n o n - s p e c i f i c a l l y adsorbed" i o n s l o s e some o f t h e i r s o l v a t i o n
w a t e r s upon a d s o r p t i o n , a t l e a s t on P t ( l l l ) , a s u r f a c e w h i c h , when
w e l l o r d e r e d , g i v e s n o t o r i o u s l y s t r a n g e voltammetry (19-20). I t a l s o

100 150 200 250

T (K)
F i g u r e 5. HF thermal d e s o r p t i o n s i g n a l s , n o r m a l i z e d t o HÔ c o v e r -
age, f o r HF/H 0 monolayer r a t i o s o f : a.) 0.12, b.) 0.15, c.) 0.20,
9
d.) 0.42, e.)^0.56, f . ) 0.75, and g.) 1.28. (Reproduced w i t h

p e r m i s s i o n from Ref. 3. C o p y r i g h t 1987 E l s e v i e r . )

5. WAGNER AND M O Y I A N Aqueous-Metal Interface in Ultrahigh Vacuum 75
Loss Energy (1/cm)

400 1200 2000 2800 3600
770
0 100 200 300 400 500

Loss Energy (mV)
F i g u r e 6. HREELS s p e c t r a f o r HJ) and HF a d s o r p t i o n and c o a d s o r p -

t i o n on P t ( l l l ) a t 100 K, HF/HJJ r a t i o i n c r e a s i n g upwards, a.) 1
monolayer (ML) H 0 , xlOO; b.) iML H 0 + 0.05ML HF, xlOO; c.) 1ML
9 9
H 0 * 0.12 ML HF; xlOO; d.) 1 ML HJ) + 0.5 ML HF, xlOO; e.) 1 ML

o
HÔ • 1 ML HF; f . ) 1 ML HF + 0.25 ML H 0 , xlOO; g.) 1 ML HF, x l 6 . 5

2
and x 110. (Reproduced w i t h p e r m i s s i o n from R e f . 3. C o p y r i g h t

1987 E l s e v i e r . )

draws i n t o q u e s t i o n t h e c o n c e p t o f a h y d r a t i o n s h e a t h s e p a r a t i n g t h e
s u r f a c e from t h e s o l v a t e d i o n s ( 2 1 ) , which would y i e l d a h i g h e r num-
ber o f w a t e r s p e r HF i n t h e f i r s t i o n i c l a y e r than i n subsequent
layers.
The HF d e s o r p t i o n peak around 160 K c o r r e s p o n d s t o t h e f r a c t i o n -
a l d i s t i l l a t i o n o f HF from t h e monohydrate phase [HJ) ] [ F ] , which
has been w e l l e s t a b l i s h e d i n b u l k s t u d i e s ( 2 2 ) . The b u l k work has
not i d e n t i f i e d any w a t e r - r i c h d i s t i n c t phases. The 136 K HF de-
s o r p t i o n peak seen f o r HF/H Q>1 i s due t o t h e l o s s o f e x c e s s
2
m o l e c u l a r HF from t h e l a y e r .
C o a d s o r p t i o n o f HF and HgO has shown t h a t we can grow i n UHV j m ,
i f n o t y e t demonstrably t h e , i o n i c aqueous environment w i t h c o n -
t r o l l e d pH and c o m p o s i t i o n .
Step 3 - Control o f e f f e c t i v e e l e c t r o d e p o t e n t i a l : + HÔ
The unique a s p e c t o f e l e c t r o c h e m i s t r y l i e s i n t h e a b i l i t y t o change

the e l e c t r o d e p o t e n t i a l
right a t the interface
e l e c t r o c h e m i c a l l y w i t h a h a l f - l e m o n , s c r a p e d z i n c ( s i n c e 1983) penny,
and copper w i r e a s opposed t o t h e massive Van de C r a a f f g e n e r a t o r and
e l e c t r i c power p l a n t r e q u i r e d f o r n o n - e l e c t r o c h e m i c a l approaches t o
t h e same f i e l d s t r e n g t h . I f UHV models a r e t o p r o v i d e u s e f u l molecu-
l a r - s c a l e i n s i g h t i n t o e l e c t r o c h e m i s t r y , some means o f c o n t r o l l i n g
t h e e f f e c t i v e e l e c t r o d e p o t e n t i a l o f t h e models must be d e v e l o p e d .
One approach t o p o t e n t i a l c o n t r o l i n UHV l i e s i n chemical p o i s -
i n g , r o u g h l y analogous t o p i n n i n g an i n e r t b u t c a t a l y t i c e l e c t r o d e a t
a g i v e n p o t e n t i a l by immersing i t i n a s o l u t i o n c o n t a i n i n g c o n t r o l l e d
c o n c e n t r a t i o n s o f both members o f a redox c o u p l e . To a p p l y t h i s
approach i n UHV we s u p p l y both members o f t h e redox c o u p l e a s s p e c i e s
a d s o r b e d , i n c o n t r o l l e d q u a n t i t i e s , from t h e gas phase. We then
a l l o w e q u i l i b r a t i o n t o occur.
The c l o s e r e l a t i o n between t h e work f u n c t i o n , measurable i n UHV,
and t h e e l e c t r o c h e m i c a l p o t e n t i a l has been e x p e r i m e n t a l l y demon-
s t r a t e d by Hansen and K o l b (23-24). Bange e t a l . (25) have p r e s e n t e d
a d i r e c t comparison between UHV and e l e c t r o c h e m i c a l d a t a ( t h e l a t t e r
c o r r e c t e d f o r d i f f u s e l a y e r e f f e c t s ) on t h e Br +H 0/Ag(110) system.
2 2
They found t h a t c o a d s o r p t i o n o f water w i t h B r Brought t h e UHV d a t a

i n t o good agreement w i t h e l e c t r o c h e m i c a l measurements. We c o n s i d e r
here t h e H + H 0 / P t ( l l l ) system ( i n which m o l e c u l a r H i s never p r e -
2 2 2
s e n t a s an adsorbed s p e c i e s ) . Because o f t h e extreme r e v e r s i b i l i t y

of hydrogen e l e c t r o c h e m i s t r y on P t , t h e e f f e c t i v e e l e c t r o d e p o t e n t i a l
s h o u l d be a s i n g l e - v a l u e d f u n c t i o n o f t h e amount o f hydrogen added t o
t h e water l a y e r . Our attgmpts t o measure work f u n c t i o n s were f r u s -
t r a t e d by a p e r s i s t a n t 10 fl path t o ground on o u r sample m a n i p u l a t o r
a t t h e t i m e . I n s t e a d , we w i l l i n f e r t h e e l e c t r o d e p o t e n t i a l , r e l a -
t i v e t o t h e p o t e n t i a l o f z e r o c h a r g e , from s p e c t r o s c o p i c e x a m i n a t i o n
of t h e t y p e s o f s p e c i e s p r e s e n t on t h e s u r f a c e a f t e r e q u i l i b r a t i o n .
F i g u r e 7 compares e l e c t r o c h e m i c a l and UHV data f o r hydrogen
a d s o r p t i o n on P t ( l l l ) . The s o l i d c u r v e , a, i s t h e c a t h o d i c sweep
from a c y c l i c voltammogram i n 0.3 M HF (20) a t 25 mV/s, w i t h a c o n -
s t a n t d o u b l e - l a y e r c h a r g i n g c u r r e n t s u b t r a c t e d . The voltammogram
p l o t s c u r r e n t I (charge/time) v e r s u s p o t e n t i a l V f o r a c o n s t a n t nega-
t i v e sweep r a t e (dV/dt=-ICI). The c u r r e n t i n t h i s p o t e n t i a l r e g i o n
i s g e n e r a l l y a s c r i b e d t o t h e d i s c h a r g e o f hydronium i o n s t o form

V (mV RHE)
100 30C
-200 0
A<D (mV)
F i g u r e 7. Comparison of ( a , s o l i d ) e l e c t r o c h e m i c a l and (b,

dashed) UHV measurements of t h e H . c o v e r a g e / p o t e n t i a l d i f f e r e n -
a
t i a l v e r s u s p o t e n t i a l on P t ( l l l ) . I.) c a t h o d i c sweep (25 mV/s)
voltammogram i n 0.3 M HF from Ref. 20, c o n s t a n t d o u b l e l a y e r cap-
a c i t y s u b t r a c t e d , b.) d8/d(A$) v e r s u s A$ p l o t d e r i v e d from A$
v e r s u s 8 p l o t of Ref. 26. P o t e n t i a l s c a l e s aligned a t zero cover-
age. A r e a s under c u r v e s correspond t o a.) 0.67 and b.) 0.73 H per
s u r f a c e P t atom.

adsorbed hydrogen atoms, w i t h one e l e c t r o n passed p e r hydrogen atom

adsorbed. The c u r r e n t t h e r e f o r e e q u a l s t h e t i m e d e r i v a t i v e o f t h e
hydrogen coverage 8 (-I=d8/dt). Given t h e c o n s t a n t p o t e n t i a l sweep
rate, the current i s d i r e c t l y proportional t o the potential deriva-
t i v e o f coverage (-1=-ICIdB/dV). S i n c e , once d i f f u s e l a y e r e f f e c t s
are c o r r e c t e d f o r , a change i n e l e c t r o c h e m i c a l p o t e n t i a l V i s e q u i v a -
l e n t t o a change i n work f u n c t i o n A$ ( r e f e r e n c e d t o t h e c l e a n s u r -
f a c e ) , t h e c u r r e n t can a l s o be t h o u g h t o f a s t h e work f u n c t i o n de-
r i v a t i v e o f hydrogen coverage (-I=-ICId8/d(A$)), a s noted on t h e
l e f t - h a n d v e r t i c a l a x i s o f F i g u r e 7. T h i s i n t e r p r e t a t i o n o f t h e
voltammogram a l l o w s d i r e c t comparison w i t h UHV d a t a f o r gas-phase
hydrogen a d s o r p t i o n .
The work f u n c t i o n change A$ o f P t ( l l l ) i n UHV a s a f u n c t i o n o f
hydrogen coverage B has been r e p o r t e d by Christmann e t a l . ( 2 6 ) .
Exchanging t h e i r x and y axes and t a k i n g t h e f i r s t d e r i v a t i v e y i e l d s
a -d8/dA$=f(A$) c u r v e , shown a s a dashed l i n e , b, i n F i g u r e 7, a n a l o -
gous t o t h e v o l t a m m e t r i c d a t a shown a s t h e s o l i d l i n e a Though t h e
same q u a n t i t i e s a r e p l o t t e
are q u i t e d i f f e r e n t , i n d i c a t i n
components do p l a y major r o l e s i n d e t e r m i n i n g t h e c o v e r a g e / p o t e n t i a l
r e l a t i o n s h i p f o r hydrogen e l e c t r o s o r p t i o n on P t ( l l l ) . UHV models o f
t h i s system s h o u l d c o n t a i n , a t t h e l e a s t , water coadsorbed w i t h t h e
hydrogen.
TPD and HREELS o f H„ + HÔ on P t ( l l l ) . Despite the intimations of

water e f f e c t s g i v e n by F t g u r e 7, c o a d s o r p t i o n o f hydrogen has l i t t l e
i f any e f f e c t on t h e thermal d e s o r p t i o n o f water. However, a s noted
i n t h e c a s e o f HF+HÔ, t h e lack o f a change i n water TPD does n o t
n e c e s s a r i l y i n d i c a t e a lack o f s i g n i f i c a n t i n t e r a c t i o n s . F i g u r e 8
shows t h e e f f e c t s o f an i n c r e a s i n g H~ predose on t h e HREELS spectrum
of a monolayer o f water adsorbed a t 90 K and t h e n f l a s h e d t o 150 K
(Wagner, F.T. and Moylan, T.E. S u r f a c e S c i . , s u b m i t t e d ) . F o r H«
doses below 0.65 L no new peaks ( i n a d d i t i o n t o t h e w a t e r - a l o n e
modes) a r e seen. T h i s i s not s u r p r i s i n g i n l i g h t o f t h e v e r y weak
HREELS f e a t u r e s produced by H.alone on P t ( l l l ) ( 2 7 ) . Above 0.65 L a
new peak grows i n a t 1150 cm" , s i m i l a r t o t h e peak seen f o r water
c o a d s o r p t i o n w i t h HF and o t h e r m i n e r a l a c j d s ; we a g a i n a s s i g n t h i s
peak t o t h e symmetric bending mode o f HÔ . U n l i k e t h e c a s e f o r HF •
HgO, no r e a c t i o n i s seen a t 100 K. F i g u r e 8 t h u s g i v e s e v i d e n c e f o r
a k i n e t i c a l l y hindered r e a c t i o n
H H H + e
a d s * 2°ads > 3°*ads "metal
which proceeds a t 150 K when t h e i n i t i a l hydrogen coverage exceeds
~20fl o f s a t u r a t i o n , b u t not a t lower hydrogen c o v e r a g e s . Note t h a t
both r e a c t a n t s and p r o d u c t s a r e f o r m a l l y reduced one e l e c t r o n w i t h
r e s p e c t t o water on an uncharged metal s u r f a c e .
The above r e a c t i o n y i e l d s an adsorbed c a t i o n which has weak
s p e c i f i c i n t e r a c t i o n s w i t h t h e s u r f a c e . The p r e s e n c e o f t h i s c a t i o n
i n t h e absence o f c h a r g e - b a l a n c i n g a n i o n s (such a s F" i n t h e HF+HÔ
case) t h u s i n d i c a t e s t h a t t h e s u r f a c e i s a t an e f f e c t i v e p o t e n t i a l
below t h e p o t e n t i a l o f z e r o charge ( p z c ) , i . e . , t h e c o u n t e r c h a r g e
r e s i d e s i n t h e m e t a l . The lack o f r e a c t i o n f o r i n i t i a l hydrogen
c o v e r a g e s below ~20% o f s a t u r a t i o n s u g g e s t s t h a t t h e e f f e c t i v e p o t e n -
t i a l o f t h e w a t e r - o n l y monolayer l i e s above t h e p z c , i . e . , where t h e

Loss Energy (1/cm)

400 1200 2000 2800 3600
200 300 400 500

Loss Energy (mV)
F i g u r e 8. HREELS s p e c t r a a t 90 K o f coadsorbed l a y e r s f l a s h e d t o
150 K showing e f f e c t o f i n c r e a s i n g predose, a l l xlOO: a.) 1 . 4 L
H 0; b.) 0.3 L H + 1 . 4 L H 0 ; c.) 0765 L H„ + 1 . 4 L H 0 ; d.) 1 L
o 0 o o
H* • 1 . 4 L H 0 ; §.) 2.5 L
2 1 . 4 L HgO; f f ) 10 L H i 1 4 L H 0 .
2 2
net c h a r g e on t h e metal i s p o s i t i v e . To form an e q u i l i b r i u m l a y e r

i n c l u d i n g adsorbed c a t i o n s one must add s u f f i c i e n t r e d u c i n g agent t o
s h i f t t h e p o t e n t i a l f i r s t down t o , and then p a s t , t h e p z c .
Comparison w i t h room-temperature electrochemistry
The UHV d a t a s u g g e s t t h a t 2 0 % o f s a t u r a t i o n hydrogen atom coverage

must be added t o t h e water monolayer t o s h i f t t h e p o t e n t i a l below t h e
pzc. E l e c t r o n s can be added t o t h e i n t e r f a c e e i t h e r by a d s o r p t i o n o f

t h e r e d u c i n g agent hydrogen or by passage of charge through an e x t e r -

nal c i r c u i t ; a f t e r e q u i l i b r a t i o n both methods of r e d u c t i o n s h o u l d
produce t h e same i n t e r f a c e p r o v i d e d t h e same number of e l e c t r o n s a r e
added. To form one hydrogen atom by r e d u c t i o n of b u l k water (or
HLO ) , one e l e c t r o n must be added t o t h e e l e c t r o d e from t h e e x t e r -
nal c r r c u i t . The gas-phase a d d i t i o n of 20% of t h e 0.73 H/Pt UHV
s a t u r a t i o n hydrogen converage i s t h u s e q u i v a l e n t t o t h e a d d i t i o n of
35 pQ/cm of c a t h o d i c charge t o t h e P t ( l l l ) / 0 . 3 M HF i n t e r f a c e .
I f one i n t e g r a t e s t h e area between t h e voltammogram i n F i g u r e 7a
and t h e d o u b l e - l a y e r c o r r e c t e d z e r o c u r r e n t l i n e , s t a r t i n g f r o m £he
o n s e t o f hydrogen a d s o r p t i o n a t 0.34 V RHE, one reaches 35 pC/cm a t
a p o t e n t i a l of 0.22 V RHE. To t h e as y e t undetermined e x t e n t t h a t
t h e low t e m p e r a t u r e UHV data i s r e p r e s e n t a t i v e of r e a l e l e c t r o c h e m -
i c a l c o n d i t i o n s , t h i s r e s u l t s u g g e s t s t h a t t h e pzc of P t ( l l l ) l i e s a t
0.22 V RHE. I t s h o u l d be noted t h a t t h i s q u a n t i t a t i v e comparison
between UHV hydrogen dosage and e l e c t r o c h e m i c a l charge i s not a f f e c -
t e d by t h e p e r c e n t a g e of H and (H«0 • e" ) p a i r s on t h e
equilibrated surface; what
e q u i v a l e n t s added t o t h
The proposed p o s i t i o n of t h e pzc l i e s j u s t a t t h e a n o d i c end of
t h e unusual b r o a d , f l a t s e c t i o n ( p e c u l i a r t o w e l l - o r d e r e d P t ( l l l ) ) of
t h e hydrogen e l e c t r o s o r p t i o n r e g i o n . T h i s f l a t s e c t i o n would then
c o r r e s p o n d t o t h e c o a d s o r p t i o n of HÔ and H; r e p u l s i o n s between
charged H~Q groups c o u l d h e l p e x p l a i n why a s t r u c t u r a l l y u n i f o r m
s u r f a c e can produce such a broad e l e c t r o s o r p t i o n peak. The s l o p i n g
s e c t i o n of t h e voltammogram above 0.22 V would c o r r e s p o n d t o a d s o r p -
t i o n of H a l o n e . A somewhat s i m i l a r i n t e r p r e t a t i o n was advanced by
Bewick and R u s s e l l ( 2 8 ) , based on EMIRS d a t a , f o r t h e low and h i g h
p o t e n t i a l main peaks i n t h e voltammogram of p o l y c r y s t a l l i n e P t i n
a c i d . They a s c r i b e d t h e low p o t e n t i a l peak t o hydrogen s t r o n g l y
a s s o c i a t e d w i t h w a t e r , w h i l e t h e h i g h p o t e n t i a l hydrogen gave no
evidence f o r strong a s s o c i a t i o n .
A w a t e r - a l o n e monolayer p o t e n t i a l above t h e pzc i s i n a c c o r d a n c e
w i t h an a b s o l u t e work f u n c t i o n measurement f o r t h e water monolayer on
P t ( l l l ) of 4.8 eV ( 2 9 ) . Comparing t h i s t o t h e hydrogen e l e c t r o d e
(4.7 eV below vacuum (30) f o r t h e normal hydrogen e l e c t r o d e NHE)
c o r r e c t e d by 7x0.059 V f o r a nominal pH 7 y i e l d s a w a t e r - a l o n e mono-
l a y e r p o t e n t i a l of +0.5 V vs. RHE a t pH 7. T h i s l i e s 0.3 V above our
proposed pzc of 0.2 V RHE. This r e l a t i v e l y high apparent p o t e n t i a l
of t h e water monolayer has been noted p r e v i o u s l y (Sass, J.K., p r i v a t e
c o m m u n i c a t i o n ) , and has r a i s e d concern about t h e r e l e v a n c e of t h e UHV
monolayer t o r e a l e l e c t r o c h e m i c a l c o n d i t i o n s , s i n c e most e l e c t r o c h e m -
i c a l measurements of t h e pzc of p o l y c r y s t a l l i n e P t have been c l o s e r
t o 0.2 V than t o 0.5 V (31). By showing t h a t t h e water monolayer
l i e s above, not a t , t h e pzc, t h e p r e s e n t Ho+HÔ data remove p a r t of
t h e a p p a r e n t d i s c r e p a n c y between t h e e l e c t r o c h e m i c a l and UHV r e s u l t s .
I f f u t u r e UHV work f u n c t i o n data show a l a r g e (~0.3 V) d e c r e a s e i n
t h e water monolayer work f u n c t i o n upon a d d i t i o n of s m a l l « 2 0 % s a t u -
r a t i o n ) amounts of hydrogen, a l l of t h e a p p a r e n t d i s c r e p a n c y c o u l d be
q u a n t i t a t i v e l y accounted f o r .
Conclusions: R o l e s f o r c r y o g e n i c UHV model d o u b l e l a y e r s
We have g i v e n examples of how t h e e f f e c t s of an aqueous e n v i r o n -

ment can be s t u d i e d i n UHV, how s o l v a t e d i o n i c s p e c i e s can be added

t o t h a t environment, and how t h e e f f e c t i v e e l e c t r o d e p o t e n t i a l can be

c o n t r o l l e d . Thus, t h e e s s e n t i a l f e a t u r e s o f t h e e l e c t r o c h e m i c a l
d o u b l e l a y e r can be reproduced i n UHV a t low s u r f a c e t e m p e r a t u r e s .
However, a b a s i c q u e s t i o n remains: why s h o u l d t h e e l e c t r o c h e m i s t be
i n t e r e s t e d i n model double l a y e r s when t h e r e a l t h i n g can be s o s i m -
p l y g e n e r a t e d by p l u n k i n g an e l e c t r o d e i n t o a l i q u i d e l e c t r o l y t e ?
UHV models o f f e r two advantages: (1) c o n t r o l o f i n t e r f a c i a l param-
e t e r s f a r more p r e c i s e than t h a t which can be a c h i e v e d i n l i q u i d , and
(2) d e t a i l e d a n a l y s i s o f f u l l y s o l v a t e d s p e c i e s by a h o s t o f comple-
mentary s u r f a c e s p e c t r o s c o p i e s , a l l a p p l i c a b l e t o t h e e x a c t same
s u r f a c e . I n t h e s t a n d a r d e l e c t r o c h e m i c a l e x p e r i m e n t we c o n t r o l t h e
e l e c t r o d e p o t e n t i a l and t h e b u l k c o n c e n t r a t i o n o f e l e c t r o l y t e spe-
c i e s . The c o n c e n t r a t i o n s o f a l l adsorbed s p e c i e s a r e n o t d i r e c t l y
c o n t r o l l e d and a r e o f t e n d i f f i c u l t o r i m p o s s i b l e t o measure, and t h e
p o s s i b i l i t y o f u n c o n t r o l l e d s u r f a c e i m p u r i t i e s i s always l u r k i n g i n
t h e background. I n t h e UHV model we d i r e c t l y c o n t r o l t h e amount o f
adsorbed s p e c i e s by c o n t r o l l e d d o s i n g from t h e gas phase; t h e depen
dent v a r i a b l e ( t h e p o t e n t i a l
t i o n . A f t e r a given compositio
p o s t u l a t e d , we can p r e p a r e t h a t c o m p o s i t i o n i n UHV, t r a n s f e r i t t o an
e l e c t r o c h e m i c a l c e l l , and s e e i f i t behaves as e x p e c t e d . Working
w i t h c r y o g e n i c model d o u b l e l a y e r s grown i n UHV, we have a v a i l a b l e
" i n s i t u " ( i . e . , w i t h d o u b l e l a y e r and s o l v e n t p r e s e n t ) measurements
of s u r f a c e s t r u c t u r e , elemental c o m p o s i t i o n , e l e c t r o n i c s t r u c t u r e ,
o x i d a t i o n s t a t e , and m o l e c u l a r c o n n e c t i v i t y (through v i b r a t i o n a l and
ion s p e c t r o s c o p i e s ) . A l l o f t h e s e t e c h n i q u e s can be a p p l i e d t o t h e
same s u r f a c e , w h i l e i n s i t u t e c h n i q u e s f o r normal spectroelectrochem-
i s t r y r e q u i r e a myriad o f s p e c i a l i z e d , o f t e n m u t u a l l y e x c l u s i v e ,
e l e c t r o d e forms and c e l l d e s i g n s .
N e v e r t h e l e s s , t h e c r y o g e n i c UHV models remain models, t h e r e l e -
vance o f which t o r e a l e l e c t r o c h e m i s t r y remain i n c o m p l e t e l y e s t a b -
l i s h e d . We can g e n e r a t e a_n e x t e n s i v e I y hydrated i o n i c environment i n
UHV, b u t i s i t t h e c o r r e c t one? Grounds f o r o p t i m i s m on t h i s p o i n t
have been demonstrated i n R e f . 25 and d i s c u s s e d l e s s c o n c r e t e l y i n
Ref. 3. Frozen e l e : t r o l y t e work (2) has demonstrated c o n s i d e r a b l e
m e c h a n i s t i c c o n t i n u i t y between normal e l e c t r o c h e m i s t r y and e l e c t r o -
c h e m i s t r y i n a p e r c h l o r i c a c i d h y d r a t e a t t e m p e r a t u r e s down t o 150 K,
but how general i s t h i s r e s u l t ?
A t t a i n m e n t o f complete answers w i l l r e q u i r e c o o r d i n a t e d a p p l i c a -
t i o n o f (1) s o l v a t e d , c r y o g e n i c UHV models, (2) t r u e i n s i t u s p e c t r o -
s c o p i e s under r e a l i s t i c c o n d i t i o n s , and (3) U H V - e l e c t r o c h e m i c a l
t r a n s f e r e x p e r i m e n t s . As non-UHV t e c h n i q u e s f o r g e n e r a t i n g c l e a n ,
w e l l - o r d e r e d e l e c t r o d e s u r f a c e s a r e developed (19) and v a l i d a t e d w i t h
UHV work ( 2 0 ) , h i g h - q u a l i t y i n s i t u s p e c t r o e l e c t r o c h e m i c a I data on
s i n g l e c r y s t a l s w i l l p r o v i d e d i r e c t p o i n t s o f comparison f o r UHV
model s t u d i e s . U H V - e l e c t r o c h e m i c a l t r a n s f e r e x p e r i m e n t s p r o v i d e a
means o f a p p l y i n g vacuum s u r f a c e s p e c t r o s c o p i e s t o r e a l electrochem-
i c a l , a l b e i t emersed and e v a c u a t e d , i n t e r f a c e s . A growing body o f
data (23-24) shows t h a t , a t l e a s t i n some c a s e s , emersion and evacu-
a t i o n do n o t d e s t r o y t h e dominant c h e m i s t r y o f t h e i n t e r f a c e . C r y o -
g e n i c UHV model work, by i d e n t i f y i n g i n which systems water e f f e c t s
a r e important and i n which they a r e not, can h e l p e s t a b l i s h t h e c a s e s
where ex s i t u UHV s p e c t r o s c o p i c data a r e t r u l y r e p r e s e n t a t i v e o f t h e
o r i g i n a l e l e c t r o c h e m i c a l i n t e r f a c e . S y n e r g i s t i c use o f t h e s e t h r e e
approaches s h o u l d p r o v i d e t h e hard, m o l e c u l a r - s c a l e , data needed t o

d e t e r m i n e t h e t r u e b a l a n c e between chemical and e l e c t r o s t a t i c e f f e c t s

a t e l e c t r o c h e m i c a l i n t e r f a c e s , and t o r e f i n e o u r p r e v i o u s , l a r g e l y
e l e c t r o s t a t i c s - b a s e d , views o f t h e d o u b l e l a y e r .
Literature Cited
1. Thiel, P. A . ; Madey, T. E. Surface S c i . Rept. 1987, 7, 211.

2. Frese, U . ; Stimming, U. J . Electroanal. Chem. 1986, 198, 409.
3. Wagner, F. T.; Moylan, T. E. Surface S c i . 1987, 182, 125.
4. Wagner, F. T.; Moylan, T. E. Surface S c i . 1987, 191, 121.
5. Wagner, F. T.; Moylan, T. E . ; Schmieg, S. J . Surface S c i . 1988,
195, 403.
6. King, R. B . ; Ackermann, M. N. J . Organomet. Chem. 1973, 67, 431.
7. Eisenberg, R.; Hendriksen, D. E. In Advances in Catalysis; Eley,
D. D.; Pines, H . ; Weisz, P. B . , Eds.; Academic: New York, 1979;
Vol. 28, p 87.
8. Mate, C. M.; Somorjai G A Surface S c i 1985 160 542
9. DeLouise, L. A . ; Winograd
10. Poelsema, B . ; Verheij
49, 1731.
11. Gilman, S. J . Phys. Chem. 1964, 68, 70.
12. Banholzer, W. F . ; Park, Y. O.; Mak, K. M.; Masel, R. I . Surface
S c i . 1983, 128, 176; R.I. Masel, private communication.
13. Taylor, R. C.; Vidale, G. L. J . Am. Chem. Soc. 1956, 78, 5999.
14. Savoie, R.; Giguere, P. A. J . Chem. Phys. 1964, 41 2698.
15. Ferriso, C. C.; Hornig, D. F. J . Chem. Phys. 1964, 41, 2698.
16. Falk, M.; Giguere, P. A. Can. J . Chem. 1957, 35, 1195.
17. Myers, R. T. J . Chem. Educ. 1976, 53, 17.
18. Bockris, J . O'M.; Reddy, A. K. N. Modern Electrochemistry;
Plenum: New York, 1977; p 131.
19. C l a v i l i e r , J.; Faure, R.; Guinet, G.; Durand, R. J . Electroanal.
Chem. 1983, 150, 141.
20. Wagner, F. T.; Ross, P. N. Jr. J . Electroanal. Chem. 1983, 150,
141; J . Electroanal. Chem., submitted.
21. Ref. 18, chap. 7.
22. Cady, G. H . ; Hildebrand, J . H. J. Am. Chem. Soc. 1930, 52, 3843.
23. Hansen, W. N . ; Kolb, D. M. J. Electroanal. Chem. 1979, 100, 493.
24. Kolb, D. M. Z. Phys. Chem. (N.F.) 1987, 154, 179.
25. Bange, K . ; Straehler, B . ; Sass, J . K . ; Parsons, R. J . Electro-
anal. Chem. 1987, 229, 87.
26. Christmann, K . ; Ertl, G.; Pignet, T. Surface S c i . 1976, 54, 365.
27. Baro, A. M.; Ibach, H . ; Bruchmann, H. D. Surface S c i . 1979, 88,
384.
28. Bewick, A . ; Russell, J . W. J . Electroanal. Chem. 1982, 132, 329.
29. Fisher, G. B. GMR-4007; GM Research Labs: Warren, MI, 1982.
30. Gomer, R.; Tryson, G. J . Chem. Phys. 1977, 66, 4413.
31. Frumkin, A. N. Petry, O. A. Electrochim. Acta 1970, 15, 391.

Chapter 6
Aromatic Polymerization on Metal Surfaces
Jay B. Benziger, N. Franchina, and G. R. Schoofs
Department of Chemica
Thin polymer films have been prepared by surface

catalysis in ultrahigh vacuum and electrochemical
deposition from solution. These two routes of synthesis
result in poly(thiophene), poly(aniline) and poly(3,5-
lutidine) films that have similar infrared spectra. These
polymer films are highly orientationally ordered; the
rings are perpendicular to the surface in
poly(thiophene) and poly(3,5-lutidine) films, and the
phenyl rings are parallel to the surface in poly(aniline).
Both the catalytic and electrochemical polymerization
reactions appear to result from electron donation from
the aromatic species to the surface producing a radical
cation that leads to electrophilic addition.
A variety of aromatic compounds can be polymerized
electrochemically to form a thin polymer filmfl -41. Many films
involving heteroatom aromatics can be made electrically conducting
or insulating through oxidation and reduction^-81. There has been
a great deal of interest in films of poly(aniline), poly(thiophene)
and poly(pyrrole) because they can be made electrically conducting,
are easily synthesized, and are fairly robust . Polymer films of
aniline, thiophene and pyrrole are readily formed on platinum
electrodes by anodic oxidation of the monomer from a solution of a
polar organic solvent, such as acetonitrilefl .21. As formed these
polymer films have associated anions and are conducting. They may
be removed from solution stored in air and used in a wide variety of
electrolyte solutions [2^9].
Polymer films may also be synthesized by direct chemical
routes[1QJ. These chemical synthesis routes generally involve some
form of electrophilic substitution using Grignard reagents or other
modified precursors. The purity and electrical properties of the
films produced from the chemical route are generally poorer than
the films produced electrochemically, but the chemical synthesis
0097-6156/88/0378-0083$06.00/0
c

routes provide insight into how the films are formed

electrochemically. Our recent investigations of the
interactions o f heteroatom species w i t h w e l l defined n i c k e l surfaces
indicated that monolayers of heteroatom aromatic compounds
adsorbed on atomically clean nickel single crystals
p o l v m e r i z e r i 1.121. F u r t h e r m o r e , it was f o u n d that s e v e r a l o f these
p o l y m e r s w e r e o r i e n t a t i o n a l l y o r d e r e d r e l a t i v e to the s u r f a c e . This
s u g g e s t s a t h i r d route f o r s y n t h e s i z i n g a r o m a t i c p o l y m e r f i l m s , a n d
suggests that it m a y be p o s s i b l e to p r o d u c e h i g h l y o r d e r e d f i l m s .
I n t h i s p a p e r w e d e s c r i b e the p r e p a r a t i o n o f t h i n p o l y m e r
f i l m s b y surface c a t a l y s i s and a n o d i c d e p o s i t i o n . T h e results i n d i c a t e
that b o t h s y n t h e s i s routes p r o d u c e o r i e n t a t i o n a l l y o r d e r e d f i l m s that
have s i m i l a r infrared spectra. It is a l s o s h o w n that t h i n o r d e r e d
films of poly(thiophene) have different electrochemical behavior
than the f i b r o u s f i l m s that are e l e c t r i c a l l y c o n d u c t i n g .
Experimental
P o l y m e r films were produce

and N i ( l l l ) s i n g l e crystals i n a standard U H V v a c u u m system ["12.131.
T h e surfaces w e r e a t o m i c a l l y c l e a n as d e t e r m i n e d f r o m l o w e n e r g y
e l e c t r o n d i f f r a c t i o n ( L E E D ) and A u g e r e l e c t r o n s p e c t r o s c o p y (AES).
M o n o m e r w a s a d s o r b e d o n the n i c k e l s u r f a c e s c i r c a 150 K a n d
r e a c t i o n w a s i n d u c e d b y r a i s i n g the t e m p e r a t u r e . Surface species
were characterized by temperature programmed reaction (TPR),
reflection infrared spectroscopy, and A E S . Molecular orientations
w e r e i n f e r r e d f r o m the s u r f a c e d i p o l e s e l e c t i o n r u l e o f r e f l e c t i o n
infrared spectroscopy. The selection rule indicates that only
m o l e c u l a r v i b r a t i o n s w i t h a d y n a m i c d i p o l e n o r m a l to the surface
w i l l be i n f r a r e d a c t i v e f 1 4 1 . thus f o r a r o m a t i c m o l e c u l e s the absence
o f a C = C stretch or a r i n g v i b r a t i o n m o d e indicates the r i n g must be
p a r a l l e l the surface.
Polymer films were produced by anodic deposition by
potentiostatic d e p o s i t i o n onto a p l a t i n u m electrode. D e p o s i t i o n was
done from 1 M s o l u t i o n s o f the m o n o m e r i n 1 M L i C 1 0 4 i n a c e t o n i t r i l e .
T h e films were characterized by c y c l i c v o l t a m m e t r y and reflection
i n f r a r e d s p e c t r o s c o p y i n an apparatus d e s c r i b e d e l s e w h e r e [15].
Results
Thiophene. T h e first e x a m p l e o f surface c a t a l y z e d p o l y m e r i z a t i o n w e

observed was the formation of thiophene o l i g i m e r s on a clean
N i ( l l l ) surface [11]. T h e T P R results s u m m a r i z e d i n F i g u r e 1
i n d i c a t e d m o l e c u l a r fragments w i t h f i v e and m o r e c a r b o n s (up to C 8
fragments were detected) from thiophene reacting on Ni(lll).
These intermediates decomposed over a wide temperature range,
approximately 400 K . T h e existence o f products w i t h m o r e than four
carbons indicated that dimers and other o l i g i m e r s were being
formed. F u r t h e r m o r e , the b r o a d t e m p e r a t u r e r a n g e f o r d i h y d r o g e n
e v o l u t i o n r e s u l t i n g f r o m d e c o m p o s i t i o n is s u g g e s t i v e o f a w i d e range
o f surface s p e c i e s . T h e b r o a d range o f d e c o m p o s i t i o n temperatures
was also observed by Zaera et al for thiophene reacting on
N i ( 1 0 0 ) [ l _ 6 ] , and by L a n g and M a s e l on Pt (111), (100) and (210) [17.].
A series of infrared spectra taken after adsorption and
s u b s e q u e n t h e a t i n g o f t h i o p h e n e o n N i ( l l l ) are s h o w n i n F i g u r e 2 .
A t the i n i t i a l a d s o r p t i o n temperature o f 170 K the i n f r a r e d s p e c t r u m

6. BENZIGERETAL. Aromatic Polymerization on Metal Surfaces 85
i i i i i i i i i *
2oo 400 600 800 1000
Temperature (K)
Figure 1. Temperature Programmed Reaction Spectra of Thiophene on Ni(111)

1400 1600 1800
Wavenumber (cm 1
)
Figure 2. Reflection infrared spectra of thiophene films (a) thiophene adsorbed
on Ni(111) at 170 K (b) thiophene adsorbed on Ni(111) at 170 K heated to
320 K (c) electrochemically grown poly(thiophene) on Pt

6. BENZIGERETAL. Aromatic Polymerization on Metal Surfaces 87
was featureless. A f t e r h e a t i n g to 3 2 0 K the infrared spectrum

s h o w e d the p r e s e n c e o f C H s t r e t c h i n g m o d e s b e t w e e n 2 8 0 0 a n d 3 1 0 0
c m ~ l , a n d C = C stretching modes at 1 5 2 0 a n d 1495 c m " * . T h e s e results
i n d i c a t e that the t h i o p h e n e w a s w i t h the r i n g p a r a l l e l t o the surface
b e l o w 2 0 0 K . A t 3 2 0 K the thiophene h a d reacted to f o r m a m o l e c u l a r
e n t i t y w i t h v i b r a t i o n a l m o d e s n o r m a l to the s u r f a c e . W e suggest
these c h a n g e s r e s u l t f r o m the s u r f a c e p o l y m e r i z a t i o n o f t h i o p h e n e .
A t t h e l o w t e m p e r a t u r e the t h i o p h e n e c a n n o t react, a n d i t p i - b o n d s
to the surface. W e have carried out extended H u c k e l calculations for
t h i o p h e n e a d s o r b e d o n a 19 a t o m N i c l u s t e r a n d f o u n d that a flat
c o n f i g u r a t i o n w i t h the thiophene r i n g 2.6 A above the surface w a s
the most s t a b l e c o n f i g u r a t i o n [see r e f . 18 f o r d e t a i l s o f t h e
computational technique]. T h e flat o r i e n t a t i o n w a s also o b s e r v e d b y
Sexton for thiophene o n Cu(100) [19], w h i c h is consistent w i t h o u r
o b s e r v a t i o n s that a r o m a t i c m o l e c u l e s t e n d t o b o n d f l a t o n m e t a l
surfaces.
A s the temperatur raised th thiophen reacted with
both structural and orientationa
s h o w the f o r m a t i o n o
i n d i c a t e the p o l y m e r m u s t h a v e C H and C = C b o n d s p e r p e n d i c u l a r t o
the surface. Z a e r a et a l f l 61 h a v e r e p o r t e d v i b r a t i o n a l s p e c t r a t a k e n
with electron energy loss spectroscopy for thiophene reacting o n a
Ni(100) surface. T h e i r spectra agree w i t h the i n f r a r e d spectra
r e p o r t e d h e r e , e x t e n d i n g the f r e q u e n c y range to b e l o w 1 0 0 0 c m " * .
B e t w e e n 9 0 a n d 185 K they o b s e r v e a c h a n g e i n the E E L s p e c t r u m
i n d i c a t i n g a surface r e a c t i o n o f t h i o p h e n e . T h e resulting absorption
b a n d s are c o m p a r e d to the a b s o r p t i o n b a n d s o f t h e t w o i s o m e r s o f
poly(thiophene) i n Table I.
Table I
Vibrational Bands o f Thiophene Derivatives
C4H4S/Ni(100)* poly(2,5-thienylene)** poly(2,4-thienylene)* *
3025 3090 C - H stretch
1450 1490 1475 C = C stretch

1408
1340 1230 1320 vcycle
1150 1170 vcycle
1070 1052 C - H i n plane

bend
850 788 820 C - H out o f

730 plane bend
* from ref. Ijg

* * from ref. 2£

There is r e m a r k a b l e agreement between the b a n d s f r o m thiophene

reacting on Ni(100) with a m i x e d isomeric form of poly(thiophene).
Furthermore, Zaera et al observed that the absorption bands all
gradually d i m i n i s h e d i n intensity between 220 and 600 K w i t h the
e v o l u t i o n o f h y d r o g e n , w h i c h is characteristic o f p o l y m e r degradation.
Z a e r a et a l attributed t h e i r results to a m e t a l l o c y c l e o n the surface. We
b e l i e v e that s u r f a c e p o l y m e r i z a t i o n o f t h i o p h e n e i s a m o r e reasonable
e x p l a n a t i o n o f the e x p e r i m e n t a l r e s u l t s f o r the f o l l o w i n g r e a s o n s : (i)
C5+ desorption products were observed; ( i i ) the broad temperature
r a n g e f o r d e c o m p o s i t i o n ; ( i i i ) the a g r e e m e n t o f the i r b a n d s b e t w e e n
t h i o p h e n e o n N i ( 1 0 0 ) a n d the i s o m e r s o f p o l y ( t h i o p h e n e ) ; a n d ( i v ) N i
catalysts are k n o w n to c a t a l y z e p o l y m e r i z a t i o n o f t h i o p h e n e in the
a b s e n c e o f h y d r o g e n \211. T h e absence o f s u l f u r c o n t a i n i n g o l i g i m e r s
a m o n g the d e s o r p t i o n p r o d u c t s is d i f f i c u l t to a c c o u n t f o r , and m a y be
the r e s u l t o f the p o l y ( t h i o p h e n e ) b o n d i n g to the s u r f a c e t h r o u g h the
sulfur atoms.
Poly(thiophene) film
potentiostatically from 1 M
Ag/AgCl(lM). The film
s o l u t i o n and p l a c e d i n 1 M L 1 C I O 4 / C H 3 C N and c y c l e d between 0 V to 2.0 V
v s . A g / A g C I to test f o r the p r e s e n c e o f p o l y m e r f i l m s . A t deposition
potentials below 1.74 V no f i l m deposition was detected, at higher
p o t e n t i a l s the f i l m s d e p o s i t i o n rate w a s m o r e r a p i d a n d n o t r e a d i l y
controlled. F o r short d e p o s i t i o n t i m e s (< 5 s) an o r a n g e - g o l d f i l m w a s
d e p o s i t e d o n the P t e l e c t r o d e . A s s u m i n g a two electron transfer per
t h i o p h e n e m o l e c u l e grafted o n t o the surface the d e n s i t y o f the g o l d f i l m
is ~ 2 x 10*5 molecules/cm^. C y c l i n g this f i l m i n e l e c t r o l y t e c a u s e d n o
change i n the c o l o r o f the f i l m . There is also very little d o p i n g
(incorporation o f perchlorate a n i o n ) i n t o the f i l m ; the t h i n orange-
g o l d f i l m c a n be d o p e d to <5% w i t h the p e r c h l o r a t e i o n . Increasing
deposition times resulted i n thicker black films. C y c l i n g these f i l m s i n
e l e c t r o l y t e s h o w e d these f i l m s c o u l d be o x i d i z e d ( d o p e d ) a n d reduced
( u n d o p e d ) as i n d i c a t e d b y the v o l t a m m o g r a m . In the r e d u c e d f o r m the
f i l m s appeared a dark red. T h e s e t h i c k e r f i l m s c o u l d be d o p e d w i t h
p e r c h l o r a t e i o n , w i t h the d o p i n g l e v e l i n c r e a s i n g w i t h i n c r e a s i n g film
t h i c k n e s s up to a m a x i m u m d o p i n g l e v e l o f a p p r o x i m a t e l y 2 5 % .
A reflection infrared spectrum of the anodically deposited
o r a n g e - g o l d f i l m i s s h o w n i n F i g u r e 2. T h e electrochemically deposited
p o l y ( t h i o p h e n e ) f i l m has an i n f r a r e d s p e c t r u m that i s v e r y s i m i l a r to
that o b t a i n e d f r o m the f i l m f o r m e d c a t a l y t i c a l l y o n N i ( l l l ) , suggesting
a c o m m o n structure. S o m e d i f f e r e n c e s i n the r a t i o o f p e a k intensities
are seen w h i c h m a y be due to d i f f e r e n c e s i n the i s o m e r i c f o r m s o f the
polymers. It w a s a l s o f o u n d that the c a t a l y t i c a l l y p r e p a r e d f i l m can
o n l y be g r o w n to m o n o l a y e r t h i c k n e s s . A d s o r p t i o n o f thiophene on a
Ni(lll) surface with a poly(thiophene) film results in thiophene
desorption during temperature programmed heating, no additional
p o l y m e r i z a t i o n w a s detected. R e f l e c t i o n spectra o f the t h i c k b l a c k f i l m s
formed electrochemically could not be obtained as they lacked
sufficient reflectivity.
S u r f a c e p o l y m e r i z a t i o n o f t h i o p h e n e s w a s f o u d to be affected b y
both surface i m p u r i t i e s and substituent g r o u p s o n the t h i o p h e n e ring.
T h e r e a c t i o n s o f t h i o p h e n e o n a N i ( l l l ) surface w i t h s u l f u r i m p u r i t i e s
was e x a m i n e d [11]. T h e s u l f u r i n h i b i t e d the p o l y m e r i z a t i o n so that the
only reactions observed were desorption o f thiophene with a small

6. BENZIGER ET AL. Aromatic Polymerization on Metal Surfaces 89
amount o f decomposition. T h i o p h e n e p o l y m e r i z a t i o n w a s also f o u n d to

be i n h i b i t e d o n d i r t y p l a t i n u m e l e c t r o d e s . It was o b s e r v e d that w i t h o u t
r i g o r o u s c l e a n i n g o f the p l a t i n u m e l e c t r o d e b e f o r e i m m e r s i o n i n t o the
thiophene solution higher potentials w e r e r e q u i r e d to o b t a i n t h i o p h e n e
p o l y m e r i z a t i o n , a n d the rate o f p o l y m e r f o r m a t i o n w a s g r e a t l y reduced.
No polymerization of 2,5-dimethylthiophene was observed either
c a t a l y t i c a l l y o n the N i ( l l l ) surface [ 1 1 ] , o r e l e c t r o c h e m i c a l l y o n a P t
electrode.
Aniline. A n i l i n e b l a c k is a w e l l k n o w n p o l y m e r o f a n i l i n e f o r m e d b y
electrophilic a d d i t i o n ^ .41. Numerous investigators have formed
poly(aniline) films by anodic deposition o f Pt and other electrode
materials. W e h a v e e x a m i n e d the i n t e r a c t i o n o f a n i l i n e w i t h c l e a n
N i ( l l l ) and N i ( 1 0 0 ) surfaces i n u l t r a h i g h v a c u u m and f o u n d a n i l i n e to
form an orientationally ordered, thermally stable polymer film.
Electrochemically prepared poly(aniline) films also show the high
degree o f orientational ordering
The evidence fo
combination of T P R , A E
a n i l i n e o n N i ( l l l ) are s u m m a r i z e d i n F i g u r e 3. After adsorption of
a n i l i n e at 170 K a n i l i n e and d i h y d r o g e n d e s o r b at 2 4 0 K . Dihydrogen,
a m m o n i a , H C N and v a r i o u s h y d r o c a r b o n p r o d u c t s are f o u n d to e v o l v e at
1000 K . T h e s e results i n d i c a t e a t h e r m a l l y v e r y stable surface s p e c i e s .
T h e A u g e r s p e c t r a d i d not c h a n g e w i t h t e m p e r a t u r e b e t w e e n 3 0 0 K and
800 K , w i t h the c a r b o n l i n e s h a p e b e i n g i n d i c a t i v e o f a m o l e c u l a r e n t i t y
[22.], and a m o l e c u l a r c o v e r a g e o f a n i l i n e based o n the C ( K L L ) / N i ( L M M )
1 5 2
and N ( K L L ) / N i ( L M M ) ratios o f 1.5 x 1 0 molecules/cm . T h e infrared
s p e c t r u m o f a n i l i n e adsorbed o n N i ( l l l ) at 165 K s h o w n i n F i g u r e 4 is
a l m o s t i d e n t i c a l to l i q u i d a n i l i n e , i n d i c a t i n g a f r o z e n m u l t i l a y e r . After
h e a t i n g to 4 0 0 K the i n f r a r e d s p e c t r u m s h o w s n o r i n g v i b r a t i o n m o d e s
1 1
i n the 1 3 5 0 - 1 8 5 0 c m " range, and no C H stretches around 3 0 0 0 c m " ; an
1
N H stretch at 3 2 0 0 c m ' is evident i n the spectrum.
T h e A E S results i n d i c a t e that the a n i l i n e c o v e r a g e i s m o r e t h a n
t w o t i m e s greater t h a n the m a x i m u m c o v e r a g e b a s e d o n v a n der W a a l s
radii. T h e T P R results s h o w this species is too stable to be a c o n d e n s e d
multilayer. H e n c e , w e c o n c l u d e that a n i l i n e p o l y m e r i z e d f o r m i n g a
v e r y stable p o l y m e r l a y e r . In a d d i t i o n , the absence o f i n f r a r e d b a n d s
corresponding to C = C s t r e t c h e s o r r i n g v i b r a t i o n s i n d i c a t e d that the
p o l y ( a n i l i n e ) f i l m was f o r m e d w i t h the p h e n y l r i n g s p a r a l l e l to surface.
T h e i n f r a r e d r e s u l t s also i n d i c a t e d that the p o l y ( a n i l i n e ) f i l m h a d N - H
bonds which were oriented perpendicular relative to the surface.
A l m o s t i d e n t i c a l results were obtained f o r the i n t e r a c t i o n of aniline
with a N i ( l l l ) surface.
Poly(aniline) films were prepared electrochemically on a Pt
e l e c t r o d e p o t e n t i o s t a t i c a l l y at 0.85 V v s A g / A g C I for 5 s f r o m a 1 M
aniline i n 1 M L i C 1 0 4 / C H 3 C N solution. T h e f i l m s were a faint blue-green
color. T h i c k e r f i l m s w e r e f o r m e d at greater p o t e n t i a l s . E v e n the v e r y
t h i n f i l m s c o u l d be o x i d i z e d and r e d u c e d . A f t e r r e m o v i n g the e l e c t r o d e
f r o m the a n i l i n e s o l u t i o n and p l a c i n g it i n e l e c t r o l y t e s o l u t i o n the f i l m
c o u l d be o x i d i z e d and reduced. O x i d a t i o n peaks o c c u r r e d at 0.2 V and 0.48
V , s c a n n i n g w a s k e p t b e l o w 1 V to a v o i d p o l y m e r d e g r a d a t i o n [7,8].
Infrared s p e c t r a o f the electrochemically prepared poly(aniline) were
taken after e m e r s i o n from the electrolyte s o l u t i o n at 0.8 V , 0.35 V and 0
V , the s p e c t r a are s h o w n i n F i g u r e 4. A t a l l three p o t e n t i a l s the i r

s p e c t r a s h o w o n l y w e a k C = C stretches o r r i n g v i b r a t i o n s i n the 1 3 5 0 -
1
1850 c m " range, i n d i c a t i n g that the p o l y ( a n i l i n e ) is f o r m e d w i t h the
p h e n y l r i n g n e a r l y p a r a l l e l to the surface. In the N H s t r e t c h i n g r e g i o n
1
(circa 3200 c m " ) one c a n see that the r e d u c e d f i l m has an N H
stretching band. A f t e r the first o x i d a t i o n the N H stretch d e c r e a s e s i n
i n t e n s i t y and shifts to l o w e r f r e q u e n c y , and after the s e c o n d o x i d a t i o n
the N H s t r e t c h v a n i s h e s . F r o m the i n f r a r e d results the r e d u c e d film
f r o m e l e c t r o c h e m i c a l d e p o s i t i o n a p p e a r e d to be a l m o s t i d e n t i c a l to the
catalytically formed film. As was observed with thiophene
p o l y m e r i z a t i o n , the c a t a l y t i c p o l y m e r i z a t i o n o f a n i l i n e w o u l d produce
only a monolayer w h i l e the electrochemical polymerization could
produce thick films.

J 0.2%
I 1 1 1 I I I I I
2800 3000 3200 3400 3600
J 0.1%
- J I I I L_
1400 1600 1800
Wavenumber (cm )
Figure 4 . Reflection infrared spectra of aniline films (a) aniline multilayer
adsorbed on Ni(111) at 165 K (b) poly(aniline) monolayer on Ni(111) at
400 K (c) electrochemically grown poly(aniline) on Pt oxidized at 0.8 V vs.
Ag/AgCI(1M) (d) electrochemically grown poly(aniline) on Pt reduced at 0.35
V v s . Ag/AgCI(1M) (e) electrochemically grown poly(aniline) on Pt reduced
at 0.0 V vs. Ag/AgCI(1M)

Pyridine. P y r i d i n e a n d its m e t h y l substituted d e r i v a t i v e s ( p i c o l i n e s and

lutidines) were found to polymerize electrochemically and, under
certain circumstances, catalytically. T h i s b e h a v i o r was not expected
because usually pyridine undergoes electrophilic substitution and
addition slowly, behaving like a deactivated benzene ring. The
interaction o f p y r i d i n e w i t h a N i ( 1 0 0 ) surface d i d not indicate any
catalytic polymerization. A d s o r p t i o n o f p y r i d i n e b e l o w 2 0 0 K resulted i n
p y r i d i n e a d s o r b i n g w i t h the r i n g p a r a l l e l to the surface. The infrared
s p e c t r u m o f p y r i d i n e a d s o r b e d at 2 0 0 K s h o w e d n o e v i d e n c e o f e i t h e r
r i n g v i b r a t i o n s or C H stretches ( F i g u r e 5). Desorption of molecular
p y r i d i n e o c c u r r e d at 2 5 0 K , and a b o v e 3 0 0 K p y r i d i n e u n d e r w e n t a
s u b s t i t u t i o n r e a c t i o n f o r m i n g an cc-pyridyl species o n the surface
[12.231. P r o m i n e n t r i n g m o d e s i n the i n f r a r e d s p e c t r u m i n d i c a t e d that
the r i n g w a s o r i e n t e d p e r p e n d i c u l a r to the s u r f a c e . The a-pyridyl
subsequently reacted f o r m i n g a variety o f species i n c l u d i n g p y r i d i n e ,
H C N , and d i h y d r o g e n that d e s o r b e d at 4 7 5 K . There was evidence o f a
s m a l l amount o f a m o r e stabl surfac specie that d e c o m p o s e d abov 600
K suggesting the p o s s i b i l i t
was a m i n o r r e a c t i o n path
M e t h y l s u b s t i t u e n t s o n the p y r i d i n e r i n g h a d a p r o f o u n d i m p a c t
on the r e a c t i v i t y o f the p y r i d i n e r i n g . 2 , 6 - L u t i d i n e d i d not react to any
appreciable extent on N i ( 1 0 0 ) [12]. The infrared spectrum o f 2,6-
l u t i d i n e s h o w e d n o C = C stretches and r i n g v i b r a t i o n s , but d i d s h o w C H
stretches. T h i s i n d i c a t e d a d s o r p t i o n o c c u r r e d w i t h the r i n g p a r a l l e l to
the surface, and the C H stretches resulted f r o m the m e t h y l g r o u p s . The
presence o f the m e t h y l g r o u p s i n h i b i t e d attack at the a - c a r b o n and
r e s u l t e d i n the l u t i d i n e d e s o r b i n g w i t h o u t r e a c t i o n . In contrast, 3,5-
lutidine adsorbed w i t h i t s r i n g p e r p e n d i c u l a r to the surface. The
i n f r a r e d s p e c t r u m f o r 3 , 5 - l u t i d i n e adsorbed o n N i ( 1 0 0 ) at 180 K s h o w n i f
F i g u r e 6 is v e r y s i m i l a r to l i q u i d l u t i d i n e . T h e C = C stretches a n d r i n g
modes are all very prominent. During temperature programmed
h e a t i n g n o l u t i d i n e w a s f o u n d to desorb f r o m the surface. Dihydrogen
was e v o l v e d i n a series o f d e s o r p t i o n peaks between 3 0 0 and 6 0 0 K , a l o n g
w i t h s m a l l a m o u n t s o f m e t h a n e and a m m o n i a . The infrared spectra
s h o w e d a g r a d u a l l o s s o f m o s t o f the a b s o r p t i o n b a n d s , but the C = C
1
s t r e t c h i n g b a n d at 1590 c m ' persisted to above 7 5 0 K . T h e T P R results
s h o w e d a m i x t u r e o f h y d r o c a r b o n s , a m m o n i a and h y d r o g e n c y a n i d e a l l
were e v o l v e d at 9 0 0 K f r o m the d e c o m p o s i t i o n o f a stable surface species.
A u g e r e l e c t r o n s p e c t r a i n d i c a t e d the C ( K L L ) l i n e s h a p e w a s that o f a
molecular entity to above 800 K . The molecular coverage after
a d s o r p t i o n at 180 K , based o n the C ( K L L ) / N i ( L M M ) and N ( K L L ) / N i ( L M M )
2
r a t i o s , w a s a p p r o x i m a t e l y 0 . 7 x 1 0 ^ c m " ; and this c o v e r a g e r e m a i n e d
nearly constant u p to 8 0 0 K . T h i s is a p p r o x i m a t e l y the m a x i m u m
coverage based on c l o s e - p a c k e d v a n der W a a l s r a d i i . These results
suggest the f o r m a t i o n o f a surface p o l y m e r o f l u t i d i n e , w h i c h d i s p l a y s
comparable thermal s t a b i l i t y to p o l y ( a n i l i n e ) . The poly(lutidine) is
different f r o m the p o l y ( a n i l i n e ) i n the o r i e n t a t i o n o f the r i n g s , as
infrared spectroscopy s h o w s p o l y ( l u t i d i n e ) has the r i n g s perpendicular
to the surface.

BENZIGER ET AL. Aromatic Polymerization on Metal Surfaces
1400 1600 1800
-1
Wavenumber (cm )
Figure 5. Reflection infrared spectra of pyridine films (a) pyridine adsorbed
on Ni(111) at 180 K (b) pyridine adsorbed on Ni(111) at 320 K (c)
electrochemically grown poly(pyridine) on Pt (d) 3,5-lutidine adsorbed on
Ni(111) at 180 K (e) 3,5-lutidine polymer on Ni(111) at 750 K (f) 2,6-
lutidine adsorbed on Ni(111) at 180 K

Figure 6. Electrophilic polymerization of thiophene. Initial rc-bonding,

formation of radical cation, electrophilic addition.

P y r i d i n e w a s f o u n d to p o l y m e r i z e o n a P t e l e c t r o d e from a
s o l u t i o n o f 1 M p y r i d i n e i n 1 M L i C 1 0 4 / C H 3 C N at potentials above 0.8 V v s
Ag/AgCI. A c o l o r l e s s f i l m w a s f o r m e d , but it c o u l d be o x i d i z e d a n d
reduced when placed in plain electrolyte solution. The infrared
s p e c t r u m o f the e l e c t r o c h e m i c a l l y f o r m e d p o l y ( p y r i d i n e ) f i l m i s s h o w n
1
i n F i g u r e 5. It d i s p l a y s a v e r y i n t e n s e , n a r r o w b a n d at 1 5 0 0 c m '
i n d i c a t i v e o f C = C stretches that are p e r p e n d i c u l a r to the s u r f a c e . 3,5
L u t i d i n e a l s o w a s p o l y m e r i z e d o n a p l a t i n u m e l e c t r o d e u n d e r the same
c o n d i t i o n s , and its i n f r a r e d s p e c t r u m is s i m i l a r to that f o r the surface
catalyzed poly(lutidine). T h e C = C s t r e t c h i n g b a n d f o r the p o l y ( l u t i d i n e )
is at s l i g h t l y h i g h e r f r e q u e n c y than that o b s e r v e d f o r p o l y ( p y r i d i n e ) ,
and a l s o is b r o a d e r . W e also attempted to p o l y m e r i z e 2 , 6 - l u t i d i n e
e l e c t r o c h e m i c a l l y but f o u n d that at p o t e n t i a l s o f l e s s t h a n 2 V n o
p o l y m e r i z a t i o n o f the 2 , 6 - l u t i d i n e was o b s e r v e d .
Pyrrole. P y r r o l e is the n i t r o g e n a n a l o g o f thiophene and is e x p e c t e d to

behave in much the same fashion Electrochemically the
polymerization of pyrrol
polymerization of pyrrol
those f o r t h i o p h e n e . O u r w o r k and the w o r k o f others suggests that the
surface catalytic p o l y m e r i z a t i o n o f p y r r o l e is also less l i k e l y than for
thiophene. Temperature programmed reactions o f pyrrole on N i ( 1 0 0 )
s h o w e d d i f f e r e n t t y p e s o f r e a c t i o n s o c c u r r e d at d i f f e r e n t h e a t i n g rates
[24.]. A t h e a t i n g rates < 10 K / s p y r r o l e d e c o m p o s e d o n N i ( 1 0 0 ) to
adsorbed carbon and n i t r o g e n , and h y d r o g e n w h i c h recombined and
d e s o r b e d as d i h y d r o g e n . A t h i g h e r h e a t i n g rates, > 50 K / s , pyrrole
appeared to p o l y m e r i z e , f o r m i n g a s u r f a c e species that decomposed
a b o v e 5 7 0 K y i e l d i n g H 2 , H C N , and v a r i o u s h y d r o c a r b o n products.
Infrared spectroscopy also reflected these differences in reaction
p a t h w a y c a u s e d b y d i f f e r e n t h e a t i n g rates. The infrared spectra for
p y r r o l e a d s o r b e d o n N i ( 1 0 0 ) i n d i c a t e that after a d s o r p t i o n at 170 K the
m o l e c u l e adsorbed w i t h its r i n g p a r a l l e l to the surface as n o C = C , o r C H
m o d e s were apparent i n the i n f r a r e d s p e c t r u m . A f t e r h e a t i n g to 4 0 0 K
at a rate o f 8 K / s the i n f r a r e d s p e c t r u m r e m a i n e d featureless, whereas
1
after h e a t i n g to 4 0 0 K at 48 K / s s m a l l features were evident at 1550 c m "
1
c o r r e s p o n d i n g to the C = C stretching, and at 3075 and 3 3 6 0 c m " resulting
from C H and N H stretches respectively. These features are weak,
c o n s i s t e n t w i t h the T P R r e s u l t s s h o w i n g that the s u r f a c e concentration
o f o l i g i m e r is l o w . P y r r o l e was also f o u n d to reorient o n P t ( l l l ) c i r c a
300 K [25].
A poly(pyrrole) film was deposited on a Pt electrode from
potentiostatic c o n d i t i o n s at 0.8 V v s A g / A g C I . T h e f i l m was c o l o r l e s s , its
p r e s e n c e w a s v e r i f i e d b y o x i d a t i o n and r e d u c t i o n o f the f i l m i n p l a i n
electrolyte solution. T h e infrared spectrum o f the e l e c t r o c h e m i c a l l y
prepared p o l y ( p y r r o l e ) i s s i m i l a r to the c a t a l y t i c a l l y p r e p a r e d films
i n d i c a t i n g the t w o f i l m s are s t r u c t u r a l l y s i m i l a r .
Discussion
The results suggest that there is a remarkable similarity in the

structure o f t h i n f i l m s f o r m e d b y a n o d i c d e p o s i t i o n o n a P t e l e c t r o d e to
those formed c a t a l y t i c a l l y on N i surfaces in ultrahigh vacuum. The

reactions that form these polymers are both suggested to be

electrophilic addition reactions. I n the case o f e l e c t r o c h e m i c a l a n o d i c
d e p o s i t i o n an e l e c t r o n is p u l l e d f r o m the a r o m a t i c ring producing a
r a d i c a l cation, s h o w n schematically for thiophene i n F i g u r e 6. The
radical cation would attack an aromatic ring as an electrophile,
resulting in chain propagation. In the case o f a c l e a n m e t a l surface
e m p t y states act as e l e c t r o n a c c e p t o r s , a g a i n p r o d u c i n g a r a d i c a l c a t i o n
that w i l l act as an electrophile. Work function measurements of
a r o m a t i c m o l e c u l e s o n P t surfaces h a v e s h o w n that the surface acts as
an a c c e p t o r f o r the n e l e c t r o n s i n the a r o m a t i c r i n g r 2 6 . 2 7 1 . The electron
donation o f the aromatic m o l e c u l e s c a n be u n d e r s t o o d i n terms o f
energy l e v e l m a t c h i n g arguments L L 8 J .
T h e c a t a l y t i c p o l y m e r i z a t i o n reaction is d i s t i n g u i s h e d from its
e l e c t r o c h e m i c a l counterpart b y the e x t e n t o f p o l y m e r i z a t i o n . Catalytic
surface p o l y m e r i z a t i o n a p p e a r s to b e l i m i t e d , w h e r e a s one c a n grow
arbitrarily thick films electrochemically. T h i s d i f f e r e n c e i s due to the
available sink for electrons to p r o p a g a t e the r e a c t i o n O n an open
c i r c u i t m e t a l s u r f a c e , so
electron acceptors. This
states, o r the p o l y m e r f i l m h i n d e r i n g e l e c t r o n transfer a c r o s s the l a y e r
as it g r o w s . E l e c t r o c h e m i c a l l y there is a c o n t i n u a l d r a i n o f e l e c t r o n s ,
l i m i t e d o n l y b y the c o n d u c t i v i t y t h r o u g h the g r o w i n g f i l m , so the film
m a y be g r o w n a r b i t r a r i l y t h i c k . There are also activation
barriers associated with both electrochemical and surface catalyzed
reactions. I n the e l e c t r o c h e m i c a l route a s u f f i c i e n t p o t e n t i a l m u s t be
a p p l i e d to a l l o w e l e c t r o n s to f l o w f r o m the adsorbate i n t o the s o l i d . The
a c t i v a t i o n b a r r i e r a s s o c i a t e d w i t h the c a t a l y t i c p a t h i s that the electrons
are t h e r m a l l y a c t i v a t e d to g o f r o m the 7E-orbitals i n the a r o m a t i c to the
empty surface states.
T h e a c t i v a t i o n a s s o c i a t e d w i t h the c a t a l y t i c p a t h a l s o a p p e a r s to
cause o r i e n t a t i o n a l c h a n g e s i n a v a r i e t y o f the m o l e c u l e s . T h i s can also
be a c c o u n t e d f o r b y the e l e c t r o p h i l i c n a t u r e o f the r e a c t i o n s . I n the
c a s e o f t h i o p h e n e , p y r r o l e a n d p y r i d i n e the h i g h e s t o c c u p i e d m o l e c u l a r
o r b i t a l s are the 7r-orbitals. T h e l o n e e l e c t r o n p a i r l i e s at l o w e r e n e r g i e s .
At l o w temperatures adsorption occurs through a multi-center bond
b e t w e e n the 7r-orbitals o f the a r o m a t i c s p e c i e s a n d the m e t a l d - o r b i t a l s ,
a n d r e s u l t s i n the r i n g b e i n g p a r a l l e l to the surface. P r o m o t i o n o f an
e l e c t r o n f r o m the l o n e e l e c t r o n p a i r to b o n d w i t h the e m p t y m e t a l d -
states a b o v e the F e r m i l e v e l r e s u l t s i n a p e r p e n d i c u l a r c o n f i g u r a t i o n as
the l o n e e l e c t r o n p a i r i s i n the p l a n e o f the r i n g . The electrochemical
deposition process effectively reduces the activation barrier for
bonding between the s u r f a c e states a n d the l o n e e l e c t r o n p a i r . By
d e c r e a s i n g the p o t e n t i a l one e f f e c t i v e l y l o w e r s the l u m o s o f the surface
reducing the activation barrier and making the perpendicular
configuration more favorable. W e h a v e c a r r i e d out e x t e n d e d Huckel
c a l c u l a t i o n s f o r p y r i d i n e a d s o r b e d o n a 17 N i a t o m c l u s t e r m o d e l l i n g
a d s o r p t i o n o n a N i ( 1 0 0 ) surface. F o r the n o r m a l d - l e v e l o f the N i atoms
the F e r m i l e v e l o f the c l u s t e r is at - 8 . 2 2 e V and the p a r a l l e l m o d e o f
p y r i d i n e b i n d i n g is 2 4 k J / m o l m o r e stable t h a n the p e r p e n d i c u l a r m o d e ;
h o w e v e r w h e n the N i d - l e v e l decreased so the F e r m i l e v e l o f the c l u s t e r
is -9.11 e V the p e r p e n d i c u l a r m o d e o f b o n d i n g to the surface becomes
more stable. T h i s a p p e a r s to e x p l a i n w h y t h i o p h e n e , pyrrole and
p y r i d i n e a l l r e a d i l y p o l y m e r i z e a n o d i c a l l y at r o o m t e m p e r a t u r e w i t h the
r i n g p e r p e n d i c u l a r to the surface.

The methyl groups on the pyridine ring result in a major

difference in the reactivity of lutidines. In 3,5-lutidine the methyl
groups act as electron donors tending to increase the stability of the TC-
bonds, and activating the ring for electrophilic attack at the a-positions.
The MOs in 3,5-lutidine show the rc-levels pushed to lower energy
relative to pyridine, while the lone pair is unaffected so there is a
greater preference for bonding through the lone electron pair. The
methyl groups also push the ring away from the surface when bonding
in the parallel orientation, also contributing to the preference for the
perpendicular orientation. In contrast the methyl groups in 2,6-
lutidine sterically hinder bonding with the lone electron pair on the
nitrogen and also do not activate the ring for electrophilic reactions.
Thus one sees little reactivity and only a parallel bonding
configuration. These effects were manifested both catalytically and
electrochemically.
Aniline polymerized differently from the other heteroaromatics
as it retained a parallel bondin
group activated the rin
polymerization reactions. Unlike the other molecules the lone electron
pair on the nitrogen in aniline lies almost co-planar with the p-orbitals
of the phenyl ring. This results in the ring parallel, or nearly parallel
to the surface independent of the reaction conditions.
Conclusions
Aromatic molecules can be polymerized catalytically on clean metal

surfaces, or electrochemically to produce oriented polymer films.
Initial adsorption of aromatic molecules occurs by electron donation
from the aromatic molecule to the surface. This electron donation
creates radical cations that can polymerize. Molecular orientation in
the films depends on the stable bonding configuration of the radical
cation. Thiophene, pyridines, and pyrrole all polymerize with the ring
substantially perpendicular to the surface, whereas aniline polymerizes
with the phenyl rings parallel to the surface. The catalytically
prepared films terminate at monolayer coverage due to availability of
surface states to act as electron acceptors, while thick electrochemically
prepared films can be prepared by providing a drain for the electrons.
Acknowledgments
The authors wishes to thank the NSF and the AFOSR for providing
financial support for this work.
Literature Cited
1. Tourillon, G; in Handbook of Conducting Polymers, Skotheim, T.A.,

ed.; Dekker, New York, 1986.
2. Diaz, A.F.; Logan, J.A.; J. Electroanal. Chem. 1980, 111, 111.
3. Mohilner, D.M.; Adams, R.N.; Argersinger, W.J., Jr.; J. Am. Chem. Soc.
1982, 84, 3618.

4. Macdiarmid, A.G.; Chiang, J.C.; Richter, A.F.; Epstein, A.J.; Synthetic

Metals 1987, 18, 285.
5. Tourillon, G.; Garnier, G.; J. Phys. Chem. 1983, 87, 2289.
6. Genies, E.M.; Vieil, E.; Synthethic Metals 1987, 20, 97.
7. Paul, E.W.; Ricco, A.J.; Wrighton, M.S.; J. Phys. Chem. 1985, 89, 1441.
8. Mermilliod,N.; Tanguy, J.; Hoclet, M.; Syed, A.A.; Synthetic Metals
1987, 18, 359.
9. Tourillon, G.; Garnier, F.; J. Electrochem. Soc. 1983, 130, 2042.
10. Kovacic, P.; McFarland, K.N.; J. Polym. Sci. Polym. Chem. 1979, 17,
1963.
11. Schoofs, G.R.; Preston, R.E.; Benziger, J.B.; Langmuir 1985, 1, 313.
12. Schoofs, G.R.; Benziger, J.B.; J. Phys. Chem. 1988, 92, 741.
13. Benziger, J.B.; Preston, R.E.; Schoofs, G.R.; Appl. Optics, 1987, 26, 343.
14. Greenler, R.G.; J. Chem. Phys. 1966, 44, 310.
15. Pang, K.P.; Benziger, J.B.; Soriaga, M.P.; Hubbard, A.T.; J. Phys. Chem.
1984, 88, 4583.
16. Zaera, F.; Kollin, E.B.; Gland J.L.; Langmuir 1987 3, 555
17. Lang,J.F.; Masel, R.I.
18. Myers, A.K.; Benziger
19. Sexton, B.A.; Surface Science 1985,163, 99.
20. Yamamoto, T.; Sanechika, K.; Yamamoto, A.; Bull. Chem. Soc. Japan
1983, 56, 1497.
21. Bonner, W.A.; Grimm, R.A.; In "The Chemistry of Organic Sulfur
Compounds"; Kharasch, N; Meyers, C.Y. Eds.; Pergamon Press: Oxford,
1966; Chapter 2.
22. Haas, W.T.; Grant, J.T.; Dooley, D.J.; Proc. 2nd Intern. Symp. on
Adsorption/DesorptionPhenomena;Ricca, F. Ed.; Academic Press:
London, 1973.
23. Wexler, R.M.; Tsai M.-C.; Friend, C.M.; Muetterties, E.L.; J. Am. Chem.
Soc. 1982, 104, 2034.
24. Schoofs, G.R.; Benziger, J.B.; Surface Science 1987 , 192 , 373.
25. Tourillon, G.; Raaen, S.; Skotheim, T.A.; Sagurton, M.; Garrett, R.;
Williams, G.P.; Surface Science 1987, 184, L345.
26. Gland, J.L.; Somorjai, G.A.; Surface Science 1974, 41, 387.
27. Gland, J.L.; Somorjai, G.A.; Surface Science 1973, 38, 157.
RECEIVED May 17, 1988

Chapter 7
Surface Chemistry of Copper Electrodes

Preliminary Studies
John L. Stickney, Charles B. Ehlers, and Brian W. Gregory
School of Chemical Science, University of Georgia, Athens, GA 30602
I n i t i a l studies o
planes of coppe
water, HCl gas, and aqueous 1mM HCl, have been
performed. An u l t r a h i g h vacuum surface analysis
instrument, d i r e c t l y coupled to an antechamber, used f o r
high pressure and s o l u t i o n experiments, was used to
investigate the surface r e a c t i v i t y of a copper single
c r y s t a l . This c r y s t a l was oriented on three faces, each
to a d i f f e r e n t low index plane. Low energy electron
d i f f r a c t i o n and Auger electron spectroscopy were used to
study the surfaces before and a f t e r each reaction. The
r e s u l t i n g structures and compositions were consistent
with previous gas phase studies i n the l i t e r a t u r e , and
evidenced s i g n i f i c a n t s t a b i l i t y f o r the copper surface
in aqueous solutions a t open c i r c u i t .
This paper describes equipment, procedures and r e s u l t s f o r

investigation o f t r a n s i t i o n metal surface r e a c t i v i t y . Specifically,
the surface r e a c t i v i t y of copper s i n g l e c r y s t a l s was examined under
conditions relevant t o the electrochemistry and corrosion of copper.
Copper i s the primary metal used i n construction o f e l e c t r o n i c
equipment. Preparation o f copper components often involves
e l e c t r o p l a t i n g , e l e c t r o p o l i s h i n g , or exposure to humid a i r . The
extensive use o f copper j u s t i f i e s a systematic examination of i t s
surface r e a c t i v i t y .
I n i t i a l studies, described here, involved the use of an
ultrahigh vacuum (UHV) surface-analytical instrument coupled to an
antechamber. The antechamber allows experiments i n solution and
electrochemical treatments without transfer o f samples outside of the
system's c o n t r o l l e d atmosphere. Focusing on the chemistry of copper
surfaces i n aqueous environments suggests the importance o f studying
the i n i t i a l stages o f surface r e a c t i v i t y with oxygen and water.
Electrochemical experiments involve e l e c t r o l y t e s ; thus t h e i r surface
r e a c t i v i t y should be studied as well.
Oxygen adsorption on the low-index planes o f copper i s one o f
0097-6156/88/0378-0099$06.00/0
c

the most extensively studied surface systems, and has been p a r t i a l l y

reviewed by Spitzer and Luth (1,2). From an electrochemical
standpoint, water adsorption i s of great interest, although copper i s
much less reactive to water than to oxygen at room temperature (3-
12). Water i s adsorbed at or above room temperature only i n the
presence of c a t a l y t i c amounts of adsorbed oxygen (4-6,8,10,11), and
i t s adsorption involves decomposition to oxygen adatoms (11).
Previous surface studies of the adsorption of e l e c t r o l y t e s , or
e l e c t r o l y t e analogues, have mostly involved CI2 (Stickney, J.L.;
Ehlers, C.B.; Gregory, B.W.; Langmuir, submitted.) *' S.E.G." The
adsorption of HC1 from both the gas phase and from solution onto the
low-index planes of copper has been recently studied in this
author's lab (S.E.G.). In general, halogens and hydrogen halides
adsorb strongly on copper surfaces, forming adlayers of halogen
atoms at low exposures, < 1000L. High exposures of halogens r e s u l t
i n formation of t h i n films of copper halides (13).
Experimental. The apparatu

Figure 1. The instrumen
optics f o r examination of the sample surface by low energy electron
d i f f r a c t i o n (LEED), a hemispherical electron analyzer f o r Auger
electron spectroscopy (AES), and a quadrupole mass spectrometer f o r
thermal desorption spectroscopy (TDS). Attached to the analysis
chamber i s an antechamber (Figure 2) into which the sample was
transferred f o r experiments involving high pressures, up to ambient,
or solutions. The antechamber allows introduction of high pressures
of reactant gases while leaving the analysis chamber at UHV
9 11
pressures, 10- to 10- Torr. A gate-valve interlock connects a
s t a i n l e s s s t e e l bellows-sealed compartment to the antechamber. This
compartment contains an electrochemical H-cell made of Pyrex glass,
complete with a glass f r i t separating the a u x i l i a r y electrode
compartment.
Extraction and t r a n s l a t i o n of the sample to the antechamber
were performed with a l i n e a r and r o t a t i o n a l feedthrough assembly
(Figure 2). The rotational feedthrough was used both to rotate the
sample between c r y s t a l faces f o r analysis and to lock the sample
holder onto the extraction rod f o r transfer into the antechamber.
The sample holder and X-Y-Z-R manipulator, located i n the analysis
chamber, were connected with four contacts: one chromel and one
alumel ( f o r the thermocouple), and two high current connectors f o r
sample heating. These four contacts were set inside a 1-1/4" I.D.
high-precision bearing. This bearing provided r o t a t i o n (which was
necessary to examine a l l three faces of the c r y s t a l ) , room f o r the
e l e c t r i c a l contacts, and clearance f o r extraction of the c r y s t a l .
Sample. The sample used i n the experiments described here was a

single c r y s t a l of copper oriented and polished on three faces. Each
of the three faces was oriented to a d i f f e r e n t low-index
crystallographic plane; the (100), the (111) or the (110). These
three faces were p a r a l l e l to a v e r t i c a l axis, allowing the study of
each, i n turn, by r o t a t i o n about t h i s axis (Figure 2). The low-index
planes could thus be studied without removing the sample from the UHV
system. More importantly, however, experiments involved equivalent
treatment of the three faces at each stage. I n i t i a l ion bombardment
took place i n a cage, s i m i l a r to an ion gauge, i n which the sample

7. STICKNEY ETAL. Surface Chemistry of Copper Electrodes 101
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7. STICKNEY ET AL. Surface Chemistry of Copper Electrodes 103
5
acted as the c o l l e c t o r i n 10- Torr of argon. A l l three faces were
bombarded at the same time, which prevented one from becoming
contaminated while the others were cleaned. Gas dosing was performed
dynamically but without a gas dosing tube so that equivalent
exposures resulted on a l l surfaces. Gas composition, p a r t i a l
pressure, and t o t a l gas exposure were monitored with a quadrupole
mass spectrometer (UTI). A Pyrex sorption pump was included i n the
dosing manifold (Figure 2). The sorption pump and high p u r i t y gas
source were used to rinse the manifold multiple times p r i o r to gas
introduction, which resulted i n higher dosent p u r i t y . Immersion of
the sample i n solution also resulted i n equivalent exposures on the
three faces. Solutions were prepared with p y r o l y t i c a l l y d i s t i l l e d
water (14) and reagent grade chemicals.
Sample pretreatment consisted f i r s t of ion bombardment which
removed the top monolayers of the sample surface, followed by
annealing at 550°C f o r 15 minutes by resistance heating. Subsequent
AES spectra were taken and monitored f o sign f contamination
LEED was used to characteriz
surfaces, insuring the reproduciblit
each experiment.
Before s o l u t i o n experiments were run, the sample was transferred
to the antechamber. Ultrahigh p u r i t y (UHP) gases, argon and nitrogen
(Matheson), were used to bring the antechamber to ambient pressure
(Figure 3b). Subsequently, the gate valve was opened (Figure 2),
and the H-cell inserted. With the H - c e l l i n p o s i t i o n , the sample was
lowered i n and solutions were delivered from pressurized b o t t l e s
exterior to the instrument.
Pump-down of the antechamber, following solution experiments,
involved sorption pumping and cryo-pumping r e s u l t i n g i n the pressure
9
decreasing from ambient to 10- Torr i n 5 minutes. The r e s u l t i n g
sample surfaces were subsequently examined by both LEED and AES a f t e r
transfer back to the analysis-chamber.
Results and Discussion
Oxygen Adsorption. I n i t i a l exposure of the copper c r y s t a l to oxygen

resulted i n formation of structures previously reported i n the
l i t e r a t u r e (1-3,15). On Cu(100), structures formed were the same as
those described by Lee and Farnsworth (15) as early as 1965.
Exposures less than 500L at c r y s t a l temperatures above 100°C
resulted i n formation of an oblique structure, characterized by
groups of four spots near the (1/2, 1/2) positions. Exposures above
500L at room temperature resulted i n the i n i t i a l formation of a
Cu(100)(/2X/2)R45-0 structure. There i s some disagreement i n the
l i t e r a t u r e as to whether t h i s pattern represents a separate
structure or whether i t i s an enhancement of a subset of spots
c h a r a c t e r i s t i c of a Cu(100)(/2X2/2)R45° structure, observed at higher
exposures (Figure 3c). The extra beams r e s u l t i n g from the 2/2
pattern vary considerably i n i n t e n s i t y as the oxygen coverage i s
4
changed. High exposures, above 2x10 L resulted i n multiple layers
of copper oxidation (Figure 3d) and a disordered LEED pattern.
Studies of oxygen adsorption on C u ( l l l ) have been reported i n
the l i t e r a t u r e to a lesser degree than studies of Cu(100) or Cu(110).
This i s primarily due to the lack of formation of an ordered
structure on C u ( l l l ) (2,17,13) at low exposures. Oxygen adsorbs on


7. STICKNEY ETAL. Surface Chemistry of Copper Electrodes 105
C u ( l l l ) to a lesser extent than on the other two low-index planes.

This adsorption r e s u l t s i n formation of an ordered structure above
3
10 L a t room temperature, which i s displayed as an oblique unit c e l l
[ ]. This pattern has been previously reported (JL6). It i s
interesting that i t has not been observed by other workers, possibly
because of the extreme O 2 exposures required and the faintness of the
pattern.
Ion scattering experiments by Niehus (17) on Cu(111) with
adsorbed oxygen indicate that the copper surface undergoes a
reconstruction. Room temperature work function measurements
evidenced no change upon adsorption of oxygen, which was interpreted
as incorporation of oxygen. Alternatively, those authors (2)
suggested that the absence of a work function change could be
interpreted as evidence f o r reconstruction, i n l i n e with the ion
scattering work (17). These results are consistent with Pritchard
and co-workers (13), who account f o r the [ ] pattern by proposing
a reconstruction of the to laye f t form adlaye havin
(/2X/2)R45° symmetry.
Oxygen adsorption o
of a (2X1) structure (1,18-22). Quantitation of the oxygen Auger
current indicated s i g n i f i c a n t l y less oxygen present when the (2x1)
was i n i t i a l l y formed, compared with a coverage of 0.5, which i s
expected f o r an oxygen structure with t h i s symmetry. The low oxygen
coverage, responsible f o r i n i t i a l formation of the (2X1), was
e s p e c i a l l y evident i n d i r e c t comparisons with oxygen coverages and
structures on the other two faces. Ion scattering experiments
(18,21,22) and X-ray adsorption (XAS) studies (19,20) suggest that
the surface undergoes a reconstruction upon oxygen adsorption,
r e s u l t i n g i n a missing row structure where every other row of <100>-
packed surface-copper atoms are removed. Oxygen atoms reside i n the
leftover short bridge s i t e s (18,20). I t thus appears that
reconstruction was catalyzed by a low coverage of oxygen, much lower
14 2
than the 5.4X10 atoms/cm expected f o r 1/2 coverage. Increasing
the oxygen coverage above 0.5 formed a c(6X2) pattern, reported
elsewhere (1,22), which was optimum near unit coverage. Uncertainty
as to whether the surface remains reconstructed (18-22) prevents
simple interpretation of the c(6X2) pattern.
Water Adsorption. As mentioned i n the introduction, water i s not

strongly adsorbed on copper a t room temperature (3-12). In the
present studies, no adsoiption was observed u n t i l extremely high
7
exposures of water (>10 L ) . At these l e v e l s , the p a r t i a l pressure
of oxygen i n the water vapor was s i g n i f i c a n t and probably responsible
for the presence of adsorbed oxygen. The same structures observed
with pure oxygen, mentioned previously, were observed i n the present
case.
The water used i n these experiments was made by p y r o l y t i c
d i s t i l l a t i o n , a process involving saturation of the d i s t i l l i n g water
vapor with oxygen and passing i t over heated platinum (14).
Extensive sparging with UHP N 2 was performed p r i o r to experiments,
removing most of the oxygen. Subsequent experiments w i l l involve a
f i n a l b o i l i n the absence of oxygen i n order to decrease the O 2
content further.
Suspension of the c r y s t a l above l i q u i d water f o r 2 minutes
resulted i n oxidation to the extent observed i n the presence of 10

Torr of water vapor or oxygen exposures over 1,000L; the 2/2 LEED
pattern was observed on Cu(100) and the c(6X2) was observed on
Cu(110). There was increased d i f f u s e i n t e n s i t y i n these patterns
over those r e s u l t i n g from exposure to pure oxygen, but the symmetry
was d i s t i n c t . No elements, other then oxygen and copper, were
evidenced by Auger spectroscopy.
Immersion of the copper c r y s t a l into water resulted i n a 25%
increase i n the oxygen Auger current on C u ( l l l ) and Cu(110), while i t
was r e l a t i v e l y unchanged on Cu(100) (Figure 3e). The 2/2 pattern
was s t i l l present on Cu(100) a f t e r emersion while the other low-
index planes displayed d i f f u s e LEED patterns with spots v i s i b l e only
at energies above 100 eV. The facts that spots were v i s i b l e above
100 eV and the minor increase i n oxygen Auger current suggest that
the oxidation was no more than two monolayers thick. This also
indicates s i g n i f i c a n t s t a b i l i t y f o r the copper surfaces at open
c i r c u i t i n water. Subsequent studies w i l l involve potential control
and examination of copper surface stability vs potential
Supporting e l e c t r o l y t e s
E l e c t r o l y t e Adsorption. I n i t i a l studies of e l e c t r o l y t e adsorption

have been performed using HC1. HC1 adsorption i n the gas phase and
from solution was investigated and i s described i n a separate paper
(S.E.G.). HC1 gas adsorbs on copper with an i n i t i a l s t i c k i n g
c o e f f i c i e n t close to 1. This adsorption rate decreases by 2 to 3
orders of magnitude a f t e r 1/2 monolayer of adsorption. Ordered
structures were observed on a l l three of the low index planes at HC1
ev-posures of 20L or l e s s : Cu(100)(/2X/2)R45°-C1, Cu(111)(/3X/3)R30°-
01 and Cu(110)c(2X2)-Cl. These patterns resemble those formed by C l 2
adsorbed on other t r a n s i t i o n metals and with other hydrogen halides

and halogens. That i s , i n general, these patterns r e s u l t from
structures which are approximately hexagonally close-packed layers of
adsorbed halogem atoms (1,2),
A series of t r a n s i t i o n structures were observed with LEED on the
Cu(llO) surface at exposures exceeding 10L. These structures
indicated that the CI atoms on the surface were undergoing
compression i n the <110> d i r e c t i o n , close packing at t h e i r van der
Waals diameter. The f i n a l ordered structure was a Cu(110)(3X2)-Cl at
a chlorine coverage of 2/3. HC1 exposures exceeding 1000L r e s u l t i n
formation of bulk copper chlorides, evidenced by increased d i f f u s e
i n t e n s i t y i n the LEED pattern, decreased copper Auger currents, and
increased chlorine Auger currents. This stage of halogen adsorption
has been extensively investigated by Sesselmann and Chuang on
p o l y c r y s t a l l i n e Cu (13).
A c r y s t a l supporting preadsorbed CI a d l a t t i c e s formed with HC1
gas, as described previously, was immersed i n water f o r one minute to
investigate the s t a b i l i t y of the CI adlayers. Subsequent examination
of the emersed (removed) c r y s t a l evidenced a p a r t i a l loss of
chlorine, about 1/3, and uptake of oxygen on both C u ( l l l ) and
Cu(llO). There was no detectable oxygen uptake on the Cu(100)
surface.
Ordered LEED patterns were evident on a l l three surfaces. A
Cu(100)(/2X/2)R45°-C1 was observed with LEED, the same pattern
present on the surface before immersion, but with a s l i g h t increase
i n spot diffuseness. A 28% decrease i n CI Auger current was observed
and was responsible f o r the degradation i n LEED pattern c l a r i t y . I t

7. STICKNEY ET AL. Surface Chemistry of Copper Electrodes 107
Figure 4. LEED pattern r e s u l t i n g from immersion of a

Cu(lll)(/3x/3)R30°-Cl structure into water. Cu(111)(/3x/3)R30°
s p l i t pattern, 60 eV.

Figure 5. LEED pattern r e s u l t i n g from immersion of a

Cu(110)c(2x2)-Cl structure into water. Cu(110)c(4x2)-Cl,O
pattern, 61 eV.

7. STICKNEY ETAL. Surf ace Chemistry of Copper Electrodes 109
appears that the remaining CI was stable under the present conditions
and dense enough to prevent oxidation of the Cu(100) surface.
Chlorine adsorbed on C u ( l l l ) was less stable, decreasing by 37%
during immersion. Initially sharp /3 spots, before immersion, were
enlarged to form triangular spots a f t e r immersion (Figure 4). The
adsorption of s i g n i f i c a n t amounts of oxygen, as well as the* decrease
in CI, may account for the s i g n i f i c a n t d i f f u s e i n t e n s i t y present i n
the patterns, but the triangular shape of the f r a c t i o n a l index spots
i s LndicHtive of a CI structure reported previously by Goddard and
Lambert. Lambert e t . a l . reported formation of a /3 " s p l i t spot"
X>attern by exposure of C u ( l l l ) to C I 2 gas at 100°C. They proposed a
Cu(111)(6/3X6/3)R30°-C1 structure at a coverage of 0.45. The present
structure (Figure 4) has less CI than was present i n the i n i t i a l /3
structure, optimally 0.33. The presence of oxygen on the surface, as
well, may substitute f o r l o s t CI, but the pattern i s better explained
by a d i f f e r e n t structure.
A /3 s p l i t spot pattern was observed i n t h i s author's lab a f t e r
immersion of a clean C u ( l l l
pattern consisted of well-resolve
positions, s i m i l a r to the patterns r e s u l t i n g from iodine adsorption
on copper UPD (24) and on A g ( l l l ) (25). The structures proposed i n
these cases (24»25) more f u l l y explain the observed " s p l i t " pattern
and CI coverage. It was proposed that a reconstruction of the
surface to one having /3 l o c a l structure, occurred and that t h i s was
responsible f o r the absence of i n t e n s i t y anywhere but at the /3
positions. This /3 l o c a l symmetry existed inside a larger unit c e l l ,
defined by a series of phase boundaries, which accounts f o r the
" s p l i t spot" spacings and orientations. I t appears that the
Cu(lll)(/3X/3)R30°-Cl surface began reconstructing to form a /3
s p l i t structure upon immersion i n water but due to loss of CI and
oxygen incorporation, d i d not form the sharp s p l i t pattern (S.E.G.).
The i n i t i a l l y present Cu(110)c(2X2)-Cl structure, converted to a
c(4X2) with considerable d i f f u s e i n t e n s i t y and streaks i n the <110>
d i r e c t i o n (Figure 5). This LEED pattern was not observed i n
experiments involving HC1 adsorption on Cu(llO), described elsewhere
(S.E.G.). A Cu(110)c(4X2) with sharp spots, and without the d i f f u s e
background and streaking, was observed a f t e r heating an extensively
oxidized, 10 Torr of 0 , 2 Figure 3d, Cu(llO) surface to 550°C and
cooling. Since t h i s Cu(110) surface contained s i g n i f i c a n t amounts of
both CI and oxygen, proposing a structure would be premature. This
result w i l l be further examined i n a series of experiments, presently
underway, involving copper electrode p o t e n t i a l dependence of surface
structure and composition.
Literature Cited
1. Spitzer, A.; Luth, H. Surface S c i . 1982, 118, 121-35.

3. Sexton, B. A. J . Vac. S c i . Technol. 1979, 16, 1033-36.
4. Au, C. T.; Breza, J . ; Roberts, M. W. Chem. Phys. Lett. 1979,
66, 340-3.
5. Au, C. T.; Roberts, M. W. Chem. Phys. Lett. 1980, 74, 472-4.
7. Mariani, C.; Horn, K. Surface S c i . 1983, 126, 279-85.

8. Bange, K.; Grider, D.; Sass, J . K. Surface S c i . 1983, 126,

437-43.
9. Anderson, S.; Nyberg, C.; Tengstal, C. G. Chem. Phys. Lett.
1984, 104, 305-11.
10. Spitzer, A.; R i t z , A.; Luth, H. Surface S c i . 1985, 152/153,
543-49.
12. Nyberg, C.; Tengstal, C. G.; Uvdal, P.; Anderson, S. J . Elec.
Spec. and Rel. Phenom. 1986, 38, 299-307.
13. Sesselmann, W.; Chuang, T. J . Surface S c i . 1986, 176, 32 & 67.
14. Conway, B. E.; Angerstein-Kozlowska, H.; Sharp, W. B. A.;
Criddle, E. E. Anal. Chem. 1973, 45, 1331.
15. Lee, R. N.; Farnsworth, H. R. Surface S c i . 1965, 3, 461.
16. Judd, R. W.; H o l l i n s , P.; Pritchard, J . Surface S c i . 1986,
171, 643-53.
17. Niehus, H. Surface S c i . 1983, 130, 41-9.
18. Bronckers, R. P. N.; De Wit A G J Surface S c i 1981 112
133-52.
19. Dobler, U.; Baberschke
Lett. 1984, 52, 1437-40.
20. Dobler, U.; Baberschke, K.; Vvedensky, D. D.; Pendry, J . B.
Surface S c i . , 1986, 178, 679-85.
21. Yarmoff, J . A.; Cyr, D. M.; Huang, J . B.; Kim, S.; Williams, R.
S. Amer. Phys. Soc. 1986, 33, 3856-68.
22. Gruzalski, G. R.; Zehner, D. M.; Wendelken, J . F. Surface S c i .
1984, 147, L623-9.
23. Goddard, P. J . ; Lambert, R. M. Surface S c i . 1977, 69, 180.
24. Stickney. J . L.; Rosasco, S. D.; Hubbard, A. T. J . Electrochem.
Soc. 1984, 131, 260.
25. S a l a i t a , G. B.; Lu, F.; Laguren-Davidson, L.; Hubbard, A. T.
J. Electroanal. Chem. 1987, 229, 1.
R E C E I V E D May 17, 1988

Chapter 8
Molecules at Surfaces in Ultrahigh Vacuum

Structure and Bonding
J. Somers, T. Lindner, and A. M . Bradshaw

Using spectroscopi
tion and photoelectro possibl
tain information on the geometry and electronic struc-
ture of adsorbed molecules as well as of adsorbed
molecular fragments resulting from simple heterogene-
ous reactions. In fact, the correct assignment of the
electronic energy levels of such species using photo-
emission i s often only possible once the molecular
orientation i s known.
Our understanding of the energetics and dynamics of molecular

adsorption on single crystal metal surfaces under ultra-high vacuum
(uhv) conditions i s presently limited by the meagre amount of i n -
formation available on the geometric structure and electronic
energy levels of surface molecules. For example, only in the case
of a few simple systems such as diatomics - and then usually CO -
are the adsorption s i t e and molecular orientation known with any
accuracy. Structural analysis via low energy electron d i f f r a c t i o n
(LEED) i s restricted to ordered overlayers. Whilst many adsorbed
molecules form regular two-dimensional arrays, i t i s by no means
the rule. For molecular fragments formed as intermediates in
heterogeneous reactions (e.g. formate, methoxy, cyano) i t i s
certainly the exception. Moreover, LEED theory at i t s present state
of development has difficulties in coping with polyatomic
molecules. There are, however, a number of techniques which do not
require the existence of an ordered array and which s t i l l give
structural information in a direct or indirect way. One p o s s i b i l i t y
i s to measure the angular distribution of ions desorbed as a result
of electron- or photon-induced electronic transitions. The
technique i s normally referred to as ESDIAD and i s described by
Madey in another chapter of the volume. Another p o s s i b i l i t y i s to
apply selection rules in photoemission to establish molecular
orientation [1] but, as we shall see below, i t i s not possible to
simultaneously determine structure and assign l e v e l s . A new
development in recent years has been the application of structural
tools based on photoabsorption and photoionisation: x-ray absorp-
0097-6156/88/0378-0111$06.00/0

tion fine structure [2] and photoelectron d i f f r a c t i o n [3]. Since

they both require a continuously tunable source of soft x-rays,
usually in the region 200 - 1000 eV photon energy, their
application i s dependent on the a v a i l a b i l i t y of synchrotron radia-
tion and suitable grazing-incidence grating monochromators [4].
(This spectral range covers the core levels of C, N and 0; 1s (or
higher) levels of heavier elements are accessible at higher photon
energy with crystal monochromators.) The measurement of the polar-
isation dependence of the near edge x-ray absorption fine structure
(NEXAFS) i s a particularly straightforward technique, i f applied
correctly, and figures prominently in this a r t i c l e .
The most direct technique for probing surface electronic
structure i s undoubtedly photoemission, or photoelectron spectro-
scopy. In a reasonable approximation, referred to as Koopmans'
theorem, the measured ionisation potentials can be equated with the
ground state o r b i t a l energies. When the molecule i s only weakly
adsorbed a comparison with the photoelectron spectrum of the cor-
responding gas phase specie
various adsorbate-induce
l i n e sources (Hel, etc.) are usually adequate. Where a strong per-
turbation of the energy levels of the molecule takes place,
assignment can only be carried out using selection rules preferably
in conjunction with polarised l i g h t . This i s p a r t i c u l a r l y true of
molecular fragments for which no comparison with gas phase species
is possible. For the application of photoemission selection rules
prior knowledge of the orientation of the molecule i s necessary.
Synchrotron radiation in the photon energy range 10 - 50 eV (the
so-called normal-incidence region) i s the obvious choice for such
investigations because of i t s tunability and i n t r i n s i c a l l y high
polarisation.
In the investigations of molecular adsorption reported here our
philosophy has been to f i r s t determine the orientation of the ad-
sorbed molecule or molecular fragment using NEXAFS and/or photo-
electron d i f f r a c t i o n . Using photoemission selection rules we then
assign the observed spectral features in the photoelectron
spectrum. On the basis of Koopmans' theorem a comparison with a
quantum chemical cluster calculation i s then possible, should this
be available. A l l three types of measurement can be performed with
the same angle-resolving photoelectron spectrometer, but on
different monochromators. In the next Section we b r i e f l y discuss
the techniques. The third Section i s devoted to three examples of
the combined application of NEXAFS and photoemission, whereby the
f i r s t - C0/Ni(100) - i s chosen mainly for didactic reasons. The
results for the systems CN/Pd(111) and HC00/Cu(110) show, however,
the power of this approach in situations where no a priori
predictions of structure are possible.
Photoionisation and photoelectron emission
Below the photoionisation threshold a core electron in a free

molecule can be excited into empty anti-bonding molecular o r b i t a l s
(m.o.'s) as well as into Rydberg states. These transitions are
observable as sharp features directly below the corresponding
absorption edge (carbon K, oxygen K etc.). Above the

8. SOMERS ET AL. Molecules at Surfaces in Ultrahigh Vacuum 113
photoionisation threshold further transitions into higher-lying

anti-bonding v i r t u a l m.o.'s w i l l occur, their broad spectral
features being superimposed on the background continuum absorption.
A l l these features associated with the existence of the molecular
potential constitute the near edge x-ray absorption fine structure
(NEXAFS) or x-ray absorption near edge structure (XANES). At higher
energies above the edge further very weak structure may be v i s i b l e
due to a scattering phenomenon. This i s the extended x-ray
absorption fine structure (EXAFS) resulting from interference
between the emitted photoelectron wave and waves backscattered from
other atoms in the molecule. (The excitation into anti-bonding
m.o.'s above the threshold may also be viewed as EXAFS-type
scattering resonances. Hence the term "shape" resonance: the energy
and width of the features depends on the shape of the molecular
potential.) When the molecule i s placed on the surface, several
factors come into play. F i r s t l y , the experiment has to be performed
quite d i f f e r e n t l y . Since the substrate i s usually a compact s o l i d
surface, a measurement
i s no longer feasible
y i e l d of Auger electrons, or the high energy portion of the
secondary electrons (partial electron yield) are measured, both
signals being proportional to the number of excited core electrons
in the immediate surface region. Upon adsorption the near edge
resonances may be shifted and their degeneracy l i f t e d or they may
even disappear as a result of the formation of the bond to the
substrate. New resonances (so-called substrate resonances) may be
observed. Since the chemisorption process invariably results in a
molecule with a single, fixed orientation and since the excitations
are subject to dipole selection rules, the transitions in NEXAFS
are polarised. This forms the basis for the determination of
molecular orientation.
Since the surface atoms are l i k e l y to be r e l a t i v e l y strong
backscatterers the extended fine structure w i l l be dominated by the
scattering from the substrate. This r e l a t i v e l y weak modulation at
higher energy i s referred to as the surface EXAFS, or SEXAFS. An
analysis of the SEXAFS can give further structural information,
most valuably, on the adsorption s i t e (for further d e t a i l s , see
Ref. [2]).
In photoelectron spectroscopy, shown schematically in Figure
1b, the electrons emitted as a result of their excitation into
states above the photoionisation threshold are analysed according
to their kinetic energy. The energy balance i s given simply by hv =
EB + EK, where EB i s the energy of a bound level and EK the k i n e t i c
energy of the photoemitted electron. The technique i s often
referred to as XPS (x-ray photoelectron spectroscopy) or ESCA
(electron spectroscopy for chemical analysis), the l a t t e r being the
o r i g i n a l acronym proposed by K. Siegbahn. If the photon energy i s
low (hv < 50 eV), such that essentially only valence electrons are
excited, then we normally refer to UPS ( u l t r a - v i o l e t photoelectron
spectroscopy) or simply photoemission. At these low photon energies
the photoionisation cross-section for valence (or outer s h e l l )
electrons i s also highest. For a molecule on a surface the primary
excitation i s a dipole transition from a molecular orbital,
modified by the interaction with the substrate, into a continuum

c) Photoelectron diffraction
Figure 1: Schematic representation of the three techniques (a)

x-ray photoabsorption (NEXAFS/SEXAFS), (b) photoelectron spec-
troscopy (photoemission) and (c) photoelectron d i f f r a c t i o n .

l e v e l . The same photoabsorption selection rules thus apply as in

NEXAFS. Whereas in NEXAFS, however, the f i n a l state i s a bound or
continuum level associated with the molecule i t s e l f and thus of
(potentially) known symmetry, the final state continuum
wavefunction in photoemission must be selected in an angle-resolved
experiment. When the molecular orientation i s also known, the
symmetry of the i n i t i a l state can be determined. How this procedure
can be used in assignment w i l l become clear in the examples below.
In photoemission there i s an interesting experimental variation
known as constant i n i t i a l state (CIS) spectroscopy, in which the
photon energy and the analysed kinetic energy are scanned
simultaneously. For the excitation out of a given occupied l e v e l , a
whole range of f i n a l states i s then sampled. This approach i s
p a r t i c u l a r l y useful in band structure studies of s o l i d s when the
momentum, or wavevector, of the f i n a l state i s also know, i . e . when
the emission direction i s also defined. By the same token, a
d i f f e r e n t i a l p a r t i a l cross-section i s measured in such an expe-
riment on a free molecule
integrated, meaning tha
collected, then the photoabsorption spectrum, or p a r t i a l photo-
ionisation cross-section, should be obtained. Putting the molecule
(or an atom) on a surface and taking a CIS spectrum of a core l e v e l
introduces, in the same way as in SEXAFS, scattering from the
substrate (Figure 1c). The resulting interferences, which depend on
the adsorption s i t e and orientation modulate the differential
cross-section; the phonomenon is normally referred to as
photoelectron d i f f r a c t i o n (PED). It has recently been shown that
the modulations in intensity are of the order of 50% of the
background signal in experiments on the C and 0 1s levels [5].
(Photoelectron d i f f r a c t i o n effects are also observed when the
photoelectron emission angle i s varied at fixed photon energy [6].
It i s thus sensible to distinguish between energy-scanned and angle-
scanned PED.) By performing model calculations for a given
structure and emission direction and comparing with experiment,
information on adsorption s i t e and orientation i s obtained. How
does the technique relate to SEXAFS? By varying the photon energy
in PED the scattered electron intensity i s distributed between the
various f i n a l state manifolds corresponding to different emission
directions. If i t were possible to angle-integrate over the whole
photoelectron current, then we would recover the SEXAFS s i g n a l .
Again, i t i s essentially the difference between a p a r t i a l cross-
section and a d i f f e r e n t i a l p a r t i a l cross-section. Before concluding
this section i t should perhaps be noted that SEXAFS has so far been
more successful in surface structural studies than photoelectron
d i f f r a c t i o n , largely because multiple scattering effects can be
neglected. On the other hand, the potential of PED has not yet been
f u l l y realised; we show some PED data below which i l l u s t r a t e t h i s
point.
Some examples
Nif 1001-C0. Figure 2 shows the NEXAFS at the C and 0 1s edges for
CO adsorbed on a Ni{100} surface at half-monolayer coverage [7].
This surface concentration corresponds to the formation of an

a) C1s b) 0 1 s
V///7///////,
e 20°
E S
Xi
e =90
c
c
1 1 1 —
I —i 1 1 1—
280 290 300 310 530 540 550 560
Photon energy (eV)
Figure 2: NEXAFS at the (a) carbon and (b) oxygen 1s edges for
Ni{100}(/2x/2)R45°-C0.

ordered overlayer designated as (/2x/2)R45° in the standard

notation. In each case spectra for two angles of the e l e c t r i c
vector relative to the surface normal, 8 E = 20° and 90°, are shown.
Two d i s t i n c t resonances can be seen, corresponding to transitions
into the bound 2TT level and into the 6a-derived level in the
continuum. We note the difference in linewidth between these two
features. Equally pronounced i s the different polarisation
dependence in each case. At 8 E = 90° the a resonance i s v i r t u a l l y
absent and the TT resonance strong. At 8 E = 20° the integrated
intensity of the a resonance i s larger than that of the TT. Starting
from the dipole matrix element <f|x|i> for an electronic
transition, i t i s easy to show [8] that for an isolated, oriented
diatomic the a resonance i s polarised along the molecular axis and
the TT resonance in a plane perpendicular to that axis. The corres-
ponding angular dependences are given by I (a) — P cosâ and I ( TT ) ~- 1
- P cosâ, where a i s the angle between the C-0 axis and the E
vector and P the degree of polarisation of the incident l i g h t . I f
the molecule i s adsorbe
surface, which we migh
this system (and there have been many!), the effective symmetry
either remains C<x,v or i s reduced to Cl| v
o r
^2v depending on the
adsorption s i t e [9]. For present purposes i t i s important to
remember that the symmetry axis remains and that the simple
polarisation dependences above s t i l l hold. Should the molecule be
t i l t e d , the symmetry w i l l drop to C and the degeneracy of the TT
s
o r b i t a l w i l l be l i f t e d . S t r i c t l y speaking, i t i s then no longer

possible to determine the angle of the C-0 axis r e l a t i v e to the
surface. This i s because the a resonance and the a' component of
the TT resonance are no longer polarised p a r a l l e l and perpendicular
to the molecular axis. They are now polarised in the single
,!
symmetry plane; the Tr(a ) component i s polarised perpendicular to
that plane. In practice, however, i t i s generally found that the a
resonance i s unaffected by the lowering of symmetry. Even the TT
resonance may not be strongly affected; the test for this of course
is the observation of a measurable s p l i t t i n g .
A simple procedure presents i t s e l f as a result of the above
discussion. We f i t calculated polarisation dependences to the
experimental data, also allowing for the p o s s i b i l i t y of a random
azimuthal orientation. If the molecule appears to be adsorbed per-
2
pendicular to the surface, the use of the cos a formulae i s
retrospectively j u s t i f i e d . If a t i l t angle emerges, then i t s value
might possibly be incorrect, unless only the a resonance has been
used in the analysis. The results from the oxygen edge for
Ni{100}(/2x/2)R45°-C0 are shown in Figure 3. The TT i n t e n s i t i e s
normalised to the edge jump have been plotted as a function of 6 E ,
the angle between the E vector and the surface normal. The data
show that the molecular axis i s perpendicular to the surface to
within 10°. The integration procedure requires that the form of the
background under the resonance i s known. We refrain, however, from
discussing background and normalisation effects here, although they
do give rise to some serious problems. We note for example that the
o resonance does not go to-zero for 0E = 90° in the oxygen data as
i t does in the C data, which i s probably due to an underlying
substrate resonance. For this reason the TT resonance was used for

the analysis; since the molecule i s clearly oriented normal to the

surface, this presents no problem. The a data at the C edge could
have been used but are less r e l i a b l e because of the poorer S/N
r a t i o (and are, incidentally, incomplete!).
Figure 4 shows two angle-resolved photoelectron spectra for CO
adsorbed on the same surface in the (/2x/2)R45° structure [10]. The
corresponding spectrum of the free molecule in the valence region
[11] contains three features due, in order of increasing ionisation
energy, to the 5a, 1TT and 4o orbitals (see inset). On the surface
only two d i s t i n c t adsorbate-derived features are observed, as in
spectrum (a). That this results from overlapping 1 TT and 5a features
can be shown in the following way [12]. Since the molecular axis i s
oriented perpendicular to the surface, the point group remains Coo V
or, i f the influence of the surface i s f e l t [1], i s reduced to C l | v
or C2v (In fact the on-top s i t e i s occupied, giving C4y The

arguments that follow are also valid for the bridge s i t e , however.)
If the photoelectron detector i s placed in the rotational axis or
in a mirror plane of th
be symmetric with respec
This constraint which i s placed on the f i n a l state lf> enables us
to orient the E vector such that the dipole matrix element i s zero
for a particular i n i t i a l state li>. This i s the essence of the
photoemission selection rules referred to above. Figure 4 i s a case
in point. It can be easily shown for the geometry of spectrum (a)
that both a-j and e states (a- and ir-derived, respectively) are
allowed. In the geometry E_L k j o f spectrum (b), where k| i s the
component of photoelectron momentum p a r a l l e l to the surface, a-j
states are forbidden. This i s often referred to as the "forbidden
geometry" experiment. If the interaction with the surface i s weak
(effective point group Ca. ) and multiple scattering unimportant in
v
the f i n a l state, this w i l l also hold when the azimuthal direction

defined by kg no longer correspond to a symmetry plane common to the
adsorbate and the surface [1,13]. In spectrum (b) the 5a- and 4o-
derived o r b i t a l s disappear and we are able to locate the 1TT
o r b i t a l . Since the separation of the 1 TT and 4o features i s roughly
that of the free molecule, i t i s clear that the formation of the
chemisorption bond has resulted in a relative s h i f t of the 5a
feature by about 3 eV: i t s ionisation energy becomes greater than
that of 1TT. Using Koopmans* theorem we can then compare this result
with o r b i t a l energy diagrams resulting from calculations performed
at various levels of sophistication [14]. These generally show that
as the Ni-CO distance decreases in the end-on configuration a l l the
levels s h i f t to lower energies, but only the 5a and 1 TT o r b i t a l s are
s i g n i f i c a n t l y perturbed by the bonding with the substrate. The
energy of the 5o changes most strongly with considerable donation
of charge from this o r b i t a l into the metal. The metal gives back
charge into the C-0 antibonding 2TT* level just as in the donor-
acceptor model of ligand bonding in coordination chemistry. This
concept of charge donation can be misleading and i t i s perhaps more
useful to think in terms of a new set of molecular o r b i t a l s for the
adsorbate/substrate complex. The 2TT* thus overlaps with metal
states of appropriate symmetry and forms an occupied bonding l e v e l
largely of metal character situated energetically somewhere in the
Ni d band. The corresponding anti-bonding level remains largely CO

8. SOMERSET AL. Molecules at Surfaces in Ultrahigh Vacuum 119
Ni(IOO) ( v ^ x ^ 2 ) r U 5 ° - C 0
01s K resonance
I \>
'A
6=30° , < /
P=085,' 1
* Is
P=085
y
0 30 60 90 120
e (°)
E
Figure 3: Polarisation dependence of the * resonance intensity

at the 0 1s edge for Ni{ 100}(/2x/2)R45°-CO. Degree of photoion-
isation, P, of the incident radiation i s taken to be 0.85 f o r
the calculated curve. 6 i s the angle of t i l t of the C-0 axis
r e l a t i v e to the surface normal. The analysis assumes no r e -
duction in symmetry from Cmy
Nit100)(&»&)R45°-CO CO gosphas*
hv=32eV Ik
49
AAA
as60°\» 59
I
Iff
b)
as0*"v..
9 = 5 0 ° "Sv.
—T"
U 12 10 8 6 4
Energy below E (eV) f
Figure 4: Angle-resolved photoelectron spectra f o r Ni{100)

(/2x/2)R45°-C0. hv = 32 eV (a) angle of incidence, a = 60°,
polar angle of emission, 6 = 0°. (b) a = 0°, 6 = 50°, E J L k|.
Inset: Gas phase photoelectron spectrum of CO at the same photon
energy. After [10] and [11].

2TT* in character and i s the unoccupied o r b i t a l giving r i s e to the TT

resonance in NEXAFS. It can also be probed with inverse photo-
emission.
Two further remarks should be made at this juncture. The f i r s t
concerns Koopmans' theorem, which turns out in some cases not to be
such a t r i v i a l approximation. In most photoemission studies to date
i t has simply been assumed that, as far as the relative energies are
concerned, the ionisation potentials can be compared d i r e c t l y with
calculation, i . e . that relaxation indeed plays a role but the s h i f t
i s the same for a l l o r b i t a l s . When intramolecular relaxation and
image charge screening are dominant this may be a reasonable
approximation. In the presence of so-called charge transfer
screening (the " u n f i l l e d o r b i t a l " mechanism), which appears for
example to affect the levels of o symmetry in adsorbed CO, this may
not be the case. The second point concerns dispersion. Due to
l a t e r a l interactions in ordered overlayers, overlap of o r b i t a l s on
adjacent molecules leads to band formation Energy dispersion e(k||)
i s then observable i
emission angle i s varied
w i l l change. This effect can be very pronounced in strongly-bound
atomic overlayers with bandwidths of 2 eV or more, but i s also
observed for molecular adsorbates. In fact, i t was f i r s t observed
for the l a t t e r in the system Ni{100}-C0 [15].
Pdf111]-CN. The usual bonding geometry for an adsorbed diatomic

molecule i s the end-on configuration where the molecular axis i s
perpendicular to the surface, as in the case of Ni[100}-C0
described above. This observation i s consistent with the behaviour
of CO, NO or N2 as ligands in co-ordination chemistry. By the same
token we would perhaps expect a surface CN species also to be
"terminally" bonded via the C atom as i s normally found in cyano
complexes. Surface vibrational spectroscopy has, however, indicated
that surface CN formed by the decomposition of C2N2 on Pd and Cu
surfaces i s adsorbed in a lying-down configuration [16]. This
result has since been confirmed by NEXAFS [17] and has led to a new
consideration of the photoemission data from adsorbed CN [18].
The N 1s NEXAFS from the system Pd{111}-CN i s shown in Figure
5a at two angles 6E = 20° and 90° in an analogous way to Figure 2.
It i s immediately apparent, however, that CN d i f f e r s considerably
in i t s orientation. For CO on Ni{100] the TT resonance i s at a
maximum for the E vector p a r a l l e l to the surface; the o resonance
peaks at 9E = 20° as the E vector approaches the surface normal.
For CN on Pd[111} not only do the features hardly change in
r e l a t i v e intensity, but a s p l i t t i n g of the TT resonance i s also
observed (apparent only as a weak shoulder on the low energy side
of the resonance at the r e l a t i v e l y low resolution of F i g . 5). This
indicates a C s point group. By consideration of the polarisation
dependence of the two components, i t can be shown that the a"
component dominates at p r a c t i c a l l y a l l angles. This i s p a r t i c u l a r l y
useful because the a/7r(a") intensity ratio can then be used for the
analysis, thus avoiding the need for normalisation (but not solving
the background problem!). Allowing for a random azimuthal orien-
tation of molecules the expected ratio i s given by I(o)/I(a") ~
2 2
[1 + P c o s 6E]/[1 - P c o s eg]. As expected, this does not give

Figure 5: (a) N 1s NEXAFS from the system Pd{100]-CN at 8 E = 20°

and 90° (b) Polarisation dependence of the O / T T intensity r a t i o .
P = 0.85. After [17].

any information on the t i l t of the CN axis. If we assume, however,

that the a resonance i s unaffected by the reduction in symmetry,
i.e. the effective point group remains Ca> , we can replace the
v
2 2 2 2 2
numerator by P(sin 8sin 6E + 2 c o s 8 c o s 9E) + (1-P)sin 8, where 8 i s
the angle of t i l t relative to the surface normal. For a p a r a l l e l -
bonded species this reduces to 1-P C O S 6 E and the intensity r a t i o
2
becomes constant. As the experimental data of Figure 5b show, the

r a t i o i s not quite constant and a best f i t to the calculated curve
is obtained for 8= 76° (± 5°). Since an angle of 14° r e l a t i v e to
the plane i s rather unlikely on a close-packed surface, we suspect
that the molecule i s indeed parallel-bonded and that some other
source of error i s responsible for the deviation. The most l i k e l y
candidate i s again a substrate scattering feature under the a
resonance: Note the small s h i f t in the energy of the a resonance
between 6E = 90° and 0E = 20° in the spectra of Figure 5a.
Although the C-N axis l i e s p a r a l l e l , or nearly p a r a l l e l , to the
metal surface, i t i s only the knowledge of the appropriate point
group which helps u
photoemission selectio
symmetry plane and the molecules show a random azimuthal
orientation, i t i s not possible, however, to perform the analysis
as above for CO. In fact, the i n t r i n s i c a l l y low symmetry prevents
conclusive experiments involving particular emission directions for
defined orientations of the E vector. The spectra in Figure 6 taken
for different polar and azimuthal emission angles at hv = 35 eV
show four adsorbate-derived features at 5- , 6.1, 7. and 9.1 eV.
2 2
Some limited success was obtained with the same forbidden geometry
experiment as above for Ni{100}-C0, although this i s , s t r i c t l y
speaking, not applicable in the present case. At 9= 70° a consider-
able reduction in the intensity of peaks 1 and 3 i s obtained on
going from E ||k|j(c) to E J L k| (d). Emission from a' o r b i t a l s i s only
forbidden for E ± k| when the E vector i s perpendicular to the
single symmetry plane. For randomly oriented symmetry planes the
reduction in intensity in this "forbidden" geometry should, at the
most, only be factor of 0.5. How many levels are expected and what
is their symmetry? From the NEXAFS we know that the lowest
unoccupied l e v e l ( s ) are 2iT-derived. The 5o- and 1-rr-derived o r b i t a l s
are thus f i l l e d and the molecule i s adsorbed essentially as CN"*.
The chemisorption bond appears to derive i t s strength mainly from
the interaction of this anionic species with i t s image charge. In
this situation we might expect a s h i f t i n g and s p l i t t i n g of the
o r b i t a l s to be the main effect rather than a rehybridisation. The
four levels are then expected to correspond to 4a, 5a, iTr(a') and
1ir(a"). On the basis of the "forbidden" geometry experiment and
other, qualitative arguments a preliminary assignment has been made
in which peaks 1 and 3 are attributed to the 5o- and 1 TT(a')-derived
levels, respectively. Peak 2, which i s the strong feature in normal
emission, appears to be 1 IT(a")-derived. The most certain assignment
is peak 4 at 9.1 eV which i s 4o-derived. Because of the low
symmetry, mixing between 4o, 5o and iTf(a') i s also possible.
Unfortunately, the cluster calculations that exist assume the end-
on adsorption geometry and a comparison with calculation i s at
present not possible.

8. S O M E R S E T AL. Molecules at Surfaces in Ultrahigh Vacuum 123
Pdfl11>-CN hv=35eV
b) / \
en
^ 0
EHk. \ /
d) ^-20
1 III '
A 3 2 1
W O
T 1 1 1 T"
10 5 E F
Binding energy (eV)
Figure 6: Angle-resolved photoemission spectra for Pd{111)-CN.

hv = 35 eV. (a) a = 70°, 8 = 0° (b) a = 70°, 6 = 20° (c) a = 0°,
9 = 70°, E ||k|(d)a = 0°, 8 = 70°, E l l q . After [18].

Cu(1101-HC00 The decomposition of formic acid on metal and oxide

surfaces i s a model heterogeneous reaction. Many studies have since
shown that i t proceeds via a surface formate species. Thus on
Cu{110} adsorbed formic acid i s found at low temperature. On
heating to - 270 K deprotonation occurs, giving r i s e to the surface
formate, which in turn decomposes at - 450 K with evolution of H2
and CO2. In previous studies, particularly with vibrational
spectroscopy, i t had been demonstrated that the two C-0 bonds are
equivalent and that the symmetry i s probably C2v [ 1 9 ] . A NEXAFS
study by Puschmann et al. [20] has subsequently shown that the
molecular plane i s oriented perpendicular to the surface and
aligned in the <110> azimuth.
Figure 7 shows NEXAFS spectra at the oxygen edge from the
system Cu[110}-HC00 with the E vector aligned in (a) the <110>
azimuth and (b) the <100> azimuth. The ir-type resonance corresponds
to excitation into the 2b2 o r b i t a l and i s expected to be polarised
perpendicular to the molecular plane. There are actually two o-type
resonances, correspondin
actually be resolved [ 2 1 ]
that the intensity of the TT resonance varies d r a s t i c a l l y as the
angle between the E vector and the surface normal i s changed. In
<110> this effect i s hardly observed, indicating that the molecular
plane i s perpendicular to the surface and aligned in the <110>
azimuth, i . e . p a r a l l e l to the atom rows of the {110} surface. (The
measurable intensity in the TT resonance when the E vector i s
oriented in the <110> azimuth i s due to incomplete polarisation of
the incident radiation.) This qualitative conclusion i s supported
by comparing the 9 E = 90° spectra in Figures 7a and 7b ( f u l l
l i n e s ) . Here we observe a drastic change in the T T / O intensity r a t i o
as the E vector ( p a r a l l e l to the surface) i s moved around from the
<110> to the <100> azimuth. A quantitative analysis of the polar
angular dependence in the <100> azimuth indicates that the
molecular plane i s indeed perpendicular to the surface, the
accuracy of the determination being ± 10° [ 2 0 ] .
Puschmann et al. also carried out a SEXAFS analysis giving an
adsorption s i t e shown as A in the inset to Figure 8. The adsorption
s i t e of the formate species on copper surfaces in general has,
however, proved to be controversial [22,23]. Most recent
photoelectron d i f f r a c t i o n data has indicated that i t i s the same
s i t e on both Cu{100} and Cu{110] and that the "aligned bridge s i t e "
(B) i s most l i k e l y . We show the corresponding photoelectron
d i f f r a c t i o n data in Figure 8 without any calculated curves or any
discussion of the level of theory-experiment agreement since this
w i l l be the subject of a forthcoming paper [24]. It has already
been mentioned above that PED d i f f e r s from SEXAFS in that a
d i f f e r e n t i a l p a r t i a l cross section i s measured. Whilst this results
in a smaller absolute signal in PED, the actual intensity
modulations are about an order of magnitude greater. In addition,
the nature of the structural information sampled d i f f e r s and the
technique i s sensitive to both distance and real space direction of
the scatterers. The adsorption s i t e information i s thus more
d i r e c t l y involved in establishing the observed interferences than
in SEXAFS, although the precision obtained for bond lengths may be
lower. Nevertheless, even at the level of qualitative comparison,

0 <110> azimuth
G =90° / *
E
\ /" "
1/ N \
V \
e =20 ,'~"7
E
o
a)
ii
<100> azimuth
< le =90°
E
0
1
N
1 1 \
\ \ * \9 = 20°
1 1 /^~N
F
1 1 /
7
/
1 ~\' /
\ 1 \ /
i'
fi
1/
//
Jl
b)
530 5A0 550 560

Photon energy (eV)
Figure 7: 0 1s NEXAFS from the surface formate species on

Cu{110}. The E vector i s aligned in (a) the <110> azimuth and i n
(b) the <100> azimuth. After [20].

the data shown in Figure 8 from the two Cu surfaces are so similar
that they cannot be reconciled with two completely different
adsorption s i t e s as suggested by the o r i g i n a l SEXAFS studies
[20,22].
Having established the orientation of the formate species on
the surface we can proceed to examine the photoemission data.
Figure 9 shows the effect of deprotonation of adsorbed formic acid
which occurs on warming the surface to above ~ 270 K. Spectrum (a)
can be assigned by comparison with the photoelectron spectrum of
the free molecule. The formate species also gives r i s e to four
spectral bands and, since the number of expected o r b i t a l s i s the
same, i t i s tempting to assume a one-to-one correspondence,
allowing of course for the change in symmetry from C to C2v s The
application of selection rules proves, however, that such an
assignment i s incorrect [25].
Figure 10 shows three spectra at hv = 25 eV with the E vector
p a r a l l e l to the surface and aligned along the <110> azimuth, i . e .
oriented in the molecula
(b) was obtained at norma
selection rules t e l l us that only levels belonging to bi in C2v w i l l
be observed. This immediately assigns two features in the spectrum
at 4.8 eV and 9.6 eV below EF. By moving the detector off-normal
into the <100> azimuth (spectrum (a), E J_ k|) emission from a2
states should be observed as well. Whereas peak 3 remains in the
same place peak 1 s h i f t s s l i g h t l y to lower binding energy indicat-
ing that i t also contains a level of a2 symmetry. Similarly, by
moving the detector off-normal into the <110> azimuth (spectrum
(c) , E || kg) ai, and bi, states are expected. Under these conditions
peak 1 moves up in binding energy, as does peak 3. In addition,
peak 4 i s observed. Thus three ai, states are also present. Peak 2
i s only v i s i b l e with E _L kj for non-normal incidence (not shown in
Figure 10), indicating that i t belongs to b2. By performing further
confirmatory experiments at other orientations of the E vector, in
particular when i t i s aligned in the <110> azimuth, a complete
assignment i s possible. Peak 1 contains three bands due to 1a2(ir),
4bi(o) and 6ai,(o) at 4.7, 4.8 and 5.1 eV below Ep, whereas peak 2
consists only of 1b2(TT) at 7.8 eV. Peak 3 contains 3bi,(a) and
5ai(o) at 9.6 and 9.7 eV; peak 4 i s due to 4ai.(o) at 13.0 eV. These
measured ionisation energies have been compared with HF-SCF
calculations for the formate ion [26] as well as with an IND0
Cu{110}-HC00 cluster calculation [27]. The relative orbital
energies from the latter, semi-empirical treatment are in
reasonable agreement with the measured binding energies although
the absolute values, as expected, are way out. The important
result from this calculation i s the correct assignment of the
1
photoelectron spectrum (via Koopmans theorem), in particular that
three levels are expected in the f i r s t band and only one in the
r
second. An analysis of the percentage ormate character in the
adsorbate-derived orbitals reveals that the 1a2, 4bi, and 6a 1,
o r b i t a l s are most strongly involved in the chemisorption bond.
Relative to the formate ion, surface formate has both lower a and TT
populations but the o population difference i s the greater. The TT
donation occurs mainly via the 1a2 o r b i t a l ; the strongest a donor

8. SOMERSET AL. Molecules at Surfaces in Ultrahigh Vacuum 127
A B
(JUU o o o
.** *u
-•*
cunbo)
Vs
a)/
0)
D °
*Q.
£ 6-
<
3H
100 200 300 400

Kinetic e n e r g y (eV)
Figure 8: Photoelectron d i f f r a c t i o n data (normal emission) f o r

the surface formate species on (a) Cu{100} and (b) Cu{110}.
Insets: A) The aligned atop s i t e and B) the aligned bridge s i t e .
After [ 5 ] .
a)
HCOOH(ad) Cu d band
a
? .\ /»ar.
la * "\ 2a
270 K
i , 1 1 1—
15 10 5 0
Energy below E p (eV)
Figure 9: (a) Photoelectron spectrum of adsorbed formic acid on

Cu{110} and (b) corresponding spectrum after formation of the
formate species above ~ 270 K. hv = 25 eV, a = 6 0 ° , E ||<110>, 9 =
6 0 ° in the <100> azimuth. After [ 2 5 ] .

1 r
15 10 5
Energy below E p (eV)
Figure 10: Angle-resolved photoelectron spectra from the system

Cu{110}-HC00 for three different emission angles, hv = 25°,
E ||<110>. After [25].

i s the 4bi, o r b i t a l . C l a s s i c a l back-bonding i s neglible because the

empty 2b2 o r b i t a l i s too high in energy.
Concluding remarks
The three examples show how the approach outlined i n the f i r s t two
sections can be successfully implemented to obtain information on
the structure and bonding of molecules and molecular fragments
adsorbed on surfaces. The system Ni{100}-C0 i s perhaps already too
well investigated and correspondingly documented to induce any sur-
prise. Moreover, i t s properties are exactly those that might have
been predicted on the basis of coordination chemistry. Not so the
system Pd{111}-CN, where the p a r a l l e l , or nearly p a r a l l e l , adsorp-
tion geometry i s confirmed and the consequences f o r the bonding
scheme are investigated. Here, the lack of an appropriate quantum
chemical calculation for adsorbed CN i s a serious drawback to
further understanding of thi interestin system Perhap th
textbook example of th
emission and theory i
are concerned here with a polyatomic surface intermediate i n a
heterogeneous reaction, the properties of which cannot be predicted
by reference to those of a free molecule. The almost complete
characterisation of the formate species on Cu{110} using a variety
of surface techniques, not least those based on photoabsorption and
photoionisation phenomena, might be regarded as an important
advance in surface chemistry.
Acknowledgments
This work has been supported financially by the Deutsche

Forschungsgemeinschaft through the Sonderforschungsbereich 6-81 and
by the Fonds der Chemischen Industrie. We also acknowledge the
contribution of our colleagues H. Conrad, R. Hemmen, P. Hollins, D.
Kilcoyne, R. Klauser, M. Kordesch, M. Surman, G. P. Williams and D.
P. Woodruff who have been associated with some of the work reviewed
in this a r t i c l e .
Literature Cited
1. Richardson, N. V.; Bradshaw, A. M. In Electron Spectroscopy:

Theory, Techniques and Applications: Baker, A.; Brundle, C. R.,
Eds.; Academic Press: London, 1981; Vol. 4, p. 153.
2. Stöhr, J . In Chemistry and Physics of Solid Surfaces;Vanselow,
V. R.; Howe, R., Eds.; Springer Ser. Chem. Phys; Springer-
Verlag: Berlin, Heidelberg 1984; Vol. 35, p. 231; Haase, J .
Appl. Phys. 1985, A38, 181.
3. Barton, J . J . ; Robey, G. W.; Shirley, D. A. Phys. Rev. 1986,
B34, 778 ; Woodruff, D. P. Surface S c i . 1986, 166, 377.
4. Johnson, R. L. In Handbook on Synchrotron Radiation; Koch,
E.-E., Ed.; North Holland: Amsterdam; 1983; Vol. 1, p.173.
5. McConville, C. F.; Woodruff, D. P.; Prince, K. C.; Paolucci,
G.; Cháb, V.; Surman, M.; Bradshaw, A. M. Surface S c i . 1986,
166. 377; Woodruff, D. P.; Kilcoyne, A. L. D.; McConville, C.

F.; Lindner, Th.; Somers, J . ; Surman, M.; Bradshaw, A. M.

Vacuum, i n press.
6. Fadley, C. S. Phys. Scripta 1987, T17, 39.
7. Somers, J . ; Hollins, P.; Lindner, Th.; Bradshaw, A. M.
unpublished results.
8. Somers, J . S.; Lindner, Th.; Surman, M.; Bradshaw, A. M.;
Williams, G. P.; McConville, C. F.; Woodruff, D. P. Surface
S c i . 1987, 183, 576.
9. Klauser, R.; Spieß, W.; Bradshaw, A. M.; Hayden, B. J . E l e c t .
Spec. Rel. Phen. 1986, 38, 187 and references therein.
10. Klauser, R.; Surman, M.; Lindner, Th.;Bradshaw, A. M. Phys.
Scripta 1987, 35, 561.
11. Plummer, E. W.; Gustafsson, T.; Gudat, W.; Eastman, D. E. Phys.
Rev. 1977, A15, 2339.
12. Allyn, C. L.; Gustafsson; T.; Plummer, E. W. S o l . State Commun.
1977, 24, 531.
13. Scheffler, M.; Bradshaw A M In The Chemical Physics of Solid
Surfaces and Heterogeneou
D. P., Eds.; Elsevier
14. There are many of these for Ni{100}-CO, we c i t e here an early
one and a recent one. Cederbaum, L. S.; Domcke, W.; von
Niessen, W.; Brenig, W. Z. Phys. 1975, B21, 381; Sung, S.-S.;
Hoffmann, R. J . Am. Chem. Soc. 1985, 107, 578.
15. Horn, K.; Bradshaw, A. M.; Jacobi, K. Surface S c i . 1978, 7 2 ,
719.
16. Kordesch, M. E.; Stenzel, W.; Conrad, H. Surface S c i . 1987,
186, 601.
17. Somers, J . ; Kordesch, M. E.; Lindner, Th.; Conrad, H.;
Bradshaw, A. M.; Williams, G. P. Surface S c i . 1987, 188, L693;
Spectrochimica Acta 1987, 43A, 1561.
18. Somers, J . ; Kordesch, M. E.; Hemmen, R.; Lindner, Th.; Conrad,
H.; Bradshaw, A. M. Surface S c i . , in press.
19. Hayden, B. E.; Prince, K. C.; Woodruff, D. P.; Bradshaw, A. M.
Phys. Rev. Lett. 1983, 51, 475.
20. Puschmann, A.; Haase, J . ; Crapper, M. D.; Riley, C. E.;
Woodruff, D. P. Phys. Rev. Lett. 1985, 57, 2598.
21. Somers, J . ; Lindner, Th.; Bradshaw, A. M., to be published.
22. Stöhr, J . ; Outka, D.; Madix, R. J . ; Döbler, U. Phys. Rev. Lett.
1985, 54, 1256.
23. Crapper, M. D.; Riley, C. E.; Woodruff, D. P. Surface Sci.
1987, 184, 121.
24. Woodruff, D. P.; McConville, C. F.; Kilcoyne, A. L. D.;
Lindner, Th.; Somers, J . ; Surman, M.; Paolucci, G.; Bradshaw,
A. M. Surface S c i . , in press.
25. Lindner, Th.; Somers, J . ; Bradshaw, A. M.; Williams, G. P.
Surface S c i . 1987, 185, 75; Hofmann, P.; Menzel, D. Surface
S c i . , in press.
26. Peyerimhoff, S. D. J . Chem. Phys. 1967, 42, 349.
27. Rodriguez J . A.; Campbell, C. T. Surface S c i . 1987, 183, 449.
RECEIVED July 12, 1988

Chapter 9
Kinetics of Ethylidyne Formation

on Platinum(111) Using Near-Edge
X-ray Absorption Fine Structure
1 2 3
F. Zaera , D. A. Fischer , R. G. Carr ,
4 4
E. B. Kollin , and J . L. Gland
1
Department of Chemistry, University of California, Riverside,
2
National Synchrotron Ligh
Upton, NY 11973
3
Stanford Synchrotron Radiation Laboratory, P.O. Box 4349-Bin 69,
Stanford, CA 94305
4
Corporate Research Science Laboratory, Exxon Research & Engineering
Company, Annandale, NJ 08801
The k i n e t i c s of ethylidyne formation from
chemisorbed ethylene on Pt(111) surfaces was studied
by using near-edge x-ray absorption f i n e structure
(NEXAFS). The feasibility of using t h i s technique
f o r studying rates of reactions was s u c c e s s f u l l y
tested f o r s a t u r a t i o n and sub-monolayer initial
coverages of the reactants. Ethylidyne formation
rates are first order in ethylene coverage over the
entire range studied. A s u b s t a n t i a l isotope e f f e c t
was observed; normal ethylene reacts about twice as
f a s t as fully deuterated ethylene. We obtained
a c t i v a t i o n energies of 15.0 and 16.7 Kcal/mole f o r
C H and C D , respectively. Hydrogen
2 4 2 4
thermal desorption spectra (TDS) were obtained f o r

both i s o t o p i c isomers. They also y i e l d e d first order
k i n e t i c s and a noticeable isotope e f f e c t . Analysis
of the hydrogen desorption peak shapes assuming a
single rate l i m i t i n g r e a c t i o n r e s u l t s in values f o r
the a c t i v a t i o n energy about 3 Kcal/mole higher than
those obtained from the isothermal NEXAFS k i n e t i c
experiments. However, these differences can be
explained by including a hydrogen recombination step
i n the i n t e r p r e t a t i o n of the TDS data.
The chemisorption and thermal decomposition of ethylene over

platinum (111) surfaces have been extensively studied by several
groups using a range of modern surface science techniques (1-3) .
Chemisorption at low temperatures i s molecular, with the
0097-6156/88/0378-0131$06.00/0

carbon-carbon bond axis p a r a l l e l to the surface and a carbon-carbon

bond length of 1.49A (4.5). Thermal desorption experiments
indicate that dehydrogenation occurs i n a stepwise fashion s t a r t i n g
around room temperature (2). After the loss of one hydrogen,
ethylene rearranges to form a new moiety, ethylidyne (^CCH^), i n
which the carbon-carbon bond stands perpendicular to the surface i n
a three-fold hollow s i t e with the a carbon bonded to three platinum
atoms and three hydrogens bonded to the ft carbon (6.7). Additional
dehydrogenation above 450K results i n the formation of hydrocarbon
fragments with C H stoichiometry, where x has a value between one
x
and two.
Although the structures of chemisorbed ethylene and ethylidyne
have been c a r e f u l l y established, the mechanism by which ethylene
transforms into ethylidyne remains a mystery. Understanding the
r e a c t i v i t y of these adsorbed hydrocarbons i s p a r t i c u l a r l y important
i n view of t h e i r role during the c a t a l y t i c hydrogenation of
ethylene. We have recently shown (8.9) that the steady state
c a t a l y t i c hydrogenation
and atmospheric pressure
i n the presence of either an ethylidyne layer or a related
hydrocarbon fragment. In order to explain these r e s u l t s , we have
proposed a mechanism i n which hydrogen atoms may be transferred from
the platinum surface to ethylene molecules weakly chemisorbed on a
second layer on top of the strongly bonded carbonaceous moieties.
We suspect that the intermediate(s) involved i n the conversion of
ethylene into ethylidyne are c l o s e l y related to those intervening i n
the mechanism f o r ethylene hydrogenation described above.
In this report we present NEXAFS results f o r the k i n e t i c s of
ethylidyne formation. Previous data i s scarce and comes mostly from
thermal desorption (TDS) experiments (2) . The only reported study
of isothermal rates of reactions for this system was done by Ogle
et. a l . using secondary ion mass spectrometry (SIMS) (10).
However, due to the d i f f i c u l t i e s i n c a l c u l a t i n g ion y i e l d s i n SIMS,
quantitation of the data i s not very r e l i a b l e , and t h e i r work was
not conclusive. We have determined here that the reaction of
chemisorbed ethylene to form ethylidyne i s f i r s t order i n ethylene
coverage. A noticeable isotope e f f e c t was observed, with a c t i v a t i o n
energies of 15.0 and 16.7 Kcal/mole f o r ^n^h a n d C
2 4 D
respectively. These values are smaller than those calculated from

TDS, but the differences can be reconciled by including the
recombination of hydrogen atoms on the surface i n the interpretation
of the thermal desorption experiments.
Experimental
The NEXAFS experiments were performed at the Stanford Synchrotron

Radiation Laboratory, beamline 1-1. This l i n e i s equipped with a
grasshopper monochromator, 1200 lines/mm, as described elsewhere
(11). The entrance and e x i t s l i t s were set at 15/zm, y i e l d i n g a
r e s o l u t i o n of AE/E=8 x 10 E (E i n eV); f o r l i g h t of 300 eV photon
energy i t resulted i n a linewidth of about 0.7 eV. We estimate the
t o ^ a l photon f l u x under those conditions to be on the order of 1 x
10 photons/sec. at 300 eV and f o r a r i n g current of 50 mA.

9. ZAERA ETAL. Ethylidyne Formation on Pt (111) 133
The end s t a t i o n consisted of a u l t r a - h i g h vacuum chamber pumped

w i t ^ a n ion and a T i sublimation pump to a base pressure i n the
10 torr range. I t was equipped with a c y l i n d r i c a l mirror
analyzer for Auger electron spectroscopy (AES), LEED optics, and
sputtering and gas dosing f a c i l i t i e s . The sample (a P t ( l l l ) c r y s t a l
prepared using standard procedures) was mounted on a manipulator for
alignment with respect to the incident beam, and could be cooled to
130K and r e s i s t i v e l y heated above 1200K. Temperatures were measured
with a type K thermocouple spotwelded to the edge of the c r y s t a l .
The sample was cleaned by Ar ion bombardment followed by annealing
to HOOK or by oxygen treatment at 900K u n t i l no impurities were
detected by AES. A l l spectra reported here were taken at saturation
coverages, that i s , a f t e r exposure to 10L of ethylene at
temperatures below 150K (1L=1X10~ t o r r . s , pressure corrected for
ion gauge s e n s i t i v i t y ) .
NEXAFS spectra were c o l l e c t e d by using a p a r t i a l electron y i e l d
(PEY) detector. This detecto consisted f channel-plate abou 5
cm i n diameter, located
of about 45° below the synchrotro
placed i n front of the channel-plate i n order to apply a retarding
f i e l d of — 2 0 0 V o l t s , so most of the secondary electrons emitted by
photon e x c i t a t i o n could be rejected, reducing the corresponding
background signal and the noise l e v e l . Photon energies were
c a l i b r a t e d using the strong absorption feature at 291.0 eV i n the
incoming beam due to carbon deposited on the beam l i n e optics
(12).
NEXAFS spectra were taken at glancing and normal incidence angles

for both ethylene and ethylidyne. Ethylene spectra were taken a f t e r
dosing at low temperatures, while ethylidyne data were acquired
a f t e r f l a s h i n g to 300K for 60 seconds. We obtained spectra
i d e n t i c a l to those previously reported (13). Figure 1 shows the
spectra obtained for ethylene and for ethylidyne at normal
incidence. The spectrum for ethylidyne displays a peak at 285.8 eV
while no features are seen i n that energy range f o r chemisorbed
ethylene. We c a r r i e d out our k i n e t i c experiments by following the
absorption signal at 285.8 eV photon energy and normal incidence.
The rate of ethylidyne formation was measured by recording the
p a r t i a l electron y i e l d signal as a function of time a f t e r s e t t i n g
the c r y s t a l temperature to a preestablished value. An example of
the r e s u l t s i s shown i n Figure 2 for the conversion of C^D^ at
264K. A jump i n the signal due to ethylidyne formation i s c l e a r l y
observed immediately a f t e r heating the sample (t = 0). The figure
i l l u s t r a t e s some t y p i c a l c h a r a c t e r i s t i c s of these experiments.
F i r s t , the background signal i s on the order of 8x10 counts per
second ( c / s ) ^ while the signal due to saturation of ethylidyne i s
about 2.5x10 c/s, y i e l d i n g a signal-to-background r a t i o of about
3% (note that each point represents counting for 10s). The absolute
noise, on the other hand, i s close to s t a t i s t i c a l (below 25 c/s for
10s counting time per point), so the signal-to-noise i s better than
10%. These values assure the f e a s i b i l i t y of the k i n e t i c experiments
even f o r s t a r t i n g coverages below 10% of saturation.
Similar experiments were done at several temperatures s t a r t i n g
with e i t h e r normal or f u l l y deuterated ethylene chemisorbed on

Pt (111), Saturated Overlayers, Normal Incidence
0.2 v/pt 4 s/pt
—I I I
275 300 325
Photon Energy (eV)
F i g . 1. NEXAFS spectra of ethylene (T-90K) and ethylidyne

(T=300K) chemisorbed on P t ( l l l ) f o r normal incidence. The d i f f e r -
ence between the spectra i s also shown to indicate the maximum f o r
ethylidyne a t 285.8 eV photon energy.

9. ZAERA ETAL. Ethylidyne Formation on Pt(l11) 135
P t ( l l l ) surfaces. The data was then normalized and p l o t t e d i n a

semilogarithmic fashion (Figure 3). These plots yielded s t r a i g h t
l i n e s , i n d i c a t i n g that the rate of reaction i s f i r s t order with
respect to ethylene coverage. The l i n e a r i t y of the graphs break
down i n the f i r s t few seconds of each run because of the time needed
for the c r y s t a l temperature to e q u i l i b r a t e . I t i s also worth
n o t i c i n g that i n some cases good q u a l i t y data was obtained f o r
coverages down to 3-5% of saturation.
Rate constants were calculated from the slopes of plots such as
H a n d C D
those shown i n Figure 3. The results f o r both C2 4 2 4
are presented i n Ahrrenius plots i n Figure 4. Each rate was
accurate to better than 20%. I t i s clear from the data that the
ethylidyne formation displays a noticeable isotope e f f e c t , s i n c e the
rates f o r normal ethylene are about twice as f a s t as those f o r the
deuterated compound. We calculated values f o r the a c t i v a t i o n energy
of 15.0 ± 1.0 and 16.7 ± 1.0 Kcal/mole f o r C H and C D , 2 4 2 4
respectively. A compensation e f f e c t i s also seen in., the

preexponential factors: 3.6x1
Previous H TDS result
2
297K, due to ethylidyne formation, does not s h i f t i n temperature at

d i f f e r e n t i n i t i a l ethylene coverages, i n d i c a t i n g that the reaction
rate i s f i r s t order (2). Based on these r e s u l t s i t was proposed
that a C-H bond breaking step i s l i m i t i n g f o r that process. The
authors reported values of 18.4 Kcal/mole and 4x10 s" f o r the
a c t i v a t i o n energy and preexponential factor respectively f o r normal
ethylene. Since these values are considerably higher than those
obtained here by NEXAFS, we decided to repeat and extend the thermal
desorption experiments.
H (2 amu) and D (4 amu) TDS from saturation C H^ and
2 2 2
C D, are shown i n Figure 5. The spectrum f o r normal ethylene i s

2
q u a l i t a t i v e l y equal to that reported by Salmeron et. a l . (2) ,

although the peaks occur at s l i g h t l y higher temperatures i n our
case. The hydrogen p a r t i a l pressure r e s u l t i n g from H desorption 2
a f t e r ethylidyne formation peaks at 305K. For deuterated ethylene

the deuterium desorption peaks at 316K, i n d i c a t i n g a slower reaction
rate i n this case. Assuming that the decomposition of ethylene i s a
one step process, analysis of the TDS peak shapes (14) y i e l d s f i r s t
order k i n e t i c s , with a c t i v a t i o n energies of 18.0 and 19.8 Kcal/mole
and preexponential factors of 7.7x10 and 4.7x10 s" . The
values for normal ethylene are, within the experimental errors, the
same as those reported by Salmerbn et. a l .
In order to understand the TDS spectra better, we d i d a computer
simulation of the thermal desorption peaks by integrating the rate
equations f o r a l l the processes involved. Although we believed that
a C-H bond breaking i s the l i m i t i n g step i n most of the TDS
temperature range, hydrogen atom recombination i s a second order
reaction and therefore may a f f e c t the o v e r a l l reaction rate at the
t a i l s of the TDS peaks. This i s indeed what we found i n our
calculations. We calculated TDS p r o f i l e s using our NEXAFS r e s u l t s
for the k i n e t i c parameters of the ethylidyne formation step, and
hydrogen recombination was simulated using data from the thermal

i 1 r n 1 1 r T 1 1 r
8.5 _ C2D4 Decomposition

Pt(lll)
... ...
c
3
O
o
c
(7)
hv
8.
E+04 J I L J I L J I I L
250 500
Time (Seconds)
F i g . 2. Time dependence of the absorption s i g n a l following a
jump i n surface temperature from 130 to 264K f o r ^2^4
chemisorbed on P t ( l l l ) . The photon energy was 285.8 eV,
incident normal to the surface.
-i 1 1 1 1 1 1 1 1 1 r-
Ethylene Conversion to Ethylidyne

on the Pt (111) Surface
E =285.8 eV
hv
1.00
O)
CO ^ - K •••••••••••• 233K
»- </) 0.50
0) c
> 0) •••••• •••••
o >*
. • • 253K
O J2
?!
CD O 0.10
271K 261K
250 500
Time (s)
F i g . 3. Time dependence of the conversion of normal ethylene

adsorbed on P t ( l l l ) to ethylidyne at four d i f f e r e n t
temperatures.

9. ZAERA ETAL. Ethylidyne Formation on Pt(l 11) 137
3
|Q~1 1 1 1 I I 1 1 ) 1 I I I I 1 I I I 1
3.5 3.75 4 4.25
TEMPERATURE (I0" K)
3
Fig. 4. Temperature dependence of the rate constants f o r

ethylidyne formation from C H (+) and from C D^ (A).
2 4 2
1 , 1 . . . . . . . 1 1
1 I l
Ethylene Decomposition Pt(IU)
w
E
=3
X>
o
<u — —
3
(
/
> 2 amu C2H4
cu
to -
o
-
—
4 amu cD
- 2 4
-
1 1 1 1 1 1 1 1 1 1 , , i I 1
250 500 750
Temperature (K)
F i g . 5. H (2 amu) and D (4 amu) thermal desorption spectra

2 2
from chemisorbed C^H^ and C D^ on P t ( l l l ) , respectively.

2
Heating rate = lOK/s.

T 1 1 1 1 r
200 300 400

Temperature (K)
Fig. 6. Computer simulation for hydrogen TDS from chemisorbed
ethylene on P t ( l l l ) : (a) F i r s t order process only, with
a c t i v a t i o n energy -=15.0 Kcal/mole (dashed l i n e ) ; (b) same as (a)
but including a hydrogen recombination step ( s o l i d l i n e ) ; (c)
experimental data (crosses). See d e t a i l s i n text.

9. ZAERA ETAL. Ethylidyne Formation on Pt(l 11) 139
desorption spectra reported by Christmann et. a l . (15). The

r e s u l t s are shown i n Figure 6. We can see that i f only the C-H bond
breaking i s considered, the simulated TDS peak i s much broader than
the experimental r e s u l t (dashed l i n e versus crosses). The shapes
are also c l e a r l y d i f f e r e n t , since the experimental data has a
sharper leading edge that the simulated peak. However, i f hydrogen
recombination i s included i n the calculations, the f i t i s greatly
improved ( s o l i d l i n e ) . I t must be pointed out that these
simulations use no adjustable parameters. There i s some uncertainty
i n the values for hydrogen recombination, since a c t i v a t i o n energy
values up to 19 Kcal/mole have been reported for hydrogen on P t ( l l l )
(16). Also, hydrogen desorption may be modified by ethylene
coadsorption. We decided to f i t our parameters to the hydrogen TDS
data from clean P t ( l l l ) from r e f . 15 (Ea - 9 Kcal/mole) and use
those values f o r the simulations of ethylene decomposition, but we
found that the results d i d not depend very strongly on the actual
numbers used as long as hydrogen desorption was faster than C-H bond
breaking at the peak of
energy f o r hydrogen desorptio
obtained no s i g n i f i c a n t changes i n the o v e r a l l simulated TDS.
F i n a l l y , the low temperature peak around 250K could also be
simulated by assuming an i n i t i a l coverage of about 0.15 of a
monolayer of coadsorbed hydrogen (from background gases).
Conclusions
We have measured the k i n e t i c s of ethylidyne formation from

chemisorbed ethylene over P t ( l l l ) surfaces. The rates of reaction
display a f i r s t order dependence on the ethylene coverage. There i s
an isotope e f f e c t , since the reaction for C H i s about twice as
2 4
f a s t as for C D . We obtain values for the a c t i v a t i o n energy of

2 4
15.0 and 16.7 Kcal/mole for the normal and deuterated ethylene,
respectively. These values are lower than those obtained from TDS
experiments, but the differences can be reconciled by taking into
account the hydrogen recombination when analyzing the thermal
desorption data.
These experiments also show the value of NEXAFS as a technique
for following the k i n e t i c s of surface processes. We have shown that
experiments can be t a i l o r e d so a s p e c i f i c reaction can be studied,
even i f gas evolution i s not involved. This represents an advantage
over thermal desorption experiments, where several steps may be
required i n order to desorb the products to be detected. Another
advantage of NEXAFS i s that rates are measured isothermally, so the
k i n e t i c parameters can be determined with accuracy. F i n a l l y , NEXAFS
i s not a destructive technique, so we need not to worry about
modifying the surface compounds while probing the system, as would
be the case with other techniques such as Auger electron
spectroscopy.
1. Baro, A.M.; Ibach, H. J . Chem. Phys. 1981, 74$16C, 4194.

2. Salmerón, M; Somorjai, G.A. J . Phys. Chem. 1982, 86, 341.

3. Zaera, F; Somorjai, G.A. In Hydrogen i n Catalysis: Theoretical

and P r a c t i c a l Aspects; Paal, Z.; Menon, P.G., Eds.; Marcel
Dekker, New York, 1987.
4. Demuth, J.E. IBM J . Res. Dev. 1978, 22, 265.
5. Hiett, P.J.; Flores, F.; Grant, P.J; March, N.M.;
Martin-Rodero, A; Senatore, G. Surf. S c i . 1984, 140, 400.
6. Kesmodel, L.; Dubois, L; Somorjai, G.A. J . Chem. Phys.

1979, 70, 2180.
7. Skinner, P; Howard, M.W.; Oxton, I.A.; Kettle, S.F.A.; Powell,
D.B.; Sheppard, N. J . Chem. Soc. Faraday Trans. 1981, 2, 77,
1203.
8. Zaera, F.; Somorjai, G.A. J . Am. Chem. Soc. 1984, 106, 2288.
9. Godbey, D.; Zaera, F.; Yates, R.; Somorjai, G.A. Surf. S c i .
1986, 167, 150.
10. Ogle, K.M.; Creighton, J.R.; Akhter,S; White, J.M. Surf. S c i .
1986, 169, 246.
11. Brown, C.; Bachrach
1978, 152, 73.
12. Stöhr, J ; Jaeger, R. Phys. Rev. B 1982, 26, 4111.
13. Koestner, R.J.; Stöhr, J . ; Gland, J.L.; Horsley, J.A. Chem.
Phys. Letts. 1984, 105, 332.
14. Chan, C.-M.; A r i s , R.; Weinberg, W.H. Appl. of Surf. S c i .
1978, 1, 360.
15. Christmann, K.; E r t l , G.; Pignet, T. Surf. S c i . 1976, 365.
16. Poelsema, B.; Mechtersheimer, G.; Comsa, G. Surf. S c i . 1981,
111, 519.
RECEIVED May 1 7 , 1988

Chapter 10
Low-Energy Electron Diffraction, X-ray

Photoelectron Spectroscopy, and Auger
Electron Spectroscopy
Lead Underpotential Deposition
on Silver Single Crystals
1
Michael E. Hanson and Ernest Yeager
Case Center for Electrochemica

Case Western Reserv University, ,
The underpotential deposition of lead has been examined
on LEED-characterized single c r y s t a l s i l v e r surfaces
with 0.1 M HF as the e l e c t r o l y t e using a s p e c i a l u l t r a -
high vacuum-electrolyte transfer system. Each of the
low index surfaces has a c h a r a c t e r i s t i c voltammetry
curve with multiple adsorption and desorption UPD peaks.
LEED studies of the UPD layers indicate unique super-
l a t t i c e s which are highly dependent on the coverage as
well as the p a r t i c u l a r single c r y s t a l surface. The UPD
layers have also been examined with AES and XPS. These
indicate that under some conditions lead i n oxidized
form i s also present on the surface a f t e r the electro-
chemical measurements, thus complicating the interpre-
t a t i o n of the LEED patterns.
The underpotential deposition (UPD) of metals on foreign metal
substrates i s of importance i n understanding the f i r s t phase of
metal electrodeposition and also as a means for preparing
electrode surfaces with i n t e r e s t i n g electronic and morphological
properties for e l e c t r o c a t a l y t i c studies. The UPD of metals on
p o l y c r y s t a l l i n e substrates exhibit quite complex behavior with
multiple peaks i n the l i n e a r sweep voltammetry curves. This
behavior i s at l e a s t p a r t i a l l y due to the presence of various low
and high index planes on the p o l y c r y s t a l l i n e surface. The
formation of various ordered overlayers on p a r t i c u l a r single
c r y s t a l surface planes may also contribute to the complex peak
structure i n the voltammetry curves.
In order to gain more insight into the dependence of the UPD
process and structure of the layer on the c r y s t a l structure of the
substrate, the UPD of lead has been studied on s i l v e r c r y s t a l
surfaces using l i n e a r sweep voltammetry. Low energy electron
d i f f r a c t i o n (LEED) has been used to examine the i n i t i a l substrate
surface as well as the UPD layers as a function of the p o t e n t i a l
1
Current address: General Electric Lighting, Nela Park, Cleveland, OH 44112
0097-6156/88/0378-0141$06.00/0
c

at which the electrode was emersed from the e l e c t r o l y t e . The

transfer of the single c r y s t a l surfaces from the ultra-high vacuum
(UHV) environment where they were prepared into the electro-
chemical environment, as well as t h e i r return to the UHV f o r post
electrochemical examination with LEED, X-ray photoelectron
spectroscopy (XPS) and Auger electron spectroscopy (AES), was
c a r r i e d out with the special system developed i n the authors'
laboratory (Figure 1).
Experimental
A detailed description of the experimental procedure i s reported

elsewhere (1). S i l v e r single crystals were obtained from Metal
Crystals Ltd., Cambridge, England, with surfaces corresponding to
the (100), (110) and (111) planes, oriented to better that 1°.
These surfaces were mechanically polished with diamond paste,
gradually decreasing the g r i t to 1 /im and then chemically polished
using previously reporte
then transferred into vacuu
surface was argon ion sputtered and then thermally annealed at
10
600°C at 1 0 " Torr.
The surface purity was checked with AES and XPS, and the
surface morphology was confirmed with LEED. For the samples used
i n the work herein reported, no impurities were observed i n the
AES or XPS p r i o r to transfer into the electrochemical environment.
The c r y s t a l was then transferred into vacuum chamber B (Figure 1)
by means of a transfer manipulator and the chamber was b a c k - f i l l e d
with u l t r a pure argon. A quasi-thin-layer c e l l with a 2 mm. gap
was then formed with an a-H(Pd) counter electrode and Pb reference
electrode. Various l i n e a r sweep voltammetry measurements were
then c a r r i e d out using 0.1 M HF + 3.0 mM PbF2 as the e l e c t r o l y t e .
Following these measurements, the single c r y s t a l electrode was
separated from the e l e c t r o l y t i c solution at a p a r t i c u l a r
controlled potential and any remaining e l e c t r o l y t e on the s i l v e r
electrode was removed i f necessary by touching the edge of the
c r y s t a l with a piece of deashed f i l t e r paper mounted on the
counter-reference manipulator assembly. The f i l t e r was precleaned
with -20% by wt. HF followed by extended washing i n t r i p l y
d i s t i l l e d water. Chamber B was then re-evacuated and the single
c r y s t a l electrode returned to chamber A at a pressure i n the 10"
10 Torr range i n about 5 minutes. LEED, XPS and AES measurements
were then c a r r i e d out.
Linear Sweep Voltammetry
Each of the low index Ag single crystals displayed mutually unique

voltammetry curves with multiple adsorption/desorption peaks
(Figure 2). The nominal features of these curves are s i m i l a r to
those obtained by other authors f o r Ag single c r y s t a l surfaces i n
HF or HCIO4 using both UHV and non-UHV methods ( 4 ^ ) .
Voltammetry curves obtained by Vitanov et a l . (8) on electro-
chemically grown A g ( l l l ) surfaces with an u l t r a low step density

TO ROUGHING PUMP
T.M.
PUMP DIODE PUMP AND TSP
(LOWER LEVEL)
CLAM 100
MANIPULATOR
MANIPULATOR

CHAMBER C
CHAMBER A
CHAMBER B

MANIPULATOR
Figure 1. Schematic diagram of the LEED - AES - XPS - e l e c t r o -
^| chemical system.
U
0.1 0.2 03 0.4 0 0.1 0.2 0.3 04 0 0.1 0.2 Q3 0.4

2+ 2
Potential(V) vs PblPb Potential (V) vs PblPb Potential (V) vs PblPb *
Figure 2. Voltammograms f o r the underpotential deposition of

lead on s i l v e r single c r y s t a l surfaces.
3
E l e c t r o l y t e : 0.1 M HF and 3 x 10" M PbF2-

Sweep rate: 10 mV/s f o r Ag(110) and A g ( l l l ) ; 20
mV/s f o r Ag(100) f i r s t sweeps.
10. HANSON AND YEAGER LEED-XPS-AES Studies on Lead UPD 145
display only one prominent adsorption/desorption peak. These

authors report that the shape of those voltammetry curves did not
change with extended sweeping within the UPD p o t e n t i a l range or
with extended p o l a r i z a t i o n at a potential more cathodic than the
adsorption peak p o t e n t i a l . On A g ( l l l ) surfaces with a higher step
density, they propose that s t r u c t u r a l transformations occur i n a
p a r t i a l adsorption layer causing the voltammetry curve to display
two a d d i t i o n a l adsorption/desorption peaks, s i m i l a r to peaks 1-1'
and 3-3' i n the present work (Figure 2c). The magnitude and
f a c i l i t y of this e f f e c t appears to be proportional to the i n i t i a l
step density of the A g ( l l l ) substrate, and the adsorbate
s t r u c t u r a l transformation results i n the growth of a d d i t i o n a l
steps.
A similar e f f e c t was observed i n our work and i n the work of
others (5), where voltammetry curves changed after extended
cycling, p a r t i c u l a r l y i f the cathodic sweep was reversed before
the f u l l Pb deposition coverage The observed "cathodic memory
e f f e c t " may be due to th
phenomenon and subsequen
tated by a high step density on a UHV-prepared or chemically
polished (6) A g ( l l l ) substrate. Post electrochemical LEED analy-
sis on Ag(lll)-Pb(UPD) surfaces provided a d d i t i o n a l evidence of a
step density increase during Pb underpotential deposition, which
w i l l be discussed l a t e r i n this text. (See Figure 3.)
Post Electrochemical Electron Spectroscopy
Pb UPD films were emersed under potential control at d i f f e r e n t

coverages and analyzed by XPS, LEED and AES. XPS spectra i n the
Pb(4f) region of many of these films (Figures 4 and 5) show 4f
electron binding energies higher than expected for Pb i n the
metallic state (Figure 6). Chemical s h i f t s are more consistent
with a PbF2 standard (Figure 5c). XPS and AES frequently detected
0,F and possibly C, although not consistently (Figure 7 ) . Clear
detection of the C(KW) peak i n Figure 7 i s obstructed by one of
the Ag peaks.
After the loss of potential control, the Pb UPD layer may
react with residual e l e c t r o l y t i c solution to generate H2 and the
Pb may be oxidized to the divalent state y i e l d i n g a layer of PbO,
Pb(0H)2 or PbF2- This i s more l i k e l y to occur with UPD of Pb on
Ag than for example on Au since the UPD potentials are more
cathodic on Ag. Thus, for AEp - 0.15 V (see Figure 2a) and
E°(Pb/PbF ) - -0.344 V i n the reaction:
2
Pb(UPD) + 2HF - PbF + 2 H 2 (1)
P
[apbF ][ H ] 2 2
E - 0.344 - 0.15 - 0.296-log (2)

a a
[ HF][ Pb(UPD)]
- 0.344 - 0.15 - 0.296-log(Q)
At equilibrium (E=0), this expression predicts log(Q) =6.5 (where

Q i s the equilibrium constant for equation 1. This c a l c u l a t i o n

0 .2 .4
2
VOLTS (vs. Pb/Pb* )
Figure 3. Summary o
3
and 3 x 10" M PbF2
Before cathodic memory e f f e c t .
After cathodic memory e f f e c t , obtained by c l o s i n g the
cathodic window and re-opening i n 10 mV increments.
P a r t i a l l y recovered curve, obtained by c l o s i n g the
anodic window and re-opening i n 10 mV increments.
T T i I i i i i | i i i r ~
>-
<
CD
ox
<
U)
Z
D
O
u
155 150 145 140 135 130

BINDING ENERGY CeV)
Figure 4. Pb(4f) XPS spectra of Pb UPD f i l m s on Ag(110).
Magnesium X-ray anode (hi/ - 1253.6 eV) .
(a) Deposition charge -» 166 /iC/cm^, 0pt> - 0.31
(b) Deposition charge - 264 /iC/cm^, 0pj> - 0.49
(c) Deposition charge = 384 /iC/cm^, $-p\y - 0 . 7 1

Figure 5. Pb(4f) XPS spectra of Pb UPD films on A g ( l l l ) .

Magnesium X-ray anode (hi/ - 1253.6 eV) .
(a) Deposition charge - 244 /iC/cm^,flp^- 0.55
2
(b) Deposition charge - 345 /iC/cm , 0p - 0.78
D
(c) PbF2 standard
Figure 6. Pb(4f) XPS spectrum ofsputteredpbfoil.magnesium

X-ray anode (hi/ - 1253.6 eV).

1
11" 1
1 1111111111111111111111111111111
10X >
Pb
dE
\ I 1I I I I 1 t I I I I I I I I I1 I I I I I I I I II I I I 1 I
50 300 550 800 1050 1300

K I N E T I C ENERGY (eV)
Figure 7. AES spectra of Pb UPD films on A g ( l l l ) . E p - 2500
eV, I - 10/iA, V = 5 V.
p m
(a) Clean A g ( l l l ) , before electrochemistry.

(b) Deposition charge - 244 /iC/cm , 0p = 0.55 2
D
2
(c) Deposition charge = 345 /xC/cm , 0p = 0.78 D

indicates that the oxidation of the Pb(UPD) i s thermodynamically

favorable, although low hydrogen overvoltage i s required to make
t h i s reaction k i n e t i c a l l y f e a s i b l e .
These XPS r e s u l t s cause great uncertainty as to the chemical
state of emersed Pb(UPD) f i l m s on Ag and v a l i d a t e questions r a i s e d
about p a r t i a l desorption of UPD f i l m s a f t e r p o t e n t i a l c o n t r o l i s
l o s t (3j_9). Nevertheless, XPS chemical s h i f t s of the Pb(4f) peaks
show a dependence on the emersion p o t e n t i a l ; i . e . the Pb coverage
before emersion. Some emersed f i l m s also displayed at l e a s t two
d i f f e r e n t chemical states of the UPD Pb (Figures 4b an 5b).
The s i g n i f i c a n c e of the post-electrochemical LEED studies i s
very uncertain because of the p a r t i a l oxidation of the UPD-Pb
layers. Nonetheless the LEED measurements were c a r r i e d out.
Superlattice geometries, as judged by LEED, were dependent on the
Pb(UPD) coverage at emersion. Figures 8 and 9 show LEED photo-
graphs and possible real-space i l l u s t r a t i o n s f o r UPD Pb on Ag(100)
at low and high emersion coverages At a low coverage (Figure 8 )
the Pb appears to adsor
substrate. At high coverag
hexagonal symmetry with two equiprobable orthogonal domains i n
which substrate r e g i s t r y i s not obeyed.
Pb s u p e r l a t t i c e geometry was also found to be dependent on
substrate geometry. Figure 10 shows a LEED photograph and
possible real-space mdoel of an emersed p a r t i a l coverage Pb(UPD)
f i l m on A g ( l l l ) . Three equiprobable hexagonal s u p e r l a t t i c e s are
present, rotated - 1 1 ° , 0° and + 1 1 ° r e l a t i v e to the hexagonal sub-
s t r a t e l a t t i c e . The poor q u a l i t y of the LEED pattern does not
permit a c l e a r observation of the s c a t t e r i n g centers i n the holes
of these honeycomb structures. The very high background i n t e n s i t y
and broad spot sizes confirm that the step and defect density of
the substrate increased during electrochemistry.
Summary
UHV-prepared Ag(100), Ag(110) and A g ( l l l ) each displayed a unique

Pb UPD voltammetry curve. Observations of the voltammetry curves
on A g ( l l l ) suggest low-coverage Pb may place-exchange with the
substrate at step s i t e s , causing an increase i n the density of
step s i t e s upon further c y c l i n g . LEED studies of Pb UPD f i l m s
detected unique s u p e r l a t t i c e geometries which were dependent upon
the coverage of Pb at emersion and the c r y s t a l l o g r a p h i c orienta-
t i o n of the Ag substrate. XPS of emersed UPD Pb f i l m s i n f e r that
much of the Pb i s i n an oxidized s t a t e , e.g. PbO or PbF2- This
may be the r e s u l t of a reaction of the UPD Pb with r e s i d u a l
e l e c t r o l y t e on the emersed surfaces to form H2 once p o t e n t i a l
control i s l o s t , since the Pb on Ag i s a r e l a t i v e l y cathodic UPD
system. I t i s uncertain but l i k e l y that t h i s oxidation a l t e r s the
geometry of the UPD Pb f i l m s as they e x i s t on the electrochemical
environment under p o t e n t i a l c o n t r o l .
This study i l l u s t r a t e s the complications that may occur i n
post-electrochemical studies of UPD layers using UHV techniques,
p a r t i c u l a r l y when the layers are thermodynamically unstable on
open c i r c u i t . Fortunately considerable progress has been reported
including papers at t h i s symposium i n the use of i n - s i t u techni-

Figure 8. LEED pattern and real-space model o f p a r t i a l

coverage UPD Pb on Ag(100). Deposition charge density before
2
emersion = 53 /xC/cm , 0p - 0.14, Ep - 27 eV.
D

. HANSON AND YEAGER LEED-XPS-AES Studies on Lead UPD
Figure 9. LEED pattern and real-space model of high coverage

UPD Pb on Ag(100). Deposition charge denisty before emersion
2
328 /iC/cm , 0 = 0.86, Ep - 27 eV.
P b

Figure 10. LEED pattern and real-space model o f p a r t i a l -

coverage UPD Pb on A g ( l l l ) . Deposition charge density before
emersion - 244 /zC/cm*, 0 » 0.55, Ep - 25 eV.
p b

ques f o r the study of the structure of layers on electrode

surfaces using synchrotron r a d i a t i o n i n low angle X-ray
s c a t t e r i n g , EXAFS (10) and X-ray standing wave techniques (11).
Acknowledgment
The authors acknowledge very h e l p f u l discussions with Dr. R. Adzic

of the I n s t i t u t e of Electrochemistry, Belgrade, concerning the
underpotential deposition of lead on single c r y s t a l s i l v e r sub-
strates a f t e r chemical p o l i s h i n g . The authors also acknowledge
support of the research by the U.S. Office of Naval Research.
References
1. M. E. Hanson, Ph.D. Thesis, Case Western Reserve U n i v e r s i t y ,

Cleveland, Ohio (1985).
2. R. R. Adzic, M. E Hanson and E Yeager J Electrochem
Soc., 131, 1730 (1984)
3. L. Laguren-Davidson
Langmuir, 4, 224 (1988).
4. W. J . Lorenz, E. Schmidt, G. Staikopv and H. Bort, 12th
Faraday Symposium, E l e c t r o c r y s t a l l i z a t i o n , Nucleation and
Phase Formation, Southampton, England (1977).
5. H. Siegentaller and K. Juttner, Electrochim. Acta, 24, 109
(1979).
6. K. Juttner, Electrochim. Acta, 31, 917 (1986).
7. A. Bewick and B. Thomas, J. Electroanal. Chem., 84, 127
(1977).
8. T. Vitanov, A. Popov, G. Staikov, E. Bodevski, W. J . Lorenz
and E. Schmidt, Electrochim. Acta, 31, 981 (1986).
9. B. C. Schardt, J . L. Stickney, D. . Stern, A. Wieckowski, D.
C. Zapien and A. T. Hubbard, Langmuir, 3, 239 (1987).
10. J . G. Gordon, O. R. Melroy, M.G. Samani, M. F. Toney and G.
L. Borges, 194th American Chemical Society National Meeting,
Symposium on Photochemical and Electrochemical Surface
Science, New Orleans, paper 186 (1987).
11. H. D. Abruna, l o c . cit., paper 185.

Chapter 11
Structural, Catalytic, Electronic, and

Electrochemical Properties of Strained-Copper
Overlayers on Ruthenium (0001)
1
D. W. Goodman and E. M . Stuve
Sandia National Laboratories
The chemical behavior of monolayer coverages of one

metal on the surface of another, i . e . Cu/Ru, Ni/Ru,
Ni/W, Pd/W, has recently been shown to be dramatically
d i f f e r e n t from that seen f o r either of the m e t a l l i c
components separately. These chemical a l t e r a t i o n s ,
which modify the chemisorption and c a t a l y t i c proper-
t i e s of the overlayers, have been correlated with
changes i n the s t r u c t u r a l and electronic properties of
the b i m e t a l l i c system. The films are found to grow i n
a manner which causes them to be strained with respect
to t h e i r bulk l a t t i c e configuration. E a r l i e r studies
have addressed the adsorption of CO and H2 on copper
overlayers on Ru(0001) as well as the measurement of
the elevated pressure k i n e t i c s of the methanation,
ethane hydrogenolysis, and cyclohexane dehydrogenation
reactions. In addition, unique electronic interface
states have been i d e n t i f i e d for this b i m e t a l l i c
system. A comparison of electrochemical (EC) and
ultrahigh vacuum (UHV) deposition methods has been
made v i a a series of co- characterization experiments
i n which Cu was deposited i n one environment (UHV or
EC) and characterized i n the other (EC or UHV). Both
EC s t r i p p i n g and temperature programmed desorption
(TPD) i n vacuum of the Cu show that the difference i n
the heat of desorption between multilayer and mono-
layer Cu is ~6 kcal/mole and i d e n t i c a l f o r both
methods.
1
Visiting Associated Western Universities summer faculty; permanent address: Department of
Chemical Engineering, BF-10, University of Washington, Seattle, WA 98195
0097-6156/88/0378-0154$06.00/0

11. GOODMAN AND STUVE Properties of Copper Overlayers 155
I t has long been recognized that the addition of impurities to metal

catalysts can produce large e f f e c t s on the a c t i v i t y , s e l e c t i v i t y ,
and resistance to poisoning of the pure metal (1). For example, the
c a t a l y t i c properties of metals can be altered greatly by the
addition of a second metal (2). A long-standing question regarding
such b i m e t a l l i c systems i s the nature of the properties of the mixed
metal system which give r i s e to i t s enhanced c a t a l y t i c performance
r e l a t i v e to either of i t s i n d i v i d u a l metal components. These
enhanced properties (improved s t a b i l i t y , s e l e c t i v i t y and/or
a c t i v i t y ) can be accounted for by one or more of several p o s s i b i l i -
t i e s . F i r s t , the addition of one metal to a second may lead to an
e l e c t r o n i c modification of either or both of the metal constituents.
This e l e c t r o n i c perturbation can r e s u l t from d i r e c t bonding (charge
transfer) or from a s t r u c t u r a l modification induced by one metal
upon the other. Secondly, a metal additive can promote a p a r t i c u l a r
step i n the reaction sequence and, thus, act s y n e r g i s t i c a l l y with
the host metal. Thirdly the additive metal can serve to block the
a v a i l a b i l i t y of c e r t a i n
a p a r t i c u l a r reaction step
involves an undesirable reaction product, then the net e f f e c t i s an
enhanced o v e r a l l s e l e c t i v i t y . Further, the attenuation by t h i s
mechanism of a reaction step leading to undesirable surface con-
tamination w i l l promote c a t a l y s t a c t i v i t y and d u r a b i l i t y .
The present studies are part of a continuing e f f o r t (3-12) to
i d e n t i f y those properties of b i m e t a l l i c systems which can be related
to t h e i r superior c a t a l y t i c properties. A p i v o t a l question to be
addressed of b i m e t a l l i c systems (and of surface impurities i n
general) i s the r e l a t i v e importance of ensemble ( s t e r i c or l o c a l )
versus e l e c t r o n i c (nonlocal or extended) e f f e c t s i n the modification
of c a t a l y t i c properties. A complete understanding of surface
impurity e f f e c t s (including alloying) i n c a t a l y s i s w i l l l i k e l y
include components of both electronic and ensemble e f f e c t s , the
r e l a t i v e importance of each to be assessed for a given reaction and
reaction conditions. An emphasis of our research has been i n the
area of addressing and p a r t i t i o n i n g the importance of these two
e f f e c t s i n the influence of a l l o y i n g and surface additives on
surface reactions.
Experimental
The studies described other than the combined ultrahigh vacuum

(UHV)-electrochemical (EC) studies involve the use of an experimen-
t a l apparatus of the type described i n references 14 and 15. This
device consists of a surface analysis chamber vacuum interlocked to
a microcatalytic reactor. Both regions are of ultrahigh vacuum
construction and capable of ultimate pressures of less than 2 times
10 t o r r . In the surface analysis chamber, techniques such as
Auger spectroscopy (AES), X-ray photoelectron spectroscopy (XPS),
u l t r a v i o l e t photoelectron spectroscopy (UPS), low energy electron
d i f f r a c t i o n (LEED), and temperature programmed desorption (TPD) are
available for sample preparation and for sample characterization
before and a f t e r reaction. The sample support assembly allows the
metal s i n g l e - c r y s t a l catalyst to be transferred i n vacuo from the

surface analysis region to the microcatalytic reactor. In the

microcatalytic reactor, reaction k i n e t i c s can be measure^ f o r single
c r y s t a l catalysts having surface areas of less than 1 cm at reac-
tant pressures up to several atmospheres.
The single c r y s t a l catalysts, ~1 cm i n diameter and 1 mm thick,
are t y p i c a l l y aligned within 0.5° of the desired orientation.
Thermocouples are generally spot-welded to the edge of the c r y s t a l
for temperature measurement. Details of sample mounting, cleaning
procedures, reactant p u r i f i c a t i o n , and product detection techniques
are given i n the related references. The c a t a l y t i c rate normalized
to the number of exposed metal s i t e s i s the s p e c i f i c a c t i v i t y , which
can be expressed as a turnover frequency (TOF), or number of mole-
cules of product produced per metal atom s i t e per second.
The electrochemical experiments were conducted i n an apparatus
consisting of an electrochemical c e l l attached d i r e c t l y to a UHV
system and has been described i n d e t a i l elsewhere (16). The
transfer between UHV and th EC accomplished v i stainles
s t e e l a i r lock vented wit
s l i d i n g t e f l o n seals provide
pheric pressure. The sample was mounted on a polished stainless
s t e e l rod around which the t e f l o n seals were compressed. A l l valves
i n the a i r lock were stainless s t e e l gate valves with v i t o n seals.
Details of the electrochemical c e l l and conditions are contained i n
reference 16. Electrochemical potentials are referred to a
saturated calomel electrode (SCE).
S t r u c t u r a l . C a t a l y t i c , and Electronic Properties. Interest i n

b i m e t a l l i c catalysts has increased steadily because of the
commercial success of these systems, which allow an enhanced a b i l i t y
to control the c a t a l y t i c a c t i v i t y and s e l e c t i v i t y by t a i l o r i n g the
c a t a l y s t composition (17-29). A key point i n these investigations,
as with the studies involving other impurities, has been determining
the r e l a t i v e importance of ensemble and electronic e f f e c t s i n
defining c a t a l y t i c behavior (29-32). I t i s advantageous to simplify
the problem by u t i l i z i n g models of a b i m e t a l l i c catalyst, which have
been made by deposition of metals on s i n g l e - c r y s t a l substrates i n a
UHV environment. A combination that has been studied extensively i n
supported catalyst research i s copper on ruthenium (Cu/Ru). The
i m m i s c i b i l i t y of copper i n ruthenium circumvents the complication of
determining the three-dimensional composition. Furthermore, d i s t i n c t
TPD features exist f o r the f i r s t monolayer of copper r e l a t i v e to
multilayer coverages (3). Thus the copper coverage can be c a l i -
brated accurately by TPD measurements as discussed i n Section I I .
A comparison of CO desorption from ruthenium (6), and from
multilayer (10 ML) and monolayer copper covered ruthenium i s shown
i n Figure 1. The CO coverage i s at saturation. The TPD features of
the 1 ML copper (peaks at 160 and 210 K) on ruthenium are at
temperatures intermediate between those found for adsorption on
surfaces of bulk ruthenium and copper, respectively. This suggests
that the copper monolayer i s perturbed e l e c t r o n i c a l l y and that this
perturbation i s manifested i n the bonding of CO. An increase i n the

desorption temperature r e l a t i v e to bulk copper indicates a s t a b i -

l i z a t i o n of the CO on the copper monolayer which suggests an
e l e c t r o n i c coupling of the CO through the copper to the ruthenium.
Model k i n e t i c studies of these Cu/Ru(0001) c a t a l y s t s have been
performed f o r methanation (7), cyclohexane hydrogenolysis (9), and
cyclohexane dehydrogenation (10) reactions. For the f i r s t two
reactions, copper serves as an inactive d i l u e n t , blocking s i t e s on a
one-to-one basis. The l a t t e r reaction i s quite d i f f e r e n t . Figure 2
shows the e f f e c t , caused by addition of copper onto ruthenium on the
rate of dehydrogenation of cyclohexane to benzene. The o v e r a l l rate
of t h i s reaction increases by approximately an order of magnitude at
a copper coverage of 0.75 ML. This translates into a s p e c i f i c rate
enhancement f o r ruthenium of -40. At higher coverages, the rate
decreases to an a c t i v i t y approximately equal to that of copper-free
ruthenium.
The rate enhancement f o r cyclohexane dehydrogenation observed
for submonolayer copper deposits may r e s u l t from changes i n the
geometric (6) and the e l e c t r o n i
overlayer r e l a t i v e to bul
may catalyze d i f f e r e n t steps of the reaction cooperatively. For
example, d i s s o c i a t i v e adsorption on bulk copper i s unfavorable
because of an a c t i v a t i o n b a r r i e r of approximately 5 kcal/mol (33).
In the Cu/Ru system, ruthenium may function as a r e s e r v o i r f o r
atomic hydrogen, which i s accessible v i a s p i l l o v e r to neighboring
copper. K i n e t i c a l l y c o n t r o l l e d s p i l l o v e r of hydrogen from ruthenium
to copper (5) i s consistent with the observed optimum reaction rate
at an intermediate copper coverage.
The unique chemical behavior seen i n CO adsorption and f o r
c e r t a i n c a t a l y t i c reactions i s mirrored i n unique p h y s i c a l and
e l e c t r o n i c properties. For example, the adsorption and growth of
copper f i l m s on the Ru(0001) surface have been studied (3,6,34-41)
by work function measurements, LEED, AES, and TPD. The r e s u l t s from
recent studies (3,6,8) indicate that f o r submonolayer depositions at
100 K the copper grows i n a highly dispersed mode, subsequently
forming two-dimensional islands pseudomorphic to the Ru(0001)
substrate upon annealing to 300 K. Pseudomorphic growth of the
copper during the f i r s t monolayer indicates that the copper-copper
bond distances are strained by almost 6% beyond the equilibrium bond
distances found f o r bulk copper. Thermal annealing to 600 K of
copper films at coverages i n excess of 2 ML r e s u l t s i n the agglomer-
a t i o n of copper into three-dimensional islands. The p a r t i c l e s
formed expose p r i m a r i l y C u ( l l l ) surfaces and p a r t i a l l y uncover the
underlying ruthenium surface. This i s the o r i g i n of the r e s i d u a l
a c t i v i t y of the copper films at coverages greater than 1 ML.
In terms of the e l e c t r o n i c properties, recent angle-resolved
photoemission (ARUPS) studies (8) also reveal unique structure, an
interface state that i s r e l a t e d to the a l t e r e d bonding of copper
f i l m s intimate to ruthenium. The ARUPS data, shown i n Figure 3, are
using Hel photon r a d i a t i o n (21.2 eV) at normal incidence and at an
electron emission angle corresponding to the e x c i t a t i o n of electrons
from states of a p a r t i c u l a r symmetry character with respect to the
c r y s t a l structure. The spectra correspond to the energy d i s t r i b u -
t i o n of photoelectrons, and are shown as a function of the coverage
of copper overlayer. The zero of electron binding energy i s the

CO thermal desorption
CO-Cu
o
0.° CO-Ru
<
100 200 300 400 500 600
Temperature (K)
Figure 1. T P D results for C O adsorbed to saturation levels o n clean Ru(0001), o n
multilayer C u , and o n a 1 M L C u covered Ru(0001). (Data from ref. 6.) (Reprinted with
permission from ref. 42. Copyright 1986 A n n u a l Reviews, Inc.)
10.0
0.0 0.2 0.4 0.6 0.8 1.0
Copper coverage (monolayers)

Figure 2. Relative rate o f reaction vs. surface C u coverage o n Ru(0001) for cyclohexane
dehydrogenation to benzene. P = 101 Torr. H /cyclohexane = 100. T = 650 K. (Data
T 2
from ref. 10.) (Reprinted with permission from ref. 42. Copyright 1986 A n n u a l Reviews,
Inc.)

T 1 1 1 1 1 r
UPS
Cu/Ru(0001) |
-5.0 - 4 . 0 - 3 . 0 -2.0 -1.0 0.0

Binding Energy (eV)
Figure 3. A R U P S energy distribution curves taken with H e l radiation at normal incidence

and an electron emission angle o f 5 2 ° shown as a function o f copper coverage. T h e
intensity o f the various curves has been normalized at the F e r m i level E The individual
f
curves are matched to their corresponding copper coverages i n monolayers by the solid
lines and the saturation behavior o f the interface state at approximately - 1 . 5 e V is
identified by the dashed lines. (Data from ref. 8.) (Reprinted with permission from ref. 43.
Copyright 1987 A m e r i c a n Association for the Advancement of Science.)

abrupt r i s e i n photoemission i n t e n s i t y , at the Fermi l e v e l . Over-

layer copper does not a l t e r appreciably the ruthenium e l e c t r o n i c
structure at binding energies less than ~1 eV except f o r an
i n t e n s i t y attenuation. Hence, the spectra can be normalized so that
they have equal i n t e n s i t y at the Fermi l e v e l . The f i n g e r p r i n t of
bulk copper i s the narrow d-band peak j u s t below 2 eV f o r copper
coverages greater than 1 ML. Below t h i s coverage the overlayer
copper causes an increase i n i n t e n s i t y i n narrow regions centered at
-1.5 and ~3.6 eV. These states remain unchanged i n energy and
r e l a t i v e i n t e n s i t y f o r copper overlayer of a dozen monolayers.
These two features exemplify the behavior of i n t e r f a c e states, which
are states that are not seen f o r e i t h e r component of a b i m e t a l l i c
surface a l l o y but which e x i s t because of the abrupt change i n elec-
t r o n i c properties at the i n t e r f a c e .
The i n t e r f a c e nature of the states shown i n Figure 3 have been
corroborated i n recent t h e o r e t i c a l c a l c u l a t i o n s (8). The c a l c u l a t e d
energy p o s i t i o n of these states i s i n close agreement with the
experimental r e s u l t s . Thei
as w e l l . These r e s u l t s
1.5 eV are of appropriate character and energy to be a c t i v e i n
environmental chemical reactions i n v o l v i n g sub- and monolayer copper
f i l m s on ruthenium.
Vacuum Desorption and Electrochemical Properties Figures 4a-4d

shows a series of TPD spectra of Cu from Ru(0001) (16) corresponding
to three regions of Cu coverage low, medium, and high. The TPD
traces were independent of the deposition parameters such as evapor-
a t i o n rate or temperature of the anneal subsequent to evaporation.
In the low coverage region (Figure 4a) the i n i t i a l buildup of Cu can
be seen. The i n i t i a l stage of Cu growth i s indicated by the
appearance of an approximately zero order desorption peak and,
f o l l o w i n g the notation of Christmann and co-workers (34), i s noted
as • This state r e f l e c t s Cu coverages up to approximately one
monolayer (one Cu atom per surface Ru atom). The saturated fi^ state
has a desorption maximum at -1210 K.
Higher Cu exposures (Figures 4b, 4c, and 4d) cause the
appearance of a second binding state, /L , with a desorption maximum
at a temperature below that of the /? state. The k i n e t i c s of the
2
desorption process of the 0^ state are approximately zero order,

i n d i c a t i n g that the rate of the desorption i s independent of the Cu
concentration on the surface. The general adsorption behavior and
peak temperatures i n Figure 4 are completely i n agreement with the
work of Christmann, et a l . (34).
The evolution of the Cu desorption f i r s t e n t a i l s f i l l i n g of the
/?2 state followed by f i l l i n g of the 0- state. As the fi^ state
grows, the fi^ state remains e s s e n t i a l l y unchanged. This i s consis-
tent with the assignment of the fi^ state to Cu-Ru i n t e r a c t i o n s and
the fi^ state to three-dimensional Cu-Cu i n t e r a c t i o n s (34). The
ordering of these TPD features imply Cu-Ru i n t e r a c t i o n s which are ~6
kcal/mole more stable than Cu-Cu i n t e r a c t i o n s (16). The growth
mechanism of the Cu overlayer i n e i t h e r case of preparation i s
suggested by the TPD r e s u l t s which are consistent with a Frank-van
der Merwe or layer-by-layer mechanism. Furthermore, the f i l l i n g of
the ft- TPD peak provides an accurate c a l i b r a t i o n point f o r a s i n g l e

I • • • J i I i I . I • I i I i I
1000 1100 1200 1300 - 0 . 2 - 0 . 1 0.0 0.1 0.2 0.3 0.4
TEMPERATURE (K) POTENTIAL (V vs SCE)
Figure 4. Left, copper TPD from a Ru(OOOl) surface at copper coverages corresponding to
a, 0.6 ML, b, 1.5 ML, c, 2.5 ML, and d, 5.2 ML. (Data from ref. 3.) Right, electrochemical
stripping curves as a function of Cu coverage (determined by AES) for vacuum deposited
Cu on Ru(0001). (Data from ref. 16.)

monolayer of Cu^which, assuming purely e p i t a x i a l growth, i s 1.59 X

10 Cu atom/cm (35).
A Ru(0001) sample, with vacuum deposited Cu, has been charac-
t e r i z e d by c y c l i c voltammetry by t r a n s f e r r i n g to an electrochemical
c e l l (16). Figures 4e-4h shows the anodic s t r i p p i n g curves f o r four
d i f f e r e n t coverages of Cu. A single s t r i p p i n g peak was observed at
+110 mV f o r 0.6 ML Cu and s h i f t e d to +145 mV f o r 5.2 ML Cu. This
peak represents the removal of the f i r s t monolayer of Cu or Cu i n
d i r e c t contact with the Ru surface. The curve f o r 5.2 ML Cu shows
an a d d i t i o n a l peak at -20 mV f o r the s t r i p p i n g of m u l t i l a y e r Cu.
The s p l i t t i n g between the m u l t i l a y e r and monolayer s t r i p p i n g peaks
of 140 mV i s equivalent to an absolute energy d i f f e r e n c e of 6.4
kcal/mole, e s s e n t i a l l y the same value found for the difference i n
apparent a c t i v a t i o n energy f o r monolayer versus m u l t i l a y e r Cu
removal by TPD techniques described above. Auger spectra recorded
a f t e r electrochemical s t r i p p i n g and removal of the electrode at +400
mV showed no signs of Cu remaining on the surface
There i s a good c o r r e l a t i o
coverage by UHV (AES o
Figure 5 compares the Cu coverage measured by AES and CV. The CV
data were c a l c u l a t e d from the integrated charge under the monolayer
and m u l t i l a y e r s t r i p p i n g peaks assuming that the s t r i p p i n g r e a c t i o n
was
2+ -
Cu , > Cu + 2 e
ads ads
J
The e r r o r i n the CV determinations was estimated to be ±25%. That

the l i n e does not go through the o r i g i n and i t s slope deviates from
u n i t y i s a t t r i b u t e d to ambiguities i n determining the proper base-
l i n e f o r i n t e g r a t i n g the charge under the CV peaks.
A t y p i c a l Auger spectrum of the sample f o l l o w i n g
electrodepostion of Cu i s shown i n Figure 6 (16). For t h i s
experiment |he sample was immersed i n a s o l u t i o n of 0.2 M HC10, and
2
0.96 mM Cu at +400 mV, cycled to -100 mV, and then back to +40 mV
at a sweep rate of 20 mV s ". The sample was held at +40 mV f o r 2
min and emersed under p o t e n t i a l c o n t r o l . I t was not r i n s e d before
t r a n s f e r to vacuum; the small droplet which remained on the
electrode was allowed to evaporate i n vacuum. Under these
conditions, one would expect that the Cu coverage was approximately
one monolayer. This i s approximately the case as the Cu/Ru r a t i o i n
Figure 6 i s 0.048 corresponding to about one monolayer of Cu (see
Figure 5).
Conclusions
These studies have shown that:

1. Cu deposited onto Ru(0001) at 100K grows i n 2-d islands v i a a
Frank-van der Merwe (layer by layer growth) mechanism up to 2
ML. The i s l a n d sizes but not the basic growth mode are a l t e r e d
by a post-deposition anneal at 900 K.
2. The structure of the f i r s t monolayer of Cu i s pseudomorphic
with respect to the Ru(0001) substrate whereas successive Cu
layers grow e p i t a x i a l l y with a C u ( l l l ) structure.

0 0.02 0.04 0.06 0.08 0.10 0.12

Cu(920)
AES RATIO
Ru(273)
Figure 5. Correlation o f electrochemical vs. Auger determination o f C u coverage. T h e

electrochemical measurements were taken from the area under the C u stripping peaks.
(Data from ref. 16.)
I 1 1 1 1 1 1 1 r
ELECTRODEPOSITED Cu/Ru(0001)
0.2M H C I 0
4
0.96 m M C u 2 +
EMERSED AT 40mV ( S C E )
' 1 • ' • ' • • I I 1

0 200 400 600 800
ELECTRON ENERGY (eV)
Figure 6. Auger spectrum after electrodeposition o f C u o n Ru(0001) from an electrolyte

2 +
of 0.2 M H C 1 0 and 0.96 m M C u . The sample was emersed without rinsing at 40 m V
4
( S C E ) . (Data from ref. 16.)

3. The adsorptive properties of 1 ML of Cu on Ru(0001) toward CO

i s markedly d i f f e r e n t than e i t h e r corresponding to CO on
Ru(0001) or CO on bulk C u ( l l l ) .
4. The a d d i t i o n of Cu to Ru(0001) r e s u l t s i n a dramatic
enhancement of the rate of cyclohexane dehydrogenation, despite
the f a c t that Cu i s much less active f o r t h i s reaction than i s
Ru.
5. ARUPS r e s u l t s have i d e n t i f i e d unique e l e c t r o n i c interface
states f o r the Cu/Ru(0001) system. These states are not
present i n e i t h e r metal separately but e x i s t because of the
abrupt change i n properties at the i n t e r f a c e .
6. The difference i n desorption energy between m u l t i l a y e r and
monolayer Cu i s e s s e n t i a l l y the same f o r Cu desorption from Ru
i n vacuum or by electrochemical s t r i p p i n g .
Acknowledgment
We acknowledge with pleasur

Department of Energy, Offic
Chemical Sciences. This work, performed at Sandia National Labora-
t o r i e s , was supported by U.S. Department of Energy Contract No. DE-
AC04-76DP00789.
References
1. Imelik, B.; Naccache, C.; Coudurier, G.; P r a l i a u d H.;
Meriaudeau, P.; Gallezot, P.; Martin, G. A.; Vedrine, J. C.,
Eds. Metal-Support and Metal-Additive Effects in Catalysts;
E l s e v i e r , 1982.
2. S i n f e l t , J . H. B i m e t a l l i c Catalysts: Discoveries, Concepts,
and Applications; John Wiley & Sons: New York, 1983.
3. Yates, J. T., Jr.; Peden, C. H. F.; Goodman, D. W. J . Catal.
1985, 94, 576.
4. Goodman, D. W.; Yates, J. T., Jr.; Peden, C. H. F. Surf. S c i .
1985 164, 417.
5. Goodman, D. W.; Peden, C. H. F. J . Catal. 1985, 95, 321.
6. Houston, J . E.; Peden, C. H. F.; B l a i r , D. S.; Goodman, D. W.
Surf. S c i . 1986, 167, 427.
7. Peden, C. H. F.; Goodman, D. W. I&EC Fundamentals. 1986, 25,
58.
8. Houston, J . E.; Peden, C. H. F.; Feibelman, P. J.; Hamann, D.
R. Phys. Rev. Lett. 1986, 56, 375.
9. Peden, C. H. F.; Goodman, D. W. J . Catal. 1987, 104, 347.
10. Peden, C. H. F.; Goodman, D. W. J . Catal. 1986, 100, 520.
11. Berlowitz, P. J . ; Goodman, D. W. Surf. S c i . 1987, 187, 463.
12. Goodman, D. W.; Peden, C. H. F. J . Chem. Soc. Faraday
Transactions I , 1987 83, 1967.
13. Goodman, D. W.; Kelley, R. D.; Madey, T. E.; Yates, J . T., Jr.
J . Catal. 1980, 63, 226.
14. Goodman, D. W. J . Vac. S c i . Tech. 1982, 20, 522.
15. Goodman, D. W. Accts. Chem. Res. 1984, 17, 194.
16. Stuve, E. M.; I n g e r s o l l , D.; Rogers, J . W., Jr.; Goodman, D. W.
Chem. Phys. L e t t s . 1988.
17. Schwab, G. M. Disc. Faraday Soc. 1950, 8, 166.
18. Dowden, D. A. J . Chem. Soc. 1950, 242.
19. H a l l , W. K.; Emmett, P. H. J . Phys. Chem. 1959, 63, 1102.

20. Sachtler, W. M. H . ; Dorgelo, G. J. H. J . Catal. 1965, 4, 654.

21. E r t l , G; Kuppers, J . J . Vac. Sci. Technol. 1972, 9, 829.
22. Sinfelt, J.; Carter, J . L . ; Yates, D. J. C. J . Catal. 1972, 24
283.
23. Williams, F. L . ; Boudart, M. J . Catal. 1973, 30, 438.
24. Stephan, J . J.; Ponec, V . ; Sachtler, W. M. H. Surf. Sci.
1975, 47, 403.
25. Helms, C. R.; Yu, K. Y . ; Spicer, W. E. Surf. Sci. 1975, 52,
217.
26. Burton, J. J.; Helms, C. R.; P o l i z z o t t i , R. S. J . Chem. Phys.
1976, 65, 1089.
27. Silverman, E. M.; Madix, R. J . J . Catal. 1979, 56, 349.
28. Ponec, V. Surf. Sci. 1979, 80, 352.
29. Bond, G. C.; Turnham, B. D. J . Catal. 1976, 45, 128.
30. Betizeau, C.; Leclercq, G.; Maural, R.; Bolivar, C.; Charcosset
H.; Frety, R.; Tournayan, L. J . Catal. 1976, 45, 179.
31. Galvagno, S.; Parravano Catal
32. De Jongste, H. C.
395.
33. Balooch, M.; Cardillo, M. J.; Miller, D. R.; Stickney, R. E.
Surf. Sci. 1975, 50, 263.
34. Christmann, K . ; Ertl, G.; Shimizu, H. J . Catal. 1980, 61, 397.
35. Shimizu, H . ; Christmann, K . ; E r t l , G. J . Catal. 1980, 61, 412.
36. Vickerman, J. C.; Christmann, K . ; Ertl, G. J . Catal. 1981, 71,
175.
37. Shi, S. K . ; Lee, H. I.; White, J . M. Surf. Sci. 1981,
102, 56.
38. Richter, L . ; Bader, S. D.; Brodsky, M. B. J . Vac. Sci. Techn.
1981, 18, 578.
39. Vickerman, J. C.; Christmann, K. Surf. Sci. 1982, 120, 1.
40. Vickerman, J. C.; Christmann, K . ; Ertl, G.; Heiman, P.;
Himpsel, F. J.; Eastman, D. E. Surf. Sci. 1983, 134, 367.
41. Bader, S. D.; Richter, L. J . Vac. Sci. Technol. 1983, A1,
1185.
42. Goodman, D. W. Annu. Rev. Phys. Chem. 1986, 37, 425.
43. Goodman, D. W.; Houston, J . E. Science 1987, 236, 403.
RECEIVED August 26, 1988

Chapter 12
Implications of Double-Layer Emersion
Wilford N. Hansen and Galen J. Hansen
Physics Department, UMC-4415 Utah State University Logan UT 84322

The intimate relationshi
sion and parameters fundamental to electrochemical
interfaces i s shown. The surface dipole layer (xS) of
80%sat. KCl electrolyte is measured as the difference
in outer potentials of an emersed oxide-coated Au
electrode and the electrolyte. The value of +0.050 V
compares favorably with previous determinations of xS.
Emersion of Au is discussed i n terms of UHV work func-
tion measurements and the relationship between emersed
electrodes and absolute half-cell potentials. Results
show that either the accepted work function value of
Hg i n N is off by 0.4 eV, or the dipole contribution
2
to the double layer (perhaps the "jellium" surface

dipole layer of noble metal electrodes) changes by 0.4
V between solution and UHV.
Emersion of an electrode from e l e c t r o l y t e w i t h i t s double l a y e r

i n t a c t i s now a w i d e l y a c c e p t e d phenomenon a n d t e c h n i q u e . Not o n l y
i s i t a phenomenon w h i c h d e s e r v e s c a r e f u l c o n s i d e r a t i o n a n d s t u d y ,
b u t a l s o a p r o c e s s w h i c h opens u p a new s e t o f e x p e r i m e n t a l methods
to the study of the electrochemical double l a y e r . E l e c t r o d e emer-
s i o n i n v o l v e s the c a r e f u l removal o f a n e l e c t r o d e from e l e c t r o l y t e
under p o t e n t i o s t a t i c c o n t r o l , u s u a l l y h y d r o p h o b i c a l i y (1-5). when
f a i r l y c o n c e n t r a t e d e l e c t r o l y t e p a r t s ("unzips") from the e l e c t r o d e
surface d u r i n g hydrophobic emersion, the double layer remains
essentially i n t a c t on the e l e c t r o d e s u r f a c e and no electrolyte
outside the double l a y e r remains. T h i s phenomenon i s n o t due t o t h e
p r e s e n c e o f o r g a n i c s o r o t h e r i m p u r i t i e s a s some h a v e suggested.
The emersion process works w e l l w i t h r i g o r o u s l y c l e a n electrode
surfaces (5).
Emersion i n v o l v e s fundamental a s p e c t s o f condensed matter
surface science and e l e c t r o c h e m i s t r y , and i t s c o n s i d e r a t i o n o f f e r s
new i n s i g h t i n t o t h e s e f u n d a m e n t a l s . F o r e x a m p l e , w h e n a new s o l i d
o r l i q u i d s u r f a c e i s made t h e a t o m s o r m o l e c u l e s may r e a r r a n g e a t
the surface to form a s u r f a c e d i p o l e l a y e r . T h i s c e r t a i n l y happens
0097-6156/88/0378-0166$06.00/0
c

12. HANSEN AND HANSEN Implications of Double-Layer Emersion 167
f o r aqueous e l e c t r o l y t e . Yet as an electrode p l u s double layer

"unzip" from the s o l u t i o n d u r i n g emersion, the double l a y e r s p e c i e s
( i n c l u d i n g surface water) are h e l d t i g h t l y on the electrode surface
a n d p r o b a b l y c a n n o t r e a r r a n g e t o f o r m a new o u t e r d i p o l e l a y e r .
T h e r e f o r e the o u t e r p o t e n t i a l o f the emersed e l e c t r o d e c o u l d w e l l be
t h e same a s t h e i n n e r p o t e n t i a l o f t h e e l e c t r o l y t e . This would
r e p r e s e n t a major b r e a k t h r o u g h i n measurement c a p a b i l i t y a n d i n o u r
understanding o f the double l a y e r . Even i f t h i s s i t u a t i o n i s o n l y
a p p r o x i m a t e l y t r u e ( t o s a y ± 2 0 mV) f o r s p e c i a l k n o w n c a s e s , i t is
s t i l l very significant. C o n s i d e r the following points. (a)
C l a s s i c a l double layer structure t h e o r i e s c o u l d b e t e s t e d i n new
ways. Present i m p l i c a t i o n s are that theories concerning the r o l e of
w a t e r may n e e d t o b e a l t e r e d . (b) S u r f a c e d i p o l e l a y e r s o f v a r i o u s
electrolytes (x s potentials) c o u l d be d i r e c t l y measured. To d a t e
these have been c o n s i d e r e d unmeasurable ( 6 - 7 ) . (c) A b s o l u t e h a l f -
c e l l p o t e n t i a l s c o u l d be d e t e r m i n e d more d i r e c t l y , a n d e i t h e r the
e l e c t r o l y t e i n n e r p o t e n t i a l 0g o r o u t e r p o t e n t i a l c o u l d be used
as the reference s t a t e ,
i n addition, there i s n
l a y e r i s p l a c e d i n UHV, o r i f t h a t change i s a m e a s u r a b l e constant,
the absolute half-cell p o t e n t i a l can be d i r e c t l y measured from
photoelectron spectroscopy data without reference to other data such
as the work f u n c t i o n o f mercury. (e) Needed r e f e r e n c e s t a t e s f o r
l i q u i d ESCA (8) c o u l d b e e a s i l y r e a l i z e d .
E m e r s i o n i n t o Ambient Gas
A s w i t h o t h e r s u b t l e phenomena, s u c h a s t h e quantum m e c h a n i c a l
b e h a v i o r o f e l e c t r o n s i n m e t a l s , we s e e k a s e l f - c o n s i s t e n t picture
which w i l l permit a d e s c r i p t i v e explanation of the observations. In
F i g u r e 1 a r e s h o w n t h e o u t e r p o t e n t i a l o f a n e l e c t r o d e (# ) M emersed
from e l e c t r o l y t e and t h e o u t e r p o t e n t i a l o f t h e e l e c t r o l y t e itself
(# )
s as a f u n c t i o n of electrode potential, b o t h measured with
r e s p e c t t o t h e r e f e r e n c e e l e c t r o d e F e r m i l e v e l a n d w i t h t h e same
K e l v i n probe. The e l e c t r o d e i n t h i s c a s e i s g o l d c o a t e d w i t h a
layer of T i 0 2 t h a t i s much t h i c k e r t h a n t h e g o l d f i l m i t s e l f and
determines the electrochemical behavior. T h i s i s one o f t h e most
i d e a l l y p o l a r i z a b l e e l e c t r o d e we have f o u n d e v e n t h o u g h i t s c a p a c i t y
i s l a r g e , about t e n percent t h a t o f g o l d . It i s also very hydro-
phobic. The e l e c t r o d e i s r o t a t i n g s o t h a t i t c o n t i n u o u s l y emerges
h y d r o p h o b i c a l l y f r o m a n 80% s a t u r a t e d K C 1 s o l u t i o n . The p r o b e was
held 1-2 mm f r o m t h e s u r f a c e o f t h e r o t a t i n g e l e c t r o d e o r the
e l e c t r o l y t e , a n d t h e p r o b e r e a d i n g o u t s i d e t h e e l e c t r o d e was t a k e n
about two seconds a f t e r emersing from the e l e c t r o l y t e . This time
l a g causes the open p r e s e n t a t i o n (hysteresis) o f the upper curve,
and the true reading i s through the center o f the open c u r v e .
Measuring the outer p o t e n t i a l o f the r o t a t i n g emersing e l e c t r o d e and
t h e e l e c t r o l y t e i s d i s c u s s e d i n more d e t a i l e l s e w h e r e ( 9 - 1 3 ) . The
5 0 mV d i f f e r e n c e b e t w e e n # M and # s i s p r o b a b l y due m a i n l y t o the
surface d i p o l e o f the s o l u t i o n , i . e . x s = ifa - # s i f 0^ i s equal to
the s o l u t i o n inner p o t e n t i a l 0g. I n any case there i s remarkable
t r a c k i n g over the p o t e n t i a l range f o r which the double l a y e r is
stable to discharge.

o x i d e - c o a t e d Au e l e c t r o d e
rotation d 2
sweep r a t
80% s a t
\ ^ ^ A .
< + 0.050 V"T £ « A ^ . - W * -
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
U (SCE) / V
F i g u r e 1. The upper c u r v e i s a c y c l i c emersogram o f a r o t a t i n g

oxide-coated Au electrode (outer p o t e n t i a l 0 vs electrode M
p o t e n t i a l U ) , measured w i t h a K e l v i n probe. (Here # is plotted M
as 0 minus the r e f . e l e c t r o d e Fermi l e v e l . )

M The l o w e r c u r v e i s
the e l e c t r o l y t e c y c l i c potentiogram ( 0 - (-U) v s U ) , b y t h e
S
same K e l v i n p r o b e . Data indicate that 0 - # s 5 0 mV a t a l l

M s
times.

W h i l e t h e above measurement was done w i t h c a r e , a n d r e p e a t e d

s e v e r a l t i m e s , i t depends o n the e l e c t r o l y t e s u r f a c e b e i n g c l e a n .
We h a v e f o u n d t h a t w i t h c a r e t h e s o l u t i o n c a n b e k e p t c l e a n s o t h a t
i t s x g remains constant to w i t h i n the p r e c i s i o n o f our instrumen-
t a t i o n (±5 mV). The g e n e r a l i t y o f t h e phenomenon s h o u l d b e t e s t e d
b y r e p e a t i n g t h e e x p e r i m e n t w i t h more e l e c t r o d e s w h i c h emerse h y d r o -
p h o b i c a l l y and g i v e s t a b l e emersed double l a y e r s . The e x p e r i m e n t
c a n a l s o be r e p e a t e d w i t h v a r i o u s e l e c t r o l y t e s . But t h i s involves
t h e q u e s t i o n o f s a l t b r i d g e p o t e n t i a l s i f t h e SCE w i t h i t s salt
b r i d g e i s t o be used w i t h v a r i o u s s o l u t i o n s . We h a v e made m e a s u r e -
ments w i t h a K e l v i n probe o v e r s o l u t i o n s a t v a r i o u s c o n c e n t r a t i o n s
o f t h e common s a l t s N a C l , N a F , L i F , K C 1 , a n d N a S 0 . 2 4 In a l l cases
r e f e r e n c e was t o t h e l e a d w i r e o f a n SCE w h i c h c o n t a c t e d t h e s o l u -
tion via a capillary. A l l s o l u t i o n s g a v e a common ^ g w i t h i n 1 0 mV.
I n t h e c a s e o f K C 1 t h e r e w a s n o c h a n g e i n 0 g ( w i t h i n 1 0 mV) f o r
s o l u t i o n s f r o m 10 M u p t o Q0% s a t . P e r c h l o r i c a c i d u p t o one
m o l a r was a l s o t e s t e d a n d g a v e l a r g e r d e v i a t i o n s due t o e i t h e r a
change i n x g o r more l i k e l
d e v i a t i o n was s t i l l l e s
v a l u e s f o r a l l a q u e o u s s a l t s o l u t i o n s d i f f e r b y l e s s t h a n 10 mV.
The d a t a a l s o i n d i c a t e t h a t s a l t b r i d g e p o t e n t i a l s u s i n g a s a t u r a t e d
KC1 b r i d g e a r e l e s s t h a n t e n m i l l i v o l t s .
A s s e e n i n F i g u r e 1, 0 Mtracks 0 and might be a p p r o x i m a t e l y
S
equal to i t . I f e q u a l , t h e n X g = +50 mV. O n t h e o t h e r h a n d , i f w e

k n e w X g f r o m i n d e p e n d e n t d a t a i t w o u l d t e l l h o w c l o s e tf i s t o $ g .
M
We now d i s c u s s t h e d a t a f r o m t h i s p o i n t o f v i e w . A good argument

c a n b e made f o r t a k i n g a v a l u e o f x g = 5 0 mV f o r concentrated
aqueous K C 1 . This i s obtained ty a r a t i o n a l i z a t i o n of results of
R a n d i e s ( 1 1 ) , Gomer a n d T r y s o n ( 1 2 ) , a n d F a r r e l l a n d M c T i g u e ( 1 3 ) .
We t a k e t h e c a r e f u l l y d e t e r m i n e d v a l u e o f x ^ O ) = 2 5 ± 1 0 mV a n d
a d d a n o t h e r 2 5 mV b e c a u s e o f t h e i o n i c s t r e n g t h o f c o n c e n t r a t e d K C 1 .
To t h e e x t e n t t h e s e d a t a a r e c o r r e c t , t h e d o u b l e l a y e r o f F i g u r e 1
d o e s i n d e e d e m e r s e s u c h t h a t </; = 0 g o v e r t h e w h o l e e m e r s i o n p o t e n -
M
t i a l range!
E m e r s i o n i n t o UHV
Now c o n s i d e r t h e s u b j e c t f r o m t h e p o i n t o f v i e w o f e m e r s i o n i n t o
u l t r a - h i g h vacuum (UHV). T h i s p r o c e s s makes p o s s i b l e a w h o l e new
s e t o f measurements, i n c l u d i n g photoelectron work f u n c t i o n deter-
mination at room temperature, identification of much-less-than-
monolayer amounts o f a t o m i c and m o l e c u l a r s p e c i e s ( i n c l u d i n g w a t e r ) ,
and the a b i l i t y t o p e r f o r m experiments w i t h super cleanliness
throughout (1,14-19). A l l t h i s i s b e a u t i f u l l y i l l u s t r a t e d i n the
work o f Koetz and coworkers (19). We h a v e t a k e n s o m e o f t h e i r d a t a
a n d r e p l o t t e d i t f o r o u r own p u r p o s e s a s shown i n F i g u r e 2 . The
work f u n c t i o n o f a g o l d e l e c t r o d e emersed a t v a r i o u s p o t e n t i a l s i s
shown. The s t r a i g h t l i n e t h r o u g h t h e p o i n t s i s p l a c e d b y u s a f t e r a
least squares f i t . The s l o p e i s 1.00 ± 0 . 0 2 . The r o o t mean s q u a r e
d e v i a t i o n o f the p o i n t s from the l i n e i s 0.07 eV. Within this
apparent accuracy the work f u n c t i o n t r a c k s the p o t e n t i a l o f emersion
e x a c t l y , even i n t o the oxide formation region! A systematic con-
s t a n t e r r o r i s h i g h l y u n l i k e l y a s measurements o f p h o t o e l e c t r o n

-.242 0.0 0.5 1.0 1.5

(0.0 NHE)
POTENTIAL (SCE)/V
F i g u r e 2 . Work f u n c t i o n o f p o l y c r y s t a l l i n e A u e l e c t r o d e emersed
from 0.1 M HC10 a s a f u n c t i o n o f emersion p o t e n t i a l .
4 The work
f u n c t i o n o f t h e c l e a n m e t a l s u r f a c e w a s 5 . 2 e V ( 1 9 ) . I f t h e NHE
absolute h a l f - c e l l potential (with respect to 0 ) i s 4.45 V , theS
bottom l i n e i s equal t o the s o l u t i o n inner p o t e n t i a l , 0 . S If i t

i s 4.85 V , the upper curve through the p o i n t s i s equal t o 0 . S
A s a l w a y s w i t h WF, t h e F e r m i l e v e l i s t a k e n a s z e r o .

onsets and the Fermi l e v e l (used f o r WF determination) i n photo-

e l e c t r o n spectroscopy are e a s i l y determined t o an accuracy w i t h i n
the observed point s c a t t e r . Incidently, t h i s s h i f t i n the electrode
work f u n c t i o n w i t h emersion p o t e n t i a l i s t i e d d i r e c t l y to the "elec-
trochemical s h i f t " of the XPS core l e v e l spectra o f emersed double
layer species shown i n the e a r l i e r pioneering work by D'Agostino and
others i n t h i s lab (15).
These r e s u l t s are remarkable! Coupled w i t h other r e s u l t s f o r
s i l v e r and platinum (19) they show that the emersed electrode work
f u n c t i o n c a n be independent of electrode m a t e r i a l (even oxide
coated) and e l e c t r o l y t e . The ^ tracks 0 g one-to-one over a large
p o t e n t i a l region, even a f t e r placement i n UHV. The apparatus used
allowed f o r emersion and placement i n UHV without exposure to a i r a t
any time.
The data of Figure 2 imply that e i t h e r (a) the surface d i p o l e
layer of the gold electrode s h i f t s by a systematic 0.4 v o l t s during
emersion and placement i n UHV o r (b) the accepted work f u n c t i o n of
mercury i n dry nitroge
explain. F i r s t , t h i s scenari
p o t e n t i a l of 4.45 V. This i s equivalent t o the value given by
T r a s a t t i and o f f i c i a l l y recommended by I.U.P.A.C. (20). I t i s a l s o
the value implied by the data of McTigue e t . a l . (13), and i s the
value obtained by t h i s laboratory (21) . However, the value i s based
on the work f u n c t i o n of pure Hg i n N o f 4.50 eV. Some t h e o r e t i c a l
2
treatments a l s o get t h i s value f o r the NHE without reference to the

WF of Hg (22) . The lower l i n e i n Figure 2 represents the work func-
t i o n of the emersed electrode, 0^, which would be measured i f the
outer p o t e n t i a l of the electrode remained equal t o the outer poten-
t i a l of the s o l u t i o n (assuming Xg i s n e g l i g i b l e ) , and i f the value
of 4.45 V f o r the NHE absolute h a l f - c e l l p o t e n t i a l i s correct so
that d^j = 4.45 when the Fermi l e v e l of the electrode equals that of
the NHE (-0.242 V vs SCE). I t i s q u i t e c l e a r that i n vacuum, the
measured work function has a systematic s h i f t from t h i s l i n e of
+0.4 eV. E i t h e r the d i p o l e surface p o t e n t i a l i s s h i f t e d 0.4 V o r
the absolute NHE h a l f - c e i l p o t e n t i a l used here i s wrong. I f the
l a t t e r i s true, i t i s because 0(Hg) i s o f f by 0.4 eV.
E i t h e r explanation of the 0.4 eV systematic s h i f t has profound
implications. I f the accepted <D(Hg) i s o f f by the 0.4 eV, then many
r e s u l t s based on <D(Hg) are a l s o i n e r r o r . This would a l s o imply
that d r a s t i c r e t h i n k i n g on the problem of work functions i n gas
ambient i s i n order. A l s o , the absolute NHE h a l f - c e l l p o t e n t i a l
would a c t u a l l y be 4.85 V. Perhaps even more s i g n i f i c a n t l y , i t would
mean that the i n s i t u double layer remains completely i n t a c t on the
electrode surface without m o d i f i c a t i o n during or a f t e r emersion and
placement i n UHV. On the other hand, i f the surface d i p o l e layer of
the emersed electrode s h i f t s by the 0.4 V during or a f t e r emersion,
i t must require some s p e c i a l mechanism. The mechanism must be
somewhat i n s e n s i t i v e to metal electrode type (since the data i n Pef.
19 f o r Au, Ag, and Pt a l l f a l l on nearly the same l i n e ) and to some
electro-oxidation. Notice that the 0.4 eV s h i f t occurs a t a l l
p o t e n t i a l s on the curve, including the pzc (pzc £ 0.1 V v s SCE).
Therefore the change i s not due t o changes i n i o n i c charge o r t o
double layer c o l l a p s e , s i n c e a t the pzc there i s no double layer i n
the usual sense. (The s h i f t due to any change i n the i o n i c double

layer w i l l increase away from the pzc, rather than remaining cons-
tant l i k e that i n Figure 2). There i s a l s o a problem i f we consider
the 0.4 eV s h i f t to be due to removal of oriented water dipoles.
One would think that the o r i e n t a t i o n and hence the p o t e n t i a l drop
due to the water layer would depend on electrode p o t e n t i a l . On the
other hand much of the double layer water may l i e between d i s c r e t e
ions where there i s very l i t t l e f i e l d . But i t i s d i f f i c u l t to
imagine a constant 0.4 V d i p o l e layer of water which i s independent
of p o t e n t i a l , noble metal, and surface oxidation. Perhaps a better
guess i s that the " j e l l i u m " d i p o l e layer at the noble metal surface
(x ) decreases by 0.4 V when place i n aqueous e l e c t r o l y t e , and then
M
increases again when i t s d i e l e c t r i c neighborhood i s replaced by

vacuum. This would be independent of p o t e n t i a l , and perhaps even of
some surface oxidation. The reason f o r such a " j e l l i u m " s h i f t may
be simply the changing of the d i e l e c t r i c constant of the phase i n
contact w i t h the metal surface. Using t h i s " j e l l i u m " concept, the
emersion of an Ti0 -coated Au electrode i s fundamentally d i f f e r e n t
2
from that of bare Au i

surface layer and i s no
From t h i s point of view, our concept that tf = 0g M
311(1
that xg can be
measured using the emersing Ti0 -coated Au electrode should be no
0
2
surprise.
The r e s u l t s of Figure 2 (and other r e s u l t s (16,19,23) require
rethinking as t o the r o l e of water i n the double layer. I t i s s t i l l
not known how much water i s present i n metal double layers emersed
i n t o gas ambient. But we have found i n previous work that the
amount of water i n the emersed double layer on Au does not change
w i t h p o t e n t i a l (23), and Koetz and Neff found that water was essen-
t i a l l y absent i n UHV (JL6) a t a l l measured p o t e n t i a l s . Results
presented here do not decide the question of how much water i s i n
the double layer i n UHV, but they may severely r e s t r i c t i t s r o l e .
Again, i f water dipoles play an important r o l e i n double layer
formation i t i s hard to see how t h e i r removal could cause a s h i f t i n
work function which i s constant with emersion p o t e n t i a l .
Conclusions
Double layer emersion continues to a l l o w new ways of studying the

e l e c t r o c h e m i c a l interphase. I n some cases a t l e a s t , the outer
p o t e n t i a l of the emersed electrode i s nearly equal to the inner
p o t e n t i a l of the e l e c t r o l y t e . There i s an intimate r e l a t i o n between
the work f u n c t i o n of emersed electrodes and absolute h a l f - c e l l
potentials. Emersion i n t o UHV o f f e r s s p e c i a l i n s i g h t i n t o the
emersion process and i n t o double layer structure, p a r t l y because
absolute work functions can be determined and are found to track the
emersion p o t e n t i a l w i t h a t most a constant s h i f t . The data c l e a r l y
c a l l f o r answers t o questions i n v o l v i n g the most basic aspects of
double layer theory, such as the r o l e water plays i n the s t r u c t u r e
and the change i n x of the electrode surface as the electrode goes
M
from vacuum or a i r to s o l u t i o n .

12. HANSEN AND HANSEN Implications ofDouble-Layer Emersion 173
Acknowledgments
This work was supported by the National Science Foundation under

grant number CHE-8508727.
We wish t o acknowledge Kendall B. Johnson f o r h i s help i n the
laboratory.
Literature Cited
1. Hansen, W.N.; Wang, C.L.; Humpherys, T.W. J . Electroanal. Chem.

1978, 90, 137.
2. Hansen, W.N.; Kolb, D.M. J . Electroanal. Chem. 1979, 100, 493.
3. Kolb, D.M.; Hansen, W.N. Surf. S c i . 1979, 79, 205.
4. Hansen, W.N. J . Electroanal. Chem. 1983, 150, 133.
5. Kolb, D.M. Z e i t . Phys. Chem. Neue Folge 1987, 154, 179.
6. Guggenheim, E.A. J. Phys Chem 1929 33 842
7. Goodisman, J.G. Electrochemistry
Wiley and Sons: New
8. Siegbahn, H. J. Phys. Chem. 1985, 89, 897.
9. Hansen, G.J.; Hansen, W.N. J . Electroanal. Chem. 1983, 150, 193.
10. Hansen, G.J, Ph.D. D i s s e r t a t i o n , Utah State U n i v e r s i t y , Utah,
1986.
11. Randles, J.E.B. Phys. Chem. L i q . 1977, 7, 107.
12. Gomer, R.; Tryson, G. J. Chem. Phys. 1977, 66, 4413.
13. Farrell, J.R.; McTigue, P. J. Electroanal. Chem. 1982, 139, 37.
14. Hansen, W.N.; Kolb, D.M.; Rath, D.; Willie, R. J. Electroanal.
Chem. 1980, 110, 369.
15. D'Agostino, A.T.; Hansen, W.N. Surf. S c i . 1986, 165, 268.
16. Neff, H.; Koetz, R. J. Electroanal. Chem. 1983, 151, 305.
17. Peuckert, M.; Coenen, F.P.; Bonzel, H.P. Surf. S c i . 1984, 141,
515.
18. Haupt, S.; Collisi, U.; Speckmann, H.D.; Strehblow, H.-H. J .
19. Koetz, E.R.; Neff, H.; Mueller, K. J. Electroanal. Chem. 1986,
215, 331.
20. T r a s a t t i , S Pure Appl. Chem. 1986, 58, 955.
21. Hansen, W.N.; Hansen, G.J. Phys. Rev. A 1987, 36, 1396.
22. Reiss, H. J. Phys. Chem. 1985, 89, 4207.
23. Hansen, G.J.; Hansen, W.N. Ber. Bunsenges. Phys. Chem. 1987,
317, 1987.
R E C E I V E D M a y 17, 1988

Chapter 13
Applications of Scanning Tunneling Microscopy

to Electrochemistry
1 2 2,3
Moris M . Dovek , Michael J . Heben , Nathan S. Lewis , Reginald M .
2 1,3
Penner , and Calvin F. Quate
1
Department of Applied Physics, Stanford University, Stanford,
CA 94305
2
The Scanning Tunneling Microscop uniqu
c a p a b i l i t i e s for the examination of electrode topography,
the v i b r a t i o n a l spectroscopic imaging of surface adsorbed
species, and the high r e s o l u t i o n electrochemical
modification of conductive surfaces. Here we discuss
recent progress i n electrochemical STM. Included are a
comparison of STM with other ex situ and in situ surface
analytic techniques, a discussion of relevant STM design
considerations, and a semi-quantitative examination of
faradaic current contributions for STM at solution-covered
surfaces. Applications of STM to the ex s i t u and in situ
study of electrode surfaces are presented.
Since i t s introduction by Binnig et al. i n 1982 (1,2), the scanning

tunneling microscope has proven to be a powerful and unique tool i n
the study of surfaces. The technique i s conceptually simple but
technologically demanding: a conducting filament of 1-10 A width at
i t s point i s placed within several angstroms of a conducting
surface, and the tunneling current i s monitored while the t i p i s
rastered across the sample surface. Surface structure has been
obtained with atomic r e s o l u t i o n i n a v a r i e t y of ambients, including
ultra-high vacuum (3-8), cryogenic f l u i d s (9-10), atmospheric
pressure of a i r (11-14), and l i q u i d solutions (vide infra).
A d d i t i o n a l l y , e l e c t r o n i c information about surfaces (15-18), and
v i b r a t i o n a l information about surface adsorbates (10) has been
obtained on atomic dimensions. Several review a r t i c l e s that
describe i n depth the accomplishments and promise of STM have been
published (19-23). Clearly, these advances i n surface
characterization have the p o t e n t i a l to impact electrochemistry i n
diverse areas, including small scale lithography, in situ
characterization of electrodes and of double layer structure,
spectroscopy of adsorbed intermediates, and e l e c t r o n i c properties of
electrode materials.
3
Address correspondence to these authors.
0097-6156/88/0378-0174$08.00/0

13. DOVEKETAL. Scanning Tunneling Microscopy 175
To date, most STM studies have focused on demonstrating the

breadth of the possible applications; consequently, there are
r e l a t i v e l y few studies of a single electrode/electrolyte interface
as compared to, for example, surface enhanced Raman spectroscopy on
the Ag/pyridine system (24-26). Application of STM to
electrochemistry w i l l require modification of current microscope
designs, and w i l l present challenges i n the integration of
electrochemical p o t e n t i a l control as well as i n techniques for data
c o l l e c t i o n and workup. In this paper, we attempt to review the
progress made i n this r e l a t i v e l y young f i e l d , and attempt to develop
some of the theory and applications germane to use of the STM i n an
electrochemical environment. We f i r s t compare STM with other ex
situ and in situ electrode surface characterization techniques. We
then discuss modifications i n microscope design that are necessary
for use i n electrochemical c e l l s , and proceed to develop a
semiquantitative discussion of the theory of STM imaging i n an
electrochemical environment We then w i l l review the uses of STM as
an ex situ tool for th
surfaces, and f i n a l l y w i l
advantage of the STM for in situ characterization and modification
of electrode interfaces.
Comparison of Scanning Tunneling Microscopy with Other Surface

Characterization Methods
At present, the STM has been demonstrated to y i e l d spectroscopic

information regarding the s p a t i a l , v i b r a t i o n a l , and e l e c t r o n i c
structure of surfaces. In a l l of these areas, the STM i s
complementary to other e x i s t i n g techniques. Also, and i n many
p o t e n t i a l applications, STM possesses unique features and
c a p a b i l i t i e s . These c a p a b i l i t i e s are discussed i n the section
below.
Structural Information. To a f i r s t approximation, the s t r u c t u r a l

information from an STM image r e s u l t s from v a r i a t i o n s i n the
e l e c t r o n i c wavefunctions of a surface due to the positions of the
surface atoms (20,27,28). Structural information can be obtained by
rastering across the surface of interest while employing negative
feedback to maintain a constant tunneling current. By monitoring
the movement of the t i p r e l a t i v e to the surface an image can be
obtained (2,29). I f the time constant of the feedback loop i s
increased so that a constant height, rather than a constant current
i s maintained, then the s p a t i a l v a r i a t i o n of the tunneling current
w i l l contain s t r u c t u r a l information (30). Manipulation of the t i p
on an angstrom l e v e l i s accomplished by use of p i e z o e l e c t r i c
materials, and further d e t a i l s regarding this process can be found
i n the section on microscope design.
In STM, the l o c a l i z e d nature of the tip-surface i n t e r a c t i o n
r e s u l t s i n an inherently s e n s i t i v e probe of surface topography.
Resolution i n the d i r e c t i o n perpendicular to the surface (the z-
direction) can be as high as 0.1 A (31), while r e s o l u t i o n i n the
l a t e r a l d i r e c t i o n can approach < 2 A (20,32). The image frame area
varies somewhat, depending upon the d e t a i l s of the microscope, but
t y p i c a l l y l i e s i n the range of 1 /xm. Due to the necessity of
producing a tunneling current, STM experiments generally require a

conducting or semiconducting surface, although the r e l a t e d atomic

force microscope (AFM) can y i e l d s i m i l a r topographical information
on i n s u l a t i n g surfaces (33-35).
As an ex situ technique f o r s t r u c t u r a l information on
surfaces, STM i s an e x c e l l e n t complement to the standard e l e c t r o n
and ion d i f f r a c t i o n probes of surface order. The STM method can
i d e n t i f y both short range order and long range p e r i o d i c i t y , as w e l l
as disordered surface layers (e.g., images of sorbic a c i d on Highly
Ordered P y r o l i t i c Graphite (HOPG), vida infra). I n contrast,
LEED requires a coherence length of ordered domains on the order
of at l e a s t 100 A to be u s e f u l (36). SEM images are t y p i c a l l y
l i m i t e d to r e s o l u t i o n of 50 A , but are u s e f u l due to t h e i r depth of
f i e l d and wide f i e l d of view (37). High r e s o l u t i o n TEM can y i e l d
images of s o l i d s to a r e s o l u t i o n of 1-2 A , but requires extensive
sample preparation and also requires that the surface atoms be i n
r e g i s t r y with the remainder of the bulk sample under study (14,38).
C l e a r l y , each technique provides valuable information which
complements the others,
would be used to obtain
under study.
For in situ surface studies under modest pressures of ambient
gases, or f o r in situ studies of surfaces i n contact with l i q u i d s ,
the ion and e l e c t r o n d i f f r a c t i o n techniques are not a v a i l a b l e . In
these systems, STM becomes one of the few techniques capable of
y i e l d i n g surface topographic information. Under c e r t a i n conditions,
surface EXAFS and X-ray standing wave techniques can y i e l d
information concerning the p e r i o d i c i t y and l a t t i c e properties of a
surface layer (39-41), however, these techniques y i e l d average
values of the desired s i g n a l over macroscopically large (mm ) beam
areas (39-41). Ellipsometry can y i e l d information concerning the
morphology of surface layers provided that s u i t a b l e models f o r the
i n t e r f a c e have been developed and confirmed by complementary
techniques (42,43). C l e a r l y , the o v e r a l l lack of in situ s t r u c t u r a l
probes of surfaces i s a major d r i v i n g force behind a p p l i c a t i o n of
STM to electrochemical i n t e r f a c e s .
V i b r a t i o n a l and E l e c t r o n i c Spectroscopy. STM has r e c e n t l y been

applied as a surface v i b r a t i o n a l spectroscopic t o o l . To date, the
a p p l i c a t i o n s have been f o r surfaces prepared under ambients, and
examined subsequently ex situ. For example, Smith et. al. (10) have
obtained v i b r a t i o n a l information from adsorbed sorbic a c i d molecules
on h i g h l y ordered p y r o l y t i c graphite substrates. I n t h i s
a p p l i c a t i o n , STM competes most c l o s e l y with EELS (44), IETS (45),
FTIR (46) and Raman spectroscopy (47). Each probe has p a r t i c u l a r
advantages with respect to s p e c t r a l range, r e s o l u t i o n and the types
of systems that may be studied. The s e l e c t i o n r u l e s that apply to
v i b r a t i o n a l spectroscopy with the STM have not yet been elucidated.
I f the i n t e r a c t i o n i s d i p o l a r i n nature, then i t might be expected
that there must be some component of the v i b r a t i o n a l mode's e l e c t r i c
dipole moment which i s p a r a l l e l to the e x c i t i n g tunneling beam i n
order to obtain a s i g n a l . A p o t e n t i a l advantage of the STM
technique i s that molecular v i b r a t i o n a l modes may be probed on an
i n d i v i d u a l molecule-by-molecule basis (10). Although the l i m i t s of
a p p l i c a b i l i t y of STM to v i b r a t i o n a l spectroscopy have only recently
begun to be explored, a d i s t i n g u i s h i n g feature i s the inherently

small " e f f e c t i v e beam s i z e " of the technique and possible geometric

information afforded by the v i b r a t i o n a l spectra (10).
STM has also been shown to provide surface e l e c t r o n i c
information (1). The most common a p p l i c a t i o n to date i n t h i s area
i s use of STM to probe the density of states i n metals and
semiconductors. Materials of i n t e r e s t to electrochemists that have
been investigated include S i (17,48), GaAs (16,49), graphite (18),
Pd (15), and Au (15). Once again, STM's unique c o n t r i b u t i o n i n
these applications arises from the small areas (ca. 2-4 A ) that are
involved i n the measurement process. These c a p a b i l i t i e s have
enabled the mapping of the s p a t i a l d i s t r i b u t i o n of e l e c t r o n i c
states. For example, c a t i o n and anion s i t e s on GaAs surfaces have
been discriminated (Stroscio, J.A.; Feenstra, R.M.; Newns, D.M.;
Fein, A.P. J . Vac. S c i . Technol. A. i n p r e s s ) ( 3 ) . E l e c t r o n i c
structure measurements of occupied states are t y p i c a l l y made with
UPS, while unoccupied states are probed by IPS (49). EELS probes
both f i l l e d and u n f i l l e d states simultaneously, and i s therefore
used i n conjunction wit
structure determination
technique, F i e l d Emission Scanning Auger Microscopy (50), u t i l i z e s
STM-like technology to e f f e c t highly l o c a l i z e d ( c a . 1 /im) Auger
electron spectroscopy. The l o c a l e l e c t r o n i c information afforded by
STM i s a valuable complement to these other techniques, and STM i s
the only one of these methods that may be applied to in situ
investigations i n condensed media.
Microscope Design f o r Electrochemical Applications
The c r i t i c a l aspects of STM design deal with the formidable task of

separating detected s p a t i a l v a r i a t i o n s of e l e c t r o n i c wavefunctions,
and signals derived therein, from spurious mechanical, a c o u s t i c a l ,
and thermally derived noise (51). Stated i n another way: the task
i s to i s o l a t e and c o n t r o l the v e r t i c a l and l a t e r a l confines of an
electron tunneling current. Important developments f a c i l i t a t i n g
t h i s goal include the introduction of magnetic l e v i t a t i o n (1), eddy
current damping (2,21), and spring supported staging (21,30) f o r
v i b r a t i o n i s o l a t i o n . S i m p l i c i t y of design was gained through the
r e a l i z a t i o n that stacked plates separated by lossy elastomers could
achieve s i m i l a r ends (52,53). High speed imaging techniques,
employable on r e l a t i v e l y smooth surfaces, were found to y i e l d an
improved signal-to-noise r a t i o (51,54) and, consequently, opened the
r e a l time imaging domain. The invention of the piezo tube scanner
by Binnig and Smith (56) further reduced the complexity of
microscopes and, since mechanical resonances of the tube occur a t
higher frequencies ( c a . 8 kHz), the tube scanner allows s t i l l
higher t i p speeds. Throughout these design evolutions the need f o r
compactness and r i g i d i t y i n the microscope body has been respected
(55).
The design c r i t e r i a f o r an in situ electrochemical STM include
the above o u t l i n e d considerations as w e l l as several needs p e c u l i a r
to an electrochemical environment. Sonnenfeld and Hansma (57)
constructed the f i r s t STM to operate under s o l u t i o n . Their work
h i g h l i g h t s two important design considerations. F i r s t l y , the t i p
and sample should be the only e l e c t r i c a l l y active parts of the
microscope exposed to s o l u t i o n . This f i r s t s o l u t i o n microscope was

designed such that the p i e z o e l e c t r i c scanning elements could remain

above the s o l u t i o n l e v e l . In taking this design consideration
further, we suggest that the t i p and sample should be the only
chemically reactive parts (e.g., metal) of the microscope exposed to
solution.
The importance of t i p insulation i s the second s i g n i f i c a n t
solution microscope design feature recognized by Sonnenfeld and
Hansma (57) . Except i n i d e a l l y pure solutions faradaic currents
w i l l always be present between the t i p and sample. I f these
currents are of the same magnitude as the tunneling currents, then
feedback control w i l l be d i f f i c u l t to maintain. Commercially
available Pt-Ir t i p s , which are glass coated except f o r about 50 /zm
at the t i p end, were employed i n an e f f o r t to reduce faradaic
currents. The most recent e f f o r t s by Sonnenfeld et. al. involved
the use of Pt-Ir t i p s with a l l but 5 /im insulated from the
e l e c t r o l y t e (58). SiO was then deposited on the uninsulated section
of the t i p by evaporation, and this d i e l e c t r i c was subsequently
removed from the very en
range with a 10 V bias betwee
Hansma, P.K.; Elings, V.; Gurley, J . ; Wickramasinghe, K.;
Sonnenfeld, R. SPIE'88 Conference Proceedings, i n press). Such tips
have also been employed i n a newer STM, shown i n Figure 1, that
employs a single tube scanner, and allows for f l u i d delivery and
removal v i a a f l u i d transfer l i n e . This approach, discussed i n
greater d e t a i l below, was successful i n that Au could be plated
from, and imaged with, these tips (58).
Other workers who have reported STM under s o l u t i o n include
Itaya et. al. (59) and Fan et. al. (Fan, F-R.F.; Bard, A.J. Anal.
Chem.. submitted). Their instruments each employ three orthogonal
p i e z o e l e c t r i c elements as t i p translators and both use glass t i p
insulation, though t h e i r t i p preparation techniques d i f f e r . In the
former case, a 10 /im Pt wire was sealed into a c a p i l l a r y and
subsequently etched, while the l a t t e r workers used a 65 /im Pt wire
which was sealed i n soft glass, turned on a lathe, and then
sonicated i n concentrated ^SO^
Morita and co-workers (60) have constructed a STM that employs
a unique 3D scanner and 3D positioner that i s constructed from
several p i e z o e l e c t r i c cubes. This microscope was subsequently
equipped with an electrochemical c e l l that allows disconnection of
the t i p and conventional 3 electrode voltammetry to be performed
(61). Itaya et. al. have gained s i m i l a r c a p a b i l i t i e s by modifying
t h e i r aforementioned STM (Itaya, K.; Higaki, K.; Sugawara, S. Chem.
Lett.. i n press).
A noteworthy advance i n the design of s o l u t i o n STMs was
achieved by Lev et. al. (Lev, 0.; Fan, F-R.F.; Bard, A.J. vL_
Electroanal. Chem.. submitted) by including a Pt " f l a g " electrode i n
the STM of Fan et. al. (Fan, F-R.F.; Bard, A.J. Anal. Chem..
submitted). A battery between the sample and this f l a g electrode,
which remains poised at the rest p o t e n t i a l of the solution, enables
the sample to be biased away from the rest p o t e n t i a l independently
of the t i p to sample bias.
We have also recently constructed a STM suitable for work
under s o l u t i o n (see F i g . 2). The s a l i e n t features of our design
include the fact that only t i p , sample, pyrex, and t e f l o n are
exposed to solution. An automatic approach mechanism allows for the

13. D O V E R E T A L . Scanning Tunneling Microscopy 179
Figure 1. Single tube piezo, s o l u t i o n STM of Sonnenfeld and

Hansma with f l u i d t r a n s f e r l i n e . Reproduced with permission of
Ref. 58. Copyright 1987 American I n s t i t u t e of Physics.

18 cm
bias wire
MACOR base II1J1IP

piezo tube
MACOR
O-ring
MACOR
RTV insulation
Figure 2. Solution STM design with single tube piezo, remote

approach and f a s t r e t r a c t c a p a b i l i t i e s , large solution
capacity, and solution-insulated t i p ( t i p design inset)
(Reprinted with permission from r e f . 98. Copyright 1988
American Institute of Physics.)

13. DOVEK ET AL. Scanning Tunneling Microscopy 181
remote operation of the microscope i n an N2 drybox and f a c i l i t a t e s

the preparation of glass coated tips v i a a f i e l d emmision process
that i s s i m i l a r to Sonnenfeld's. The microscope can be operated
with a reference electrode, counter electrode, and bi-potentiostat
to provide the above mentioned c a p a b i l i t i e s used by Lev and co-
workers. A more complete discussion of this microscope design can
be found elsewhere (Dovek, M.M.; Heben, M.J.; Lang, C.A.; Lewis,
N.S.; Quate, C F . Rev. S c i . Instr. . submitted).
Currents i n an Electrochemical STM Experiment
The key behind the imaging c a p a b i l i t i e s of the STM i s the a b i l i t y to

control and monitor the tunneling current between the t i p and the
sample. To a f i r s t approximation, the tunneling current i s r e l a t e d
to the interelectrode spacing, d, by the expression (1,30):
i oc AE exp(-2/cd) [1]
where K i s the decay constan

b a r r i e r , and A E i s the tunneling bias. For a t y p i c a l value of K —
t
1.0 A" and a constant bias, equation [1] predicts a decrease i n the
tunneling current of an order of magnitude with a 1 A decrease i n
the tip-substrate distance. Thus, equation [1] requires that t i p -
sample spacings of less than 10 A be employed for imaging at
moderate biases (AE < 1 V) i n STM (20).
t
In any imaging and spectroscopic mode of the STM, a bias i s

required between the sample and the t i p . In an electrochemical
solvent, faradaic current between the t i p and sample can i n t e r f e r e
with, and sometimes completely obscure, the tunneling current. This
undesirable s i t u a t i o n makes i t very d i f f i c u l t to control the
feedback and to maintain a constant tunneling gap between the t i p
and the sample. For example, i n our laboratory, we have found that
feedback control i s l o s t on our present microscope i f the faradaic
current, i p , assumes a value greater than one-half that of the
tunneling current, i . t Use of p a r t i a l l y insulated t i p s a l l e v i a t e s
this condition, but unfortunately, does not completely eliminate the
problem (57).
For the operation of an STM i n a conventional two-electrode
configuration, the presence or absence of s i g n i f i c a n t faradaic
current i n the tip-sample c i r c u i t depends on three factors: 1) the
redox p o t e n t i a l ( s ) of the solution species, 2) the r e v e r s i b i l i t y of
the electron transfer events for the dissolved redox couple(s), and,
3) the extent to which solution species are permitted access to the
tunneling gap. We have i d e n t i f i e d four l i m i t i n g cases of
electrochemical interest, and discuss each separately below.
Case I: Pure Liquids and Inert E l e c t r o l y t e s . In the absence of

s i g n i f i c a n t impurity currents, no faradaic current w i l l flow i f the
applied bias between the t i p and substrate, AE , i s less than the
t
t o t a l p o t e n t i a l difference, AEp , required to drive faradaic

r e v
reactions at the STM t i p and at'the substrate. This condition can

be e a s i l y calculated from the electrochemical p o t e n t i a l data for the
solvent/electrolyte system under study. This s i t u a t i o n i s most
l i k e l y to exist i n pure l i q u i d s or i n solutions of nonelectroactive
e l e c t r o l y t e s where the faradaic reactions at both electrodes are

associated with solvent or e l e c t r o l y t e e l e c t r o l y s i s . The bias

window available f o r imaging under these circumstances can be 1 V or
more. In pure water at room temperature, f o r example, AEp - 1.2 r
V (62). In such cases, i t may be unnecessary to employ insulated

STM t i p s . From a p r a c t i c a l standpoint, however, such t i p s are
desirable since the magnitude of the r e s i d u a l (impurity) faradaic
current present at any tunneling bias i s reduced.
Case I I : Reversible or Quasi-Reversible Redox Species. I f the t i p -

sample bias i s s u f f i c i e n t to cause the e l e c t r o l y s i s of s o l u t i o n
species to occur, i . e . , A E > AEp , the proximity of the STM t i p
t r e v
to the substrate surface (d < 10 A) implies that the behavior of an

insulated STM tip-substrate system may mimic that of a two-electrode
thin-layer c e l l (TLC)(63). At the small interelectrode distances
required f o r tunneling, a steady-state concentration gradient with
respect to the oxidized (Ox) and and reduced (Red) e l e c t r o a c t i v e
species should be established between the t i p and the substrate and
the r e s u l t i n g steady-stat
r e s u l t of the convectio
solution. In many cases, t h i s steady state current i s predicted to
overwhelm the convective currents, so t h i s s i t u a t i o n i s of concern
when STM imaging under electrochemical conditions (64).
Davis et. al. (64) have calculated the steady-state thin-layer
current component for a series of electrode geometries. In t h e i r
derivation, these authors have assumed that the flux between the
electrodes i s one-dimensional (perpendicular to the plane).
P a r t i c u l a r l y relevant to the STM geometry are the equations f o r the
current i n a conical electrode/planar electrode TLC, I , and those c o n
for a hemispherical electrode/planar electrode TLC, l^sph (64):

2 1/2
I c o n - (1 + <* ) (0.5 - /4 l n (1 + 2/ )) 7 7 [2]
^sph - In (1 + 7-D [3]
In the above equations, a i s the conical aspect r a t i o , r/h; 7 i s the

r a t i o of the cone or hemisphere radius to the interelectrode
distance, r/d; and I, the dimensionless faradaic current (either
I c o n or Ij^sph) t i s the r a t i o between the one-dimensional current
a n < t n e
contribution, i ^ L C * H a t i n g current for an i s o l a t e d
hemispherical electrode, i ^ p ^ (see Eq. 5)(64): S
1
TLC
I - [4]
^sph
A p l o t of I for both conical and hemispherical geometries i s
shown i n Figure 3. The thin-layer current component f o r these two
geometries becomes s i g n i f i c a n t for interelectrode distances on the
order of the cone/hemisphere radius; i . e . , that of the steady state
d i f f u s i o n layer thickness for microelectrodes with these geometries.
At smaller distances, d < r, the values of I f o r these two cases
diverge. The value of I f o r the hemisphere/plane system approaches
i n f i n i t y at small r , i n analogy to twin planar electrode TLC's. In
contrast the cone/plane TLC reaches a l i m i t i n g value (64) at small
interelectrode separations. D i g i t a l simulations performed by the

i v s o r c o n i c a a n a r t w o
Figure 3. i TLc/ F hsph * ? ^
F l"Pl electrode
c e l l (A) and'hemispherical-planar two electrode c e l l (B).
Calculated using Eqs. 2 and 3 (64).

authors i n d i c a t e that l a t e r a l (non-one-dimensional) d i f f u s i o n can be

expected to contribute less than 10% of the t o t a l current for the
hemisphere/plane case and for an interelectrode distance, d < 0.01 r
(64). I t should be noted that the accuracy of Equations 2 & 3 has
not yet been demonstrated experimentally.
Equations 3 & 4 permit the faradaic current to be estimated for
a hemispherical t i p geometry and small values of 7; i . e . , a t the
l i m i t of small interelectrode distances. At a t y p i c a l tunneling
distance of 10 A, assuming the t i p radius, r — 1 /xm ( 7 — 10" ), and
D - 10" cm sec" , the concentration of e l e c t r o a c t i v e species
corresponding to i - 1 nA i s 0.24 /zM. At the l i m i t of large
T L C
interelectrode spacings, ( i . e . , 7 » 1) the steady-state d i f f u s i o n -

layer thickness r < d, and Figure 3 shows that the one-dimensional
g s
TLC current, i , component w i l l be small. Assuming the current,

T L C
u n ( e r
Hisph' * these circumstances i s l i m i t e d by d i f f u s i o n to a
hemispherical microelectrode at the STM t i p , i t s magnitude w i l l be
given by (65):
ihsph
C O "I
Thus, f o r R = 1 jum and D - 10 cm sec" , a 1 nA l i m i t i n g current

i s obtained for concentrations of e l e c t r o a c t i v e species, C / i — o x r e (
1.6 /iM. These c a l c u l a t i o n s suggest that i n the presence of a

r e v e r s i b l e redox couple at micro-molar concentrations, even STM t i p -
sample biases of A E < 10 mV w i l l drive a faradaic current that i s
t
comparable to that of the tip-sample tunneling current. STM imaging

under such circumstances i s l i k e l y to be experimentally demanding
using conventional feedback methodology.
This constraint may be relaxed somewhat f o r quasi-reversible
redox couples. I n t h i s case, a s i g n i f i c a n t overpotential, ry, (r; - E
E m a e
" r e v ^ ' y ^ associated with the generation of faradaic current
at one or both electrodes. Thus, i t may be possible to exceed the
faradaic p o t e n t i a l window (AE > A E ) without drawing s i g n i f i c a n t
t r e v
faradaic current due to the f a c t that reactions a t one or both

electrodes are k i n e t i c a l l y slow. I n t h i s case, the e f f e c t i v e
faradaic p o t e n t i a l window i s given by, A E - rj + 77 + A E (ip <
F a c r e v
0.5 i ) . At smaller biases, feedback c o n t r o l can be maintained, and

t
STM imaging ought to be possible. This case, however, has not as

yet been demonstrated and a l l STM images of s o l u t i o n covered
surfaces to date have been obtained with biases conforming to Case I
conditions.
I t should be noted here that the u l t r a t h i n - l a y e r c e l l s (UTLC)
which r e s u l t from the close approach of an STM t i p to a conducting
substrate may have important e l e c t r o a n a l y t i c a l applications i n
studies other than STM imaging (64). This i s because extremely
large current densities should be attainable i n such c e l l s , and also
because of the f a s t t r a n s i t times (e.g., 50 nsec f o r d - 10 nm) for
reactants across the c e l l . Thus, such UTLC's might f a c i l i t a t e the
determination of f a s t heterogeneous rate constants or the study of
reactive electrochemical intermediates (64).
Case I I I : I r r e v e r s i b l e Electron Transfer or Insoluble Products.

Steady-state currents due to one-dimensional f l u x between the STM
t i p and substrate w i l l not e x i s t i f e i t h e r , 1) the products at both
electrodes are i n s o l u b l e , or, 2) the electron transfer reactions at

both electrodes are i r r e v e r s i b l e . In both of these cases, the f l u x

to both electrodes w i l l only be that supplied from bulk d i f f u s i o n
into the gap.
Although from a d i f f u s i o n a l standpoint, these two cases are
i n d i s t i n g u i s h a b l e , i t should be noted that STM imaging during the
deposition of insoluble products on e i t h e r the substrate or t i p i s
l i k e l y to be experimentally challenging. The accumulation of more
than ca. 10 A of n o n e l e c t r o n i c a l l y conductive material on the
substrate or t i p , for example, w i l l prevent the feedback from
e s t a b l i s h i n g the distances required f o r tunneling. Depositions of
conductive materials on the STM t i p (e.g., metals) w i l l probably
r e s u l t i n detrimental changes i n i t s geometry which reduce
r e s o l u t i o n . One experimentally accessible case may prove to be the
deposition of e l e c t r o n i c a l l y conductive materials on the substrate.
e.g., metal p l a t i n g . In t h i s case, c o n t r o l of the tunneling current
i s possible providing the deposition rate does not exceed the
response time of the feedback c i r c u i t .
I f the t o t a l curren
to the STM t i p , Case I I
electrode (one electrode) t h i n - l a y e r c e l l (63). Murray and
coworkers (66) have shown that for long e l e c t r o l y s i s times,
d i f f u s i o n to a planar microdisk electrode TLC can be treated as
purely c y l i n d r i c a l d i f f u s i o n , provided that the layer thickness i s
much smaller than the disk diameter (66). In contrast to the
r e v e r s i b l e case discussed above (Case I ) , the currents i n t h i s
scenario should decrease gradually with time at a rate that i s
dependent on the t i p radius and the thickness of the interelectrode
gap. Thus, for s u f f i c i e n t l y narrow tip/sample spacings, d i f f u s i o n
may be constrained s u f f i c i e n t l y ( i p decayed) at long e l e c t r o l y s i s
times to permit the imaging of surfaces with STM.
Case IV: S p a t i a l Exclusion From the Tunneling Gap. Throughout the

discussion of d i f f u s i o n above, we have assumed that the STM t i p
behaves as a microelectrode, i . e . , possesses a small metal area that
i s exposed to s o l u t i o n . This i s t y p i c a l l y the case with
commercially a v a i l a b l e , glass insulated STM t i p s where the exposed
metal surface area i s t y p i c a l l y 10 - 50 /xm (57,58). Moreover, the
discussion has also assumed that d i f f u s i o n a l processes between the
STM t i p and substrate are unperturbed by s t e r i c e f f e c t s due to the
presence of the narrow gap which separates these electrodes during
tunneling. However, at t y p i c a l tunneling distances, d < 10 A, i t i s
conceivable that e l e c t r o a c t i v e species w i l l be squeezed out of the
tip-sample region and precluded from reacting at e i t h e r the STM t i p
or the substrate. A l t e r n a t i v e l y , i t may be possible to prepare
insulated STM t i p s with geometries which prevent e l e c t r o a c t i v e
species from i n t e r a c t i n g with exposed metal at the t i p . We have
preliminary experimental r e s u l t s (vide infra) which suggest that
these conditions can be met i n p r a c t i c a l STM t i p s . Thus, the
s p a t i a l exclusion of e l e c t r o a c t i v e species from the tunneling gap i s
considered here to be a fourth d i s t i n c t c l a s s i f i c a t i o n f o r the
imaging of solution-covered surfaces.

Ex Situ Electrochemical Applications of STM
Predictably, the f i r s t STM studies of electrode surfaces were ex-

situ investigations of electrodes that were prepared i n solution and
subsequently imaged either in vacuo or i n a i r . Several
representative examples, i l l u s t r a t i n g the uses of STM to date, are
discussed i n this section.
Electrode Surface Topography. STM images of electrochemically

pretreated platinum surfaces were f i r s t obtained i n UHV by Baro and
coworkers (67) . The images reported by these workers were the f i r s t
s t r u c t u r a l images of electrode surfaces that had been exposed to
solution under p o t e n t i a l control. In an i n i t i a l series of
experiments, P t ( l l l ) single c r y s t a l electrodes were subjected to a
large amplitude, square-wave p o t e n t i a l perturbation (1M ^SO^, E-^ -
1.4 V, E - 0.05 V vs. NHE, f - 2.5 kHz ), and were imaged (at
2
nanometer resolution) before and a f t e r the electrochemical

treatment. The c y c l i c voltammogram
recorded as a function o
wave program, revealed an increase i n the amount of "strongly"
adsorbed H (E - 0.28 V)) as compared to "weakly" adsorbed H (E -
0.12V). This was consistent with the development of micro-
c r y s t a l l i n e regions of Pt(100) on the P t ( l l l ) surface (67). STM
images of the electrochemically treated surfaces revealed the
development of atomically smooth facets on some regions of the
surface, which was consistent with the proposed development of
Pt(100) m i c r o - c r y s t a l l i t e s . On the basis of both STM and
electrochemical examination of Pt surfaces that were i n i t i a l l y
either p o l y c r y s t a l l i n e Pt or P t ( l l l ) oriented c r y s t a l s , the authors
concluded that p r e f e r e n t i a l development of Pt(100) m i c r o c r y s t a l l i t e s
occurs with a p p l i c a t i o n of the square-wave, electrochemical
perturbation (67).
Subsequent STM examinations of electrochemically pretreated
platinum surfaces i n a i r by Baro and coworkers (68) and by Fan and
Bard (Fan, F-R.F.; Bard, A.J. Anal. Chem.. submitted) have focused
on i d e n t i f y i n g changes i n the surface topography effected by
electrochemical a c t i v a t i o n . In related experiments, Fan and Bard
have imaged Pt single c r y s t a l s and annealed p o l y c r y s t a l l i n e Pt
surfaces at nanometer resolution before and a f t e r the exposure of
these surfaces to adsorbates such as I^ and ethyl acetate. Images
of the adsorbate-covered surfaces exhibited a q u a l i t a t i v e l y rougher
topography as compared to clean Pt surfaces. However, the
resolution i n these images was i n s u f f i c i e n t to permit i d e n t i f i c a t i o n
of these surface features.
Morita et. al. (69) have obtained STM images of e l e c t r i c a l l y
insulating, electrochemically generated, AI2O3 b a r r i e r layers. The
AI2O3 surfaces to be imaged were coated with t h i n (40-300 A)
conductive metal films i n order to make them suitable for STM
analysis. Images such as that shown i n Figure 4 possess resolution
i n excess of that routinely available from SEM images of these
surfaces. This work demonstrated the a p p l i c a b i l i t y of STM to the
examination of electrochemically passivated surfaces (69).
It i s i n t e r e s t i n g to note that none of the STM work on metal
surfaces ( i . e . , Pt and Al) discussed above yielded images with
atomic resolution. In fact, although atomic resolution images of

DOVEK ET AL. Scanning Tunneling Microscopy 187
Figure 4 . STM images of AI2O3 b a r r i e r oxide formed anodically

at an applied p o t e n t i a l of 20 V i n Aq. 20 w/v% H S0^. Surface
2
was coated with 300 A of Pt-Pd a l l o y p r i o r to imaging. The

image at l e f t i s a composite of the s i x STM images at r i g h t
which were obtained with y-piezo o f f s e t voltages as shown.
Reproduced with permission of Ref. 69. Copyright 1986 Japanese
Journal of Applied Physics.

semi-metals such as graphite are routinely obtained i n ex situ STM

of these surfaces, the free electron nature of metals has previously
been thought to be an impediment to resolving close-packed metal
surfaces at atomic resolution. Notably, the close-packed surface of
gold ( A u ( l l l ) ) has recently been imaged i n both a i r and UHV at
atomic resolution by Hallmark et. al. (8). This implies that atomic
resolution imaging of metallic electrode surfaces may be possible i n
the near future. Curiously, the studies of the A u ( l l l ) surface
reported an observed corrugation of 0.3 A, which i s substantially
greater than that expected from t h e o r e t i c a l calculations (70). The
reasons f o r this discrepancy are not clear as of t h i s date.
Adsorbate Properties. Much recent STM a c t i v i t y has focused on the

examination of adsorbate covered surfaces. Although i n several
instances nonelectrochemical techniques, such as gas phase
adsorption methods, have been employed to prepare these surfaces,
several of these systems warrant mention here because s i m i l a r
adsorbates are routinel
Gimzewski et. al. (71
submonolayer coverages on p o l y c r y s t a l l i n e s i l v e r v i a sublimation in
vacuo. These workers then imaged these surfaces i n UHV with the
STM. Individual copper phthalocyanine molecules were resolved at a
series of tip-sample biases from 250 mV - 700 mV ( t i p +) at a
constant current of 0.35 nA (71). At the lowest tunneling biases on
this i n t e r v a l (narrowest tip-sample spacings), forms with d i s c - l i k e
geometries and diameters of ca. 10 A were observed, as expected i f
CuPc were s i t t i n g f l a t on the surface. As the bias was increased to
values > 600 mV (resulting i n a greater tip-sample spacing), the
shape of the observed images narrowed u n t i l a majority assumed a
cone-like geometry. S i g n i f i c a n t l y , stable images of i n d i v i d u a l CuPc
molecules were usually observed adjacent to surface roughness. In
the absence of observable roughness, stable, stationary CuPc
molecules were only infrequently encountered. Instead, d i f f u s i o n of
CuPc molecules was observed across the STM image window at rates of
ca. 2 A/min (71). These observations demonstrate the p o t e n t i a l for
obtaining surface d i f f u s i o n c o e f f i c i e n t s for adsorbed species with
STM. The studies with phthalocyanines are also important from the
view of e l e c t r o c a t a l y s i s .
Smith et. al. (10) have obtained images of adsorbed sorbic acid
(SA) molecules on highly ordered p y r o l y t i c graphite substrates
(HOPG) i n l i q u i d helium. Sub-monolayer coverages of sorbic acid
(C5H7COOH) were obtained by spin-casting films from SA/benzene
solutions. Images of elongated structures (Fig. 5) were associated
with SA p a r t i a l l y covering the surface. These images appeared to be
composed of several SA molecules, each of which possesses dimensions
2 A x 8 A . At the l i q u i d He temperatures employed for imaging i n
t h i s study, gap conductivity (dl/dV) vs. t i p bias spectra obtained
with the STM t i p positioned over SA molecules revealed peaks at
energies corresponding to v i b r a t i o n a l modes of adsorbed SA molecules
as determined by IETS (72). Such spectra were t y p i c a l l y dominated
either by C=C and C-H modes, or by C=0 and C-0 modes, suggesting that
for a given p o s i t i o n of the STM t i p over the SA molecule, tunneling
current was o r i g i n a t i n g primarily from the alkene end of SA
molecules, or from the carboxyl moiety (10). This example i s the
f i r s t to demonstrate the p o t e n t i a l of STM f o r extracting

Figure 5. Sorbic a c i d molecules on HOPG as reported by Smith

et. al. (10). This surface was prepared by spin-coating a
d i l u t e sorbic acid-benzene s o l u t i o n onto a f r e s h l y cleaved HOPG
substrate. Images of the surface were obtained i n l i q u i d
helium. The elongated structure shown was representative of
those present on surfaces prepared with t h i s procedure.

spectroscopic information s e l e c t i v e l y for adsorbed molecules on a

molecule by molecule basis.
In addition to the two cases discussed above, images of
surfaces coated with other organic adsorbates such as cadmium
arachidate Langmuir-Blodgett films, (73), DNA (74), di-methyl and
di-2-ethylhexyl phthalate (75), and K-24 l i q u i d c r y s t a l s (Foster,
J.S.; Frommer, J.E. Nature. submitted) have been obtained i n recent
publications.
Surfaces modified with polymer films (cf.,76-78) and s e l f -
organizing molecular assemblies (79,80) have been of p a r t i c u l a r
i n t e r e s t to electrochemists. Albrecht et. al. (Albrecht, T.R.;
Dovek, M.M.; Lang, C.A.; Quate, C.F.; Kuan, W.J.; Frank, C.W.;
Pease, R.F.W. J . Appl. Phvs.. submitted) have employed both STM and
atomic force microscopy (AFM) to image, and STM to modify,
poly(octadecyl acrylate) (PODA) films on HOPG. The films were
prepared using Langmuir-Blodgett techniques. In t h i s work, single
PODA chains were observed on surfaces containing submonolayer
coverages of the polymer
obtained was consistent
used i n t h i s study. C r y s t a l l i n e - l i k e domains of p a r a l l e l polymer
bundles were also present on such surfaces. Modification of the
polymer-covered surface was effected by applying a 100 nsec voltage
pulse of ca. 4.1 V to the tunneling bias. In c r y s t a l l i n e regions of
the polymer coating, the a p p l i c a t i o n of the voltage pulse resulted
i n the disordering of the polymer chains and i n the apparent
cleaving of polymer bonds r e s u l t i n g i n the production of shorter
PODA oligomers. The mechanism for polymer bond cleavage i n the STM
experiment may be s i m i l a r to that observed previously i n electron-
beam i r r a d i a t i o n of PMMA r e s i s t s .
Lithography With the STM: Nonelectrochemical Methods. The prospect

of atomic density information storage has spurred applications of
the STM as a surface modification t o o l . In this application, the
anisotropic current density d i s t r i b u t i o n generated by an STM t i p i s
exploited to "write" on a substrate surface. Features with c r i t i c a l
dimensions < 5 nm have been written i n UHV, i n a i r , and under
liquids.
Although the mechanism by which modification of surfaces i n
UHV occurs i s not clear for a l l cases, l o c a l heating e f f e c t s appear
to have effected the observed modification of glassy materials such
as Pdg-^Si^g (81) and R t ^ Z r ^ (82). The fluence of electrons from
an STM t i p has been used to accomplish nanometer scale electron beam
lithography of CaF coated substrates (83). A somewhat d i f f e r e n t
2
strategy has been employed by S i l v e r et. al. (84). These workers

used the e l e c t r i c f i e l d s of >10 V/cm present i n the tunneling gap
to generate a micro-plasma i n the presence of an organo-metallic gas
(dimethyl cadmium). The organometallic compound was reduced by the
plasma, and metal deposited i n 20 - 50 nm features on the cathode
(substrate) surface (84). A number of recent papers (85-87) report
the introduction of Angstrom scale modifications to metal surfaces
by the a p p l i c a t i o n of large tip-sample voltages (AE > 2V). t
Notably, these modifications have occurred both i n nonpolar l i q u i d s

and i n a i r , although the mechanism by which such features are
produced i s not as yet c l e a r . F i n a l l y , the STM t i p i t s e l f has been

used to "micro machine" (88) surfaces by operating the STM with the
t i p i n contact with a substrate.
Lithography With the STM: Electrochemical Techniques. The

nonuniform current density d i s t r i b u t i o n generated by an STM t i p has
also been exploited for electrochemical surface modification
schemes. These applications are treated i n t h i s paper as d i s t i n c t
from true in situ STM imaging because the electrochemical
modification of a substrate does not a priori necessitate subsequent
imaging with the STM. To date, a l l electrochemical modification
experiments i n which the t i p has served as the counter electrode,
the STM has been operated i n a two-electrode mode, with the
substrate surface acting as the working electrode. The tip-sample
bias i s t y p i c a l l y adjusted to drive electrochemical reactions at
both the sample surface and the STM t i p . Because i t has as yet been
impossible to maintain feedback control of the z-piezo ( t i p -
substrate distance) i n the presence of s i g n i f i c a n t faradaic current
(vide infra), a l l electrochemica
date have been performe
L i n et. al. (89) reported the f i r s t electrochemical
modification of an electrode surface that was implemented with an
STM. These workers electrochemically etched an illuminated GaAs
surface with a 4 V bias ( t i p -) i n the presence of 5 mM NaOH, 1 mM
EDTA i n either aqueous or a c e t o n i t r i l e solutions. Figure 6 shows an
SEM image of a l i n e etched on a GaAs surface using t h i s procedure.
Gas evolution at the t i p cathode was prevented by adding a
depolarizer such as nitrobenzene. In order to maintain a t i p -
substrate distance of ca. 1 /xm during the etching of l i n e s , the
surface of the semiconductor was imaged with the STM i n a i r , the
resultant topographical data was stored on a computer disk, and the
t i p path was retraced during the etching process. Etched l i n e
widths of 2.0 /im and 0.3 /xm were achieved i n t h i s seminal study
(89).
Subsequent attempts at electrochemical lithography have focused
p r i n c i p a l l y on electrochemical metal deposition. The
electrochemical deposition of metal features on the surface of a
d i s s i m i l a r metal i s complicated by the fact that nucleation events
always precede bulk metal p l a t i n g (90). Thus, although the goal i s
generally to deposit a metal feature at a l o c a t i o n d i r e c t l y under
the STM t i p , nucleation often occurs p r e f e r e n t i a l l y at surface
defect s i t e s that can be located microns away from t h i s l o c a t i o n
(Dovek, M.M.; Heben, M.J. unpublished r e s u l t s , Stanford University;
August, 1987). This problem i s most pronounced for deposition on
atomically smooth and unreactive surfaces such as basal plane-
oriented HOPG, and i s manifested i n large nucleation overpotentials
for the deposition of metals such as Ag and Cu (91). Thus, well
controlled electrochemical modifications of these surfaces have not
been demonstrated.
Schneir et. al. have avoided the nucleation problem by using
the same metal (Au) for both deposition and substrate (Schneir, J . ;
Hansma, P.K., Elings, V.; Gurley, J . ; Wickramasinghe, K.;
Sonnenfeld, R. SPIE'88 Conference Proceedings, i n press). These
workers employed glass insulated STM t i p s to write 300 - 500 nm Au
l i n e s at a bias of 3.0 V and a tip-sample spacing of 1 /xm. Craston
et. al. (Craston, D.H. ; L i n , C.W. ; Bard, A.J. J . Electrochem. S o c .

Figure 6. Scanning electron micrograph (SEM) of n-GaAs surface

electrochemically etched with a scanning electrochemical and
tunneling microscope (SETM). Etching was accomplished i n Aq. 5
mM NaOH, 1 mM EDTA. Photoelectric current - 0.7 A*A, Scan rate
- 0 . 1 /im/sec, bias voltage - 4 V. T i p was moved i n an "L"
pattern. Reproduced with permission of Ref. 8 9 . Copyright 1987
The Electrochemical Society Inc.

submitted) have achieved s i m i l a r r e s o l u t i o n by electrochemically

+
reducing metal ions (Cu and Ag ) exchanged into Nafion-coated
substrates. I n t h i s case, deposition can occur only at p o s i t i o n s on
the membrane p h y s i c a l l y contacted by the STM t i p .
C l e a r l y , the r e s o l u t i o n attained by electrochemical methods has
not yet approached that a v a i l a b l e with the other techniques
discussed above. Decreasing the tip-sample distance from the 1 fim
employed i n previous experiments ought to l o c a l i z e the current
density d i s t r i b u t i o n and improve r e s o l u t i o n . However, as noted
above, maintaining a smaller tip-sample spacing i s l i k e l y to be
d i f f i c u l t i n the absence of tunneling current feedback c o n t r o l . For
t h i s reason, s i g n i f i c a n t improvements i n electrochemical p l a t i n g
r e s o l u t i o n may depend on the development of techniques f o r
maintaining feedback c o n t r o l l e d tunneling distances on the order of
1 - 10 nm.
In Situ STM Studies of L i q u i d and Solution Covered Electrode

Surfaces
One of the most s i g n i f i c a n t applications of STM to electrochemistry

would involve the a p p l i c a t i o n of the f u l l spectroscopic and imaging
powers of the STM f o r electrode surfaces i n contact with
e l e c t r o l y t e s . Such operation should enable the electrochemist to
access, f o r the f i r s t time, a host of a n a l y t i c a l techniques i n a
r e l a t i v e l y simple and straightforward manner. I t seems reasonable
to expect at t h i s time that atomic r e s o l u t i o n images, I-V spectra,
and work function maps should a l l be obtainable i n aqueous and
nonaqueous electrochemical environments. Moreover, the evolution of
such information as a function of time w i l l y i e l d new knowledge
about key electrochemical processes. The current state of STM
applications to electrochemistry i s discussed below.
Atomic r e s o l u t i o n STM images of HOPG i n water, and images at
lower r e s o l u t i o n of Au i n aqueous 2 mM NaCl s o l u t i o n s , were f i r s t
reported by Sonnenfeld and Hansma (57). HOPG images were obtained
using t o t a l tip-sample biases of 100 mV ( t i p -) and t o t a l currents
(faradaic + tunneling) of 50 nA. The f a c t that i n d i v i d u a l solvent
molecules d i d not appear i n these STM images was a t t r i b u t e d to the
f a c t that t h e i r high v e l o c i t y r e l a t i v e to the t i p speed r e s u l t e d i n
time averaging (57). Itaya and Sugawara (59) subsequently reported
images of HOPG i n aqueous 0.05 M H S0^ i n the presence of r e s i d u a l
2
faradaic currents of 0.2 nA (AE - 100 mV, t i p - ) . L i u et. al. (92)

t
obtained one dimensional traces with a r e s o l u t i o n of ca. 30 nm of

solution-covered, metal-coated, integrated c i r c u i t s . I n t h i s case,
the authors used a t o t a l current of 5 - 25 nA, which included a
s u b s t a n t i a l distance-dependent faradaic current component, to
c o n t r o l the interelectrode distance with a conventional feedback
arrangement (92).
Sonnenfeld et. al. (58) have used STM to determine the
topography of etched (0.05 v/v% Br /MeOH) and polished GaAs
2
surfaces. STM images of these surfaces were obtained both i n

aqueous 0.01 M KOH and i n concentrated aqueous NHÔH. GaAs surfaces
exposed to the chemical etchant and polished with lens paper
exhibited average roughnesses of 1 nm over i n t e r v a l s of 5 to 1000
nm. Occasional 100 nm scale defects were also present on such
surfaces. STM images of etched GaAs surfaces i n 0.01 M aqueous KOH

remained unchanged over periods of several minutes (58).

I n t e r e s t i n g l y , the GaAs l a t t i c e could not be resolved at these
solution-covered surfaces, despite the f a c t that previous atomic
r e s o l u t i o n images of GaAs i n UHV have been reported (3,16).
Work by Schneir, Hansma and others (86,93) has extended the
l i s t of pure l i q u i d s s u i t a b l e f o r STM studies by demonstrating
imaging c a p a b i l i t i e s with a s e r i e s of nonpolar organic l i q u i d s , such
as p a r a f f i n o i l and fluorocarbon grease. These l i q u i d s have the
advantage of possessing greater v i s c o s i t y than aqueous s o l u t i o n s ,
and hence e x h i b i t inherently smaller r e s i d u a l currents. These
workers were able to a t t a i n tip-substrate biases (ca. 3 V) greater
than those r o u t i n e l y possible i n a i r or i n aqueous s o l u t i o n s . In
addition, these l i q u i d s were found to improve the signal-to-noise of
the STM atomic r e s o l u t i o n images, p o s s i b l y due to improved
v i b r a t i o n a l damping c h a r a c t e r i s t i c s as a r e s u l t of the l i q u i d layer
(86,93). The authors suggest that nonpolar, organic l i q u i d s may
serve to protect a i r s e n s i t i v e or otherwise r e a c t i v e surfaces, and
hence f a c i l i t a t e the imagin
conditions.
As noted above, Schneir, Hansma and coworkers have also used
the greater biases a v a i l a b l e i n nonpolar organic l i q u i d s (~ 3 V) to
f a c i l i t a t e the surface modification of gold surfaces (87). The
features introduced with t h i s procedure were imaged i n s i t u under a
fluorocarbon grease. Gold mounds, i n i t i a l l y ca. 10 nm i n diameter,
decreased i n height and broadened over a period of 24 h as a r e s u l t
of d i f f u s i o n . Preliminary s e l f - d i f f u s i o n c o e f f i c i e n t s f o r gold
atoms at these surfaces of D - 10 - 10 cm sec" were
estimated from the observed rate of change of height with time.
This i s the f i r s t instance i n which s o l i d - s t a t e - l i k e d i f f u s i o n
c o e f f i c i e n t s have been estimated from STM images. Thus, i t seems
l i k e l y that room temperature d i f f u s i o n c o e f f i c i e n t s might be
obtained with STM f o r w e l l characterized systems i n the future (87).
Itaya et. al. (Itaya, K.; Higaki, K.; Sugawara, S. Chem. L e t t . .
i n press) have examined the nano-topography of p o l y c r y s t a l l i n e Pt
electrode surfaces immersed i n aqueous, 0.1 M ^SO^ i n analogy to
the ex situ work with electrochemically a c t i v a t e d Pt electrodes
discussed above. Increases i n the surface area of Pt electrodes
accompanying c y c l i n g i n t h i s e l e c t r o l y t e are associated with
e l e c t r o f a c e t i n g of the electrode surface as previously reported by
Baro and coworkers. The c r y s t a l l o g r a p h i c o r i e n t a t i o n of these
facets, however, i s not apparent i n the images reported by these
authors.
Using the unique four-electrode STM described above, Bard and
coworkers (Lev, 0.; Fan, F-R.F.; Bard, A.J. J . E l e c t r o a n a l . Chem..
submitted) have obtained the f i r s t images of electrode surfaces
under p o t e n t i o s t a t i c c o n t r o l . The current-bias r e l a t i o n s h i p s
obtained f o r reduced and anodically passivated n i c k e l surfaces
revealed that the exponential current-distance r e l a t i o n s h i p expected
for a tunneling-dominated current was not observed at the oxide-
covered surfaces. On t h i s b a s i s , the authors concluded that the
n i c k e l oxide layer was e l e c t r i c a l l y i n s u l a t i n g , and was greater than
ca. 10 A i n thickness. Because accurate p o t e n t i a l c o n t r o l of the
substrate surface i s d i f f i c u l t i n a conventional, two-electrode STM
configuration, the a b i l i t y to decouple the tip-substrate bias from

the substrate p o t e n t i a l ought to f a c i l i t a t e the future study of

electrode processes by STM.
Sonnenfeld and Schardt (94), and Schneir et. a l . (Schneir, J . ,
Hansma, P.K.; E l i n g s , V.; Gurley, J . ; Wickramasinghe, K.;
Sonnenfeld, R. SPIE'88 Conference Proceedings, i n press) have both
reported in situ STM images of electrode surfaces on which metals
have been electrochemically deposited. Morita et. al. (61) have
examined Ag surfaces i n situ i n the presence of c h l o r i d e ion.
Figure 7 shows an STM image obtained by Sonnenfeld and Schardt (94)
of a Ag i s l a n d on the atomically smooth surface of HOPG i n 0.05 M
AgClO^. This work provides i n s i g h t into the mechanism by which
nucleation processes occur on smooth surfaces. Because i n each of
the three above cases, images such as that shown i n Figure 7 have
been obtained i n the presence of a r e v e r s i b l e redox couple ( i . e .
+
e i t h e r M /M° or AgCl/Cl"), they represent the most demanding
conditions under which published STM images have been obtained under
s o l u t i o n . As such, i t i s important to understand why STM imaging
under these conditions i
p o l a r i t y i s selected, bot
of Case I STM imaging.
The s i l v e r deposition experiments of Sonnenfeld and Schardt
(94) provide a representative example. A f t e r the deposition of
s i l v e r on HOPG, the f r e s h l y plated surface was imaged i n the
presence of aqueous 0.05 M AgClO^ ( F i g . 7)(94). Assuming a
p o s i t i v e t i p p o l a r i t y i s used, the STM t i p w i l l function as an anode
and i t s p o t e n t i a l w i l l be that necessary to o x i d i z e water, E H 0/02& 2
- -+0.95 V (pH - 7). The substrate cathode w i l l drive the reduction

of s i l v e r ion at the s i l v e r plated substrate at a formal p o t e n t i a l
of E +/ g - +0.72 V. Thus, an imaging window of A E - 230 mV i s
c Ag A p
a v a i l a b l e , inside of which neither electrochemical r e a c t i o n w i l l

occur. Very d i f f e r e n t consequences r e s u l t with the opposite
p o l a r i t y ( t i p - ) . S i l v e r i s anodically dissolved from the substrate
at a r e v e r s i b l e p o t e n t i a l of +0.72 V, and s i l v e r ion plates at the
t i p cathode at the same r e v e r s i b l e p o t e n t i a l . Moreover, two-
electrode TLC current enhancements are expected since the product at
+
the substrate (Ag ) i s the reactant at the STM t i p . I n t h i s
+
configuration, the Ag /Ag system represents an example of Case I I
imaging, which, as noted above, i s l i k e l y to be d i f f i c u l t with
conventional, glass-coated STM t i p s . For t h i s reason, Sonnenfeld
and Schardt succeed i n imaging Ag-plated HOPG i n the presence of 50
+
mM A g at s u b s t a n t i a l (e.g. 100 mV) biases and p o s i t i v e t i p
p o l a r i t i e s (94).
Thus, a l l of the above studies have involved Case I imaging
conditions (vide supra). That i s , i n each instance, the applied
biases used f o r imaging were less than that required to drive
faradaic reactions at both t i p and sample. Figure 8 shows a HOPG
image obtained under 1 M NaCl at AE - 550 mV ( t i p +) which i s
t
representative of images achieved i n 1 M NaCl at biases of + 1.5 V

and i n solutions of 1 M NaCl, 0.1 M Fe(CN)g /0.1 M Fe(CN) *~ 6
solutions at biases of + 0.8 V (Dovek, M.M.; Heben, M.J.; Lewis,

N.S.; Penner, R.M.; Quate, C F . manuscript i n preparation). Since
the tunneling current employed i n both cases was 1 nA, we believe
that these images represent the f i r s t examples of Case IV imaging.
This r e s u l t indicates that imaging may i n f a c t be possible under the
experimentally demanding Case IV conditions, and implies that STM

Figure 7. STM images of a s i l v e r i s l a n d on HOPG i n aqueous 0.05

M AgClO^. Image was obtained with a glass-coated P t - I r t i p at
a bias of 100 mV ( t i p +) and i - 16 nA without removing the
t
f r e s h l y Ag plated surface from the p l a t i n g s o l u t i o n .

Reproduced with permission of Ref. 94. Copyright 1986 American
I n s t i t u t e of Physics.

DOVEK ET AL. Scanning Tunneling Microscopy 197
Figure 8. STM image of the basal-plane surface of HOPG obtained

in 1 M NaCl. Bias = 550 mV ( t i p +), i = 1 nA. Image was
t
obtained i n the fast scan mode. Dark spots, separated by

2.5 A, correspond to large tunneling currents.

operation may be completely decoupled from electrochemical

enviroments.
Summary
I t should be apparent from the discussion above that STM possesses

tremendous p o t e n t i a l f o r the e l u c i d a t i o n of processes a t the
e l e c t r o d e - e l e c t r o l y t e interface. P a r t i c u l a r l y promising are the
prospects f o r in situ studies of electrode surfaces. V i b r a t i o n a l ,
e l e c t r o n i c , and s t r u c t u r a l information i s obtainable on an atomic
scale f o r electrodes of importance to basic electrochemical studies.
Although r e l a t i v e l y few electrochemical applications have been
demonstrated to date, the a v a i l a b i l i t y of commercial instrumentation
(cf.,95-97) ought to increase the a c c e s s i b i l i t y of STM to
electrochemists and widespread use of the technique i s expected i n
the near future.
Acknowledgments
We acknowledge the f i n a n c i a l assistance of the O f f i c e of Naval

Research, Grant # N00014-85-K-0805. We also acknowledge the
assistance of Bruce J . Tufts. NSL also acknowledges support as a
Dreyfus Teacher-Scholar and as a A.P. Sloan Fellow.
1. Binnig, G.; Rohrer, H.; Gerber, Ch.; Wiebel, E. App. Phys. Lett.
1982, 40, 178-80.
2. Binnig, G.; Rohrer, H.; Gerber, Ch.; Weibel, E. Phys. Rev.
L e t t . , 1982, 49, 57-61.
3. Feenstra, R.M.; Stroscio, J.A.; Tersoff, J . ; Fein, A.P.
Phys.Rev. Lett. 1987, 58, 1192-95.
4. J a k l e v i c , R.C.; E l i e , L. Phys. Rev. L e t t . 1988, 60, 120-23.
5. Becker, R.S.; Golovchenko, J.A.; Swartzentruber, B.S. Phys.Rev.
L e t t . 1985, 54, 2678-80.
6. Binnig, G.; Rohrer, H.; Gerber, Ch.; Weibel, E. Phys.Rev. Lett.
1983, 50, 120-23.
7. Hamers, R.J.; Avouris, Ph.; Bozso, F. Phys. Rev. L e t t . 1987, 59,
2071-74.
8. Hallmark, V.M.; Chiang, S.; Rabolt, J.F.; Swalen,J.D.; Wilson,
R.J. Phys. Rev. Lett. 1987, 59, 2879-82.
9. Slough, C.G.; McNairy, W.W.; Coleman, R.V.; Drake, B.; Hansma,
P.K. Phys. Rev. B 1986 34, 994-1005.
10. Smith, D.P.E.; K i r k , M.D.; Quate, C . F . J. Chem. Phys. 1987, 86,
6034-38.
11. Miranda, R.; Garcia, N.; Baro, A.M.; Garcia, R.; Pena, J.L.;
Rohrer, H., Appl. Phys. Lett. 1985, 47, 367-69.
12. Park, S.; Quate, C . F . Appl. Phys. L e t t . 1986 48, 112-14.
13. Abraham, D.W.; S a t t l e r , K.; Ganz, E.; Mamin, H.J.;Thomson, R.E.;
Clarke, J . Appl. Phys. Lett. 1986, 49, 853-55.
14. Carim, A.H.; Dovek, M.M.; Quate, C . F . ; S i n c l a i r , R.; Vorst, C.
Science 1987, 237, 630-33.
15. Kaiser, W.J.; J a k l e v i c , R.C. IBM J . Res. Develop. 1986, 30, 411-
16.

16. Stroscio, J.A.; Feenstra, R.M.; Fein, A.P. Phys. Rev. L e t t . 1987
58, 1668-71.
17. Hamers, R.J.; Tromp, R.M.; Demuth, J.E. Phys. Rev.Lett. 1986,
56, 1972-75.
18. Binnig, G.; Fuchs, H.; Gerber, Ch.; Rohrer, H.; Stoll, E.;
T o s a t t i , E. Europhys. L e t t . 1986 31, 1-36.
19. Quate, C . F . Phys. Today 1986, August, 26-33.
20. Hansma, P.K; Tersoff, J . J. Appl. Phys. 1987, 61, R1-R23.
21. Binnig, G.; Rohrer, H. S c i . Am. 1985, August, 50-56.
22. Feuchtwang, T.E.; Cutler, P.H. Phys. Scr. 1986, 35,132-40.
23. A r v i a , A.J. Surf. S c i . 1987 181, 78-91.
24. Fleischmann, M.; Hendra, P.J.; McQuillan, P.J. Chem. Phys. 1964
26, 163-67.
25. Jeanmaire, D.L.; Van Duyne, R.P. J. Electroanal.Chem. 1974, 84,
1-20.
26. Albrecht, M.G.; Creighton, J.A. J. Am. Chem. Soc. 1977, 99,
5215-17.
27. Tersoff, J . ; Hamann
28. Lang, N.D. Phys. Rev
29. Binnig, G.; Rohrer, H. Surf. S c i . 1983, 126, 236-44.
30. Bryant, A.; Smith, D.P.E.; Quate, C . F . Appl. Phys. L e t t . 1986,
48, 832-34.
31. Chiang, S.; Wilson, R.J. Anal. Chem. 1987, 59, 1267A-70A.
32. Binnig, G.; Rohrer, H. Physica B&C 1984 127B, 37-45.
33. Binnig, G.; Gerber, Ch.; Stoll, E.; Albrecht, T.R.; Quate, C.F.
Europhys. Lett. 1987 3, 1281-86.
34. Heinzelmann, H.; Grutter, P.; Meyer, E.; Hidber, H.;
Rosenthaler, L.;Ringger, M.; Guntherodt, H.-J., Surf. S c i . 1987
189/190, 29-35.
35. Albrecht, T.R.; Quate, C . F . J . Appl. Phys. 1987, 62, 2599-602.
36. Heinz, K.; Muller, K. In S t r u c t u r a l Studies of Solids Springer
Tracts in Modern Physics: New York, 1982; v o l . 91, pp 1-17.
37. Broers, A.N. Rev. S c i . I n s t r . 1969 40, 1040-45.
38. A l l e n , F.M.; Smith, B.K.; Buseck, P.R. Science 1987 238, 1695-
97.
39. Blum, L.; Abruna, H.D.; White, J.; Gordon II, J.G.; Borges,
G.L.; Samant, M.G.; Melroy, O.R. J. Chem. Phys. 1986, 85, 732-
38.
40. Samant, M.G.; Borges, G.L.; Gordon II, J.G.; Melroy, O.R.; Blum,
L.; J . Am. Chem. Soc. 1987, 109, 5970-74.
41. M a t e r l i k , G.; Schmah, M.; Zegenhagen, J . ; Uelhoff, W. Ber.
Bunsenges. J . Phys. Chem. 1987, 91, 292-96.
42. Kruger, J. I n Advances in Electrochemistry and Electrochemical
Engineering; Muller, R.H., Ed.; Wiley and Sons: New York, 1973;
v o l . 9, pp 227-280.
43. Muller, R.H. In Advances in Electrochemistry and Electrochemical
Engineering; Muller, R.H., Ed.; Wiley and Sons: New York, 1973;
v o l . 9, pp 167-226.
44. Lehwald, S. and Ibach, H. In Vibrations at Surfaces; Caudano,
R., Gilles, J.-M. and Lucus, A.A. Eds.; Plenum Press: New York,
1982; pp 137-152.
45. Wolf, E.L. P r i n c i p l e s of Electron Tunneling Spectroscopy; Oxford
U n i v e r s i t y Press: New York, 1985, Chapter 10.
46. Pons, S., Davidson, T.; Bewick, A. J. Electroanal. Chem. 1984,
160, 63-71.

47. Birke, R.L., Lombardi, J.R., and Sanchez, L.A. In

Electrochemical and Spectroscopic Studies of B i o l o g i c a l Redox
Components; Kadish, K. Ed.; ACS Symposium Series No.210;
American Chemical Society: Washington, DC, 1981; p 69.
48. Feenstra, R.M.; Stroscio, J.A.; Fein, A.P. Surf. S c i . 1987, 181.
295-306.
49. Demuth, J . ; Avouris, P. Phys. Today 1983, November, p 62.
50. Reihl, B.; Gimzewski, J.K. Surf. S c i . 1987, 189/190, 36-43.
51. Bryant, A. Ph.D. d i s s e r t a t i o n , Stanford University, June, 1986.
52. Binnig, G.; Gerber, C.; Marti, O. IBM Tech. D i s c l . B u l l . 1984
27, 3137.
53. Gerber, Ch.; Binnig, G.; Fuchs, H.; Marti, O.; Rohrer, H. Rev.
S c i . Instr. 1986 57, 221-24.
54. Bryant, A.; Smith, D.P.E.; Quate, C . F . Appl. Phys. Lett. 1986
48, 832-834.
55. Pohl, D.W. IBM J . Res. Develop. 1986, 30, 417-27.
56. Binnig, G.; Smith, D.P.E. Rev. S c i . Instru. 1986 57, 1688-89.
57. Sonnenfeld, R.; Hansma
58. Sonnenfeld, R.; Schneir
D.E. Appl. Phys. Lett. 1987 50, 1742-44.
59. Itaya, K.; Sugawara, S. Chem. Lett. 1987, 1927-30.
60. Morita, S.; Okada, T.; Ishigame, Y.; Mikoshiba, N. Surf. S c i .
1987 181, 119-25.
61. Morita, S.; Otsuka, I.; Okada, T.; Yokoyama, H.; Iwasaki, T.;
Mikoshiba, N. Jap. J . Appl. Phys. 1987 26, L1853-55.
62. Bard, A.J.; Faulkner, L.R. Electrochemical Methods: Fundamentals
and Applications; John Wiley & Sons: New York, 1980, p 699.
63. Hubbard, A.T.; Anson, F.C. In E l e c t r o a n a l y t i c a l Chemistry;
Bard, A.J., Ed.; Marcel Dekker: New York, 1970; v o l . 4, p 129.
64. Davis, J.M.; Fan, F-R.F.; Bard, A.J. J . Electroanal. Chem. 1988,
238, 9-31.
65. Wightman, R.M. Anal. Chem. 1981, 53, 1126A-31A.
66. Geng, L.; Reed, R.A.; Longmire, M.; Murray, R.W. J . Phys. Chem.
1987, 91, 2908-14.
67. Gomez, J . ; Vasquez, L.; Baro, A.M.; Garcia, N.; P e r d r i e l , C.L.;
Triaca, W.E.; Avria, A.J. Nature 1986 323, 612-14.
68. Vasquez, L.; Gomez, J . ; Baro, A.M.; Barcia, N.; Marcos, M.L.;
Velasco, J.G.; Vara, J.M.; Arvia, A.J.; Presa, J . ; Garcia, A.;
Aguilar, M. J . Am. Chem. Soc. 1987, 109, 1730-33.
69. Morita, S.; Itaya, K.; Mikoshiba, N. Jap. J . Appl. Phys. 1986
25, L743-45.
70. Batra, I.P.; Barker, J.A.; Auerbach, D.J. J . Vac. S c i . Technol.
A 1984, 2, 943-47.
71. Gimzewshi, J.K.; S t o l l , E.; S c h l i t t l e r , R.R. Surf. S c i . 1987,
181, 267-77.
72. H a l l , J.T.; Hansma, P.K. Surf. S c i . 1978, 76, 61-76.
73. Smith, D.P.E.; Bryant, A.; Quate, C.F.; Rabe, J.P.; Gerber, Ch.;
Swalen, J.D. Proc. Natl. Acad. S c i . USA 1987, 84, 969-72.
74. Binnig, G. B u l l . Am. Phys. Soc. 1986, 31, 217.
75. Foster, J.S.; Frommer, J.E.; Arnett, P.C. Nature 331, 324-26.
76. Wrighton, M.S. Science 1986, 231, 32-37.
77. Murray, R.W. Acc. Chem. Res. 1980, 13, 135-41.
78. Buttry, D.A.; Anson, F.C. J . Am. Chem. Soc. 1983, 105, 685-89.
79. M i l l e r , C.J.; Majda, M. J . Am. Chem. Soc. 1986, 108, 3118-20.

80. Finklea, H.O.; Robinson, L.R.; Blackburn, A.; Richter, B.;

A l l a r a , D.; Bright, T. Langmuir 1986, 2, 239-44.
81. Ringger, M.; Hidber, H.R.; Schlog, R.; Oelhafen, P.; Guntherodt,
H.J. A p pl. Phys. Lett. 1985, 46, 832-34.
82. Staufer, U.; Wiesendanger, R.; Eng, L.; Rosenthaler, L.; Hidber,
J.R.; Guntherodt, H.-J. Appl. Phys. Lett. 1987, 51, 244-46.
83. McCord, M.A.; Pease, R.F.W. J . Vac.Sci.Technol. B 1987, 5,
430-33.
84. S i l v e r , R.M.; Ehrichs, E.E.; de Lozanne, A.L. Appl. Phys. L e t t .
1987, 51, 247-49.
85. Becker, R.S.; Golovchanko, J.A.; Swartzentruber, B.S. Nature
1987, 325, 419-21.
86. Schneir, J . ; Hansma, P.K. Langmuir 1987, 3, 1025-27.
87. Schneir, J . ; Sonnenfeld, R.; M a r t i , O.; Hansma, P.K.; Demuth,
J.E.; Hamers, R.J. J . Appl. Phys. 1988, 63, 717-21.
88. McCord, M.A.; Pease, R.F.W. Appl. Phys. Lett. 1987, 50, 569-70.
89. L i n , C.W.; Fan, F-R.F.
134, 1038-39.
90. Kolb, D.M. I n Advances in Electrochemistry and Electrochemical
Engineering; Gerischer, H. and Tobias,C.W., Eds.; John Wiley &
Sons: New York, 1978; v o l . 2, p 125.
91. Morcos, I . J. Electroanal. Chem. 1975, 66, 250-57.
92. L i u , H-Y.; Fan, F-R.F.; L i n , C.W.; Bard, A.J. J. Am. Chem. Soc.
1986, 108, 3838-39.
93. Giambattista, B.; McNairy, W.W.; Slough, C.G.; Johnson, A.;
Bell, L.D.; Coleman, R.V.; Schneir, J . ; Sonnenfeld, R.; Drake,
B.; Hansma, P.K. Proc. Nat. Acad. S c i . USA 1987, 84, 4671-74.
94. Sonnenfeld, R.; Schardt, B.C. Appl. Phys. Lett. 1986, 49, 1172-
74.
95. Nanoscope, D i g i t a l Instruments, Inc., 5901 Encina Rd., Goleta,
CA 93117.
96. WA Technology Inc., 41 Accord Park Drive, Norwell, MA 02061.
97. M c A l l i s t e r Technical Services, Inc., 2414 S i x t h Street,
Berkeley, CA 94710.
98. Dovek, M.M.; Heben, M.J.; Lang, C.; Lewis, N.S.; Quate, C.F.
Rev. S c i . I n s t r . , i n press.

Electrochemical Surface Science:
Molecular Phenomena at Electrode Surfaces
ACS SYMPOSIUM SERIES 378
ERRATA
On page 182, the sentence below equation 3 should read
In the above equations, a is the conical aspect ratio, r/h; 7 is the

ratio of the interelectrode distance to the cone or hemisphere
radius, d/r; and I, the dimensionless faradaic current (either I con
or I ), is the ratio between the one-dimensional current

hsph
contribution, i ^ ^ and the limiting current for an isolated

hemispherical electrode, i . (see Eq. 5) (64):
h
On page 183, thex-axis in Figure 3 should read
gamma = d/r

Chapter 14
Electrochemical Surface Characterization

of Platinum Electrodes Using Elementary
Electrosorption Processes at Basal
and Stepped Surfaces
J. Clavilier
Laboratoire d'Electrochimie Interfaciale du Centre National

de la Recherche Scientifique 1 Place A Briand 92195 Meudon
An attempt has been made at using voltammetry of hydrogen

adsorption-desorption on platinum as a tool for in-situ
checking the crystalline surface structure of platinum at
the atomic level. The behaviour of Pt(111), Pt(100) and
stepped surfaces i s discussed in connection with the rôle
of the long-range order on the unusual adsorption states.
Application is made to the investigation of surface chan-
ges as the effect of annealing and characterization of
platinum black crystallites.
E l e c t r o c h e m i s t r y of surface processes a t s o l i d metal e l e c t r o d e s i s
undergoing a profound change due t o t h emastery of t h eu s e o f metal
s i n g l e c r y s t a l s as electrodes i n p a r a l l e l with t h eother techniques
of s u r f a c e s c i e n c e .
By c o m p a r i n g t h e e l e c t r o c h e m i c a l p r o p e r t i e s o f s e l e c t e d m e t a l s i n g l e
c r y s t a l s with basal o r i e n t a t i o n s , and then i n t r o d u c i n g s u r f a c e d e -
f e c t s i n a w e l l - d e f i n e d manner l i k e p e r i o d i c a r r a y s o f monoatomic
steps, t h eelectrochemical response of t h eelectrode surface gains a
p h y s i c a l meaning which approaches t h es u r f a c e processes a t t h e ato-
mic l e v e l o f t h e s u r f a c e . T h i s b e c o m e s t h e m a j o r way f o r t h e r e n e w a l
o f s u r f a c e e l e c t r o c h e m i s t r y w h i c h i s now a p r o m i s i n g b r a n c h o f s u r -
face science.
Among t h e m e t a l e l e c t r o d e s w i t h s u r f a c e s t r u c t u r e s e n s i t i v e p r o p e r -
t i e s , t h e f i r s t ones t o be considered a r ethose with e l e c t r o c a t a l y t i c
a c t i v i t y , such a s p l a t i n u m group m e t a l s . Thus p l a t i n u m i s t h e most
a t t r a c t i v e material because of i t s exceptional spectrum of c a t a l y t i c
p r o p e r t i e s and i t s good s t a b i l i t y i n v a r i o u s e l e c t r o l y t i c media.
A f e w y e a r s a g o p l a t i n u m was t h o u g h t t o b e a w e l l known s o l i d
electrode and i t s adsorption and e l e c t r o c a t a l y t i c p r o p e r t i e s widely
investigated, p a r t i c u l a r l y i t s adsorption properties f o r hydrogen
and o x y g e n . Thus smooth p o l y c r y s t a l l i n e s u r f a c e s , f i n e l y d i v i d e d
p a r t i c l e s , were c h a r a c t e r i z e d both b y t h e e x i s t e n c e o f two main
electrochemical hydrogen adsorption s t a t e s i . e . weakly and s t r o n g l y
bonded h y d r o g e n more e a s i l y o b s e r v a b l e w i t h t h e l a t t e r e l e c t r o d e s
than with t h eformer. Extremely r e p r o d u c i b l e hydrogen adsorption
0097-6156/88/0378-0202$06.00A)
c

14. CLAVILIER Surface Characterization of Platinum Electrodes 203
s t a t e s are observed a f t e r a p p l i c a t i o n of the " a c t i v a t i o n " p r o c e d u r e ,

f i r s t a p p l i e d t o s m o o t h p l a t i n u m s a m p l e s by Hammett ( I K A r e v i e w of
w o r k on p l a t i n u m a c t i v a t i o n was p u b l i s h e d i n 1967 b y J a m e s ( 2 ) w h i c h
g i v e s a c o m p l e t e d i s c u s s i o n of the q u e s t i o n at t h a t time.
T h i s p r o c e d u r e was a p p l i e d t o p l a t i n u m s i n g l e c r y s t a l e l e c t r o d e s b y
W i l l (3) i n h i s p i o n n e r i n g work t o a s s i g n t h e w e a k l y and s t r o n g l y
bonded hydrogen to s u r f a c e c r y s t a l l i n e h e t e r o g e n e i t y . Will's
e x p e r i m e n t s h a v e s h o w n t h a t t h e w e a k l y b o n d e d h y d r o g e n was t h e m a j o r
s p e c i e s on t h e P t ( 1 1 0 ) a c t i v a t e d e l e c t r o d e w h i l e t h e s t r o n g l y b o n d e d
h y d r o g e n was t h e m a j o r o n e o n t h e a c t i v a t e d P t ( i O O ) s u r f a c e . He
m i s i n t e r p r e t e d t h e s p e c i e s a d s o r b e d on t h e ( 1 1 1 ) o r i e n t a t i o n f o r t h e
r e a s o n s we w i l l s e e b e l o w . I n t h i s w o r k t h e a c t i v a t i o n was f i r s t
c o n s i d e r e d as a p r o c e d u r e f o r the e l e c t r o c h e m i c a l c l e a n i n g of the
surface. Nevertheless the author concluded that a change in c r y s -
t a l l i n e s u r f a c e s t r u c t u r e was t h e c o n s e q u e n c e o f a c t i v a t i o n b y
r e p e a t e d o x i d a t i o n and r e d u c t i o f th oriented platinu surfaces
U n t i l r e c e n t l y the r e s u l t i n
as w e l l as i t s e x a c t n a t u r
Clean and Well-Ordered Platinum Surfaces for Electrochemical Purpose
a) I n i t i a l l y c l e a n s u r f a c e s . I n o r d e r t o a v o i d t h e d i f f i c u l t i e s
r e l a t e d to the a c t i v a t i o n procedure for o b t a i n i n g e f f i c i e n t adsor-
bing platinum surfaces, platinum s i n g l e c r y s t a l s with oriented
s u r f a c e s w e r e c l e a n e d and c h a r a c t e r i z e d by u s i n g u l t r a h i g h v a c u u m
t e c h n i q u e (UHV) t h e n t r a n s f e r r e d i n t o a n e l e c t r o c h e m i c a l c e l l (4).
The use of a t h i n l a y e r c e l l r e d u c e d t h e amount of a d s o r b a b l e so-
l u t i o n i m p u r i t i e s (5) i n t e r f e r i n g w i t h h y d r o g e n a d s o r p t i o n .
E x p e r i m e n t s c a r r i e d o u t i n t h i s way c o n f i r m e d W i l l ' s c o n c l u s i o n s o n
t h e o r i g i n o f t h e two h y d r o g e n a d s o r p t i o n s t a t e s and s h o w e d
d e f i n i t e l y t h a t e l e c t r o s o r b e d h y d r o g e n c o u l d be u s e d as a s u r f a c e
sensitive probe.Nevertheless i f we c o n s i d e r t h e e l e c t r o c h e m i c a l
r e s u l t s obtained with clean platinum oriented surfaces prepared
d u r i n g UHV e x p e r i m e n t s , s t u d i e d i n t h e r a n g e o f p o t e n t i a l o f t h e
r e v e r s i b l e a d s o r p t i o n - d e s o r p t i o n of h y d r o g e n , the amount of a d s o r b e d
h y d r o g e n was n o t t h e s a m e w i t h t h e v a r i o u s e x p e r i m e n t a l d e v i c e s u s e d .
T h i s q u a n t i t y was r e m a r k a b l y d i f f e r e n t f o r t h e ( 1 1 1 ) o r i e n t a t i o n ,
v a r y i n g f r o m 0 . 0 3 t o 0.4 o f a m o n o l a y e r ( 6 ) , ( 7 ) . When s u c h a n
e l e c t r o d e was a c t i v a t e d , a f t e r f e w c y c l e s o f e l e c t r o c h e m i c a l
a d s o r p t i o n and d e s o r p t i o n of o x y g e n , t h e amount of h y d r o g e n a d s o r b e d
was i n c r e a s e d a n d t h e v o l t a m m e t r i c p r o f i l e o f h y d r o g e n a d s o r p t i o n
d e s o r p t i o n was c h a n g e d ( 8 ) . T h e g e n e r a l b e h a v i o u r o f t h e (111)
o r i e n t a t i o n o f p l a t i n u m was i n d i c a t i v e t h a t t h e t e c h n i q u e u s e d d i d
not succeed i n p r e p a r i n g c l e a n s u r f a c e s a f t e r the c o n t a c t with the
e l e c t r o l y t e was e s t a b l i s h e d . A n o t h e r r o u t e f o r c l e a n s u r f a c e
p r e p a r a t i o n , c l e a n t r a n s f e r of t h e s a m p l e and c l e a n c o n t a c t w i t h t h e
e l e c t r o l y t e was required.
b> C l e a n p l a t i n u m s u r f a c e s i n c o n t a c t w i t h an e l e c t r o l y t i c s o l u t i o n .
The t e c h n i q u e w h i c h h a s b e e n d e v e l o p e d s i n c e 1980 c o n s i s t s i n u s i n g
the c a t a l y t i c p r o p e r t i e s of p l a t i n u m f o r o x i d a t i o n of c a r b o n a c e o u s
and s u l p h u r s u r f a c e compounds w h i c h a r e t h e m a j o r c o n t a m i n a n t s of
the s u r f a c e of p l a t i n u m samples exposed t o the atmospheric

e n v i r o n m e n t and w h i c h r e a d s o r b a t t h e s u r f a c e a f t e r a p p l i c a t i o n o f
c l e a n i n g p r o c e d u r e i f n o s p e c i a l c a r e i s t a k e n . The r e m o v a l o f
i m p u r i t i e s was a c h i e v e d b y h e a t i n g t h e p l a t i n u m i n a g a s - o x y g e n
f l a m e and q u e n c h i n g t h e s a m p l e i n t o a s t r e a m of u l t r a p u r e w a t e r
during c o o l i n g i n a i r . A d r o p l e t o fwater stayed attached to the
o r i e n t e d s u r f a c e of the c r y s t a l p r o t e c t i n g i t a g a i n s t back
c o n t a m i n a t i o n b y d e c r e a s i n g t o a g r e a t e x t e n t the r a t e of t r a n s f e r
of i m p u r i t i e s from atmosphere to the s u r f a c e (9).
T h e p l a t i n u m s i n g l e c r y s t a l s t r e a t e d i n t h i s way a r e s m a l l s p h e r i c a l
p l a t i n u m b e a d s w i t h a d i a m e t e r r a n g i n g f r o m 1.5 t o 1.9 mm o b t a i n e d
by m e l t i n g o f a w i r e . T h e y a r e o r i e n t e d , c u t and p o l i s h e d a c c o r d i n g
t o t h e t e c h n i q u e d e s c r i b e d i n (10.) w i t h a n a c c u r a c y w i t h i n 3 m i n u t e s
of the nominal o r i e n t a t i o n . A f t e r p o l i s h i n g , the samples are
annealed at 1300°-1500°C to e l i m i n a t e the perturbed s u r f a c e l a y e r .
In t h e i n i t i a l e x p e r i m e n t s r e p o r t e d i n r e f . ( 9 ) t h e t h e r m a l
decontamination t r e a t m e n t was c a r r i e d o u t a t h i g h t e m p e r a t u r e (t >
9 0 0 ° C ) . T h i s t e c h n i q u e ha bee improved i orde maintai th
q u a l i t y of the c r y s t a l f o
procedure the s i n g l e c r y s t a
flame but heated i n d i r e c t l y through the thermal c o n d u c t i o n of the
p l a t i n u m w i r e . The t e m p e r a t u r e o f a n n e a l i n g i s n e a r l y 5 0 0 ° C f o r few
s e c o n d s , t h e n t h e c r y s t a l i s c o o l e d i n a i r and q u e n c h e d when i t s
9
temperature i s n e a r l y 2 0 0 C i . e . when c a t a l y t i c o x i d a t i o n o f i m p u -
r i t i e s coming i n t o contact with the s u r f a c e ceases to be e f f i c i e n t .
This thermal treatment a p p l i e d for surface decontamination must b e
d i s t i n g u i s h e d from the treatment f o r s u r f a c e r e - o r d e r i n g which
r e q u i r e s higher annealing temperatures a s an example w i l l
demonstrate below.
P l a t i n u m s u r f a c e s w i t h (111) and (100) o r i e n t a t i o n s t r e a t e d i n t h i s
u
way h a v e b e e n c h e c k e d b y u s i n g L E E D c h a r a c t e r i z a t i o n o n a s
r e c e i v e d " s a m p l e s , both showed the c h a r a c t e r i s t i c LEED p a t t e r n with
t h e i r r e s p e c t i v e ( l x l ) s u r f a c e s y m m e t r y . The non o b s e r v a t i o n of t h e
( 5 x 2 0 ) s y m m e t r y f o r t h e ( 1 0 0 ) o r i e n t a t i o n was d u e t o t h e p r e s e n c e o f
r e s i d u a l adsorbed i m p u r i t i e s at the s u r f a c e of "as r e c e i v e d " s a m p l e s .
Simply t h i s c o n f i r m s the c r y s t a l l i n e s u r f a c e q u a l i t y of the p l a t i n u m
samples prepared according to t h i s technique (10).
Voltammetry for Surface A n a l y s i s and Structural Characterization
It may b e s e e n i n f i g . l a n e x a m p l e of s u r f a c e a n a l y s i s b y u s i n g
voltammetry. Inthese experiments the thermally t r e a t e d samples,
have been put i n c o n t a c t with the s o l u t i o n a t a c o n t r o l l e d p o t e n t i a l
c h o s e n i n s u c h a way t h a t n o o r n e g l i g i b l e c u r r e n t t r a n s i e n t s w e r e
d e t e c t e d when t h e s a m p l e s c o n t a c t e d t h e s o l u t i o n . T h i s a l l o w s t h e
a n a l y s i s of i n i t i a l s u r f a c e c o n d i t i o n s ( l U . T h e oxygen a d s o r b e d
d u r i n g t h e t h e r m a l t r e a t m e n t i s r e d u c e d i n t h e f i r s t n e g a t i v e sweep
i n t h e p o t e n t i a l r a n g e 0.9-0.6 V/R.H.E. The amount o f e l e c t r i c
c h a r g e f o r t h i s r e d u c t i o n i s a c h a r a c t e r i s t i c q u a n t i t y and
c o r r e s p o n d s t o t h e maximum c o v e r a g e w h i c h i s f o r m e d o n e a c h
o r i e n t a t i o n by the thermal treatment i n a i r .
In t h e s u b s e q u e n t p r o c e s s , w h i c h i s h y d r o g e n a d s o r p t i o n , e a c h
o r i e n t a t i o n h a s i t s maximum a d s o r p t i o n a c t i v i t y . H y d r o g e n i s
a d s o r b e d i n a n amount c o r r e s p o n d i n g t o one H adatom per s u r f a c e P t
atom o f t h e (111) and (100) o r i e n t a t i o n s and s i g n i f i c a n t l y more f o r

CLAVILIER Surface Characterization of Platinum Electrodes
F i g u r e 1. F i r s t v o l t a m m o g r a m s o f f l a m e - t r e a t e d p l a t i n u m ,
basal o r i e n t a t i o n s . Standard experimental conditions f o r
a l l f i g u r e s s e l e c t r o l y t e 0 . 5 M H S 0 « ; s w e e p r a t e : 5 0 mV.s~
2

P t ( l l O ) due t o i t e n d e n c y f o r t h i s o r i e n t a t i o n t o u n d e r g o t h e (1x2)
s u r f a c e r e c o n s t r u c t i o n . E v i d e n t l y both t h e r m a l l y a d s o r b e d o x y g e n and
e l e c t r o c h e m i c a l l y adsorbed hydrogen are r e l a t e d through the surface
d e n s i t y of p l a t i n u m atoms. T h i s s e t of i n i t i a l d a t a i s i n d i c a t i v e o f
t h e c l e a n l i n e s s of s a m p l e s p r e p a r e d and t r a n s f e r r e d b y t h i s m e t h o d .
The a v a i l a b i l i t y of c l e a n p l a t i n u m s u r f a c e s w i t h d e f i n e d o r i e n t a t i o n
in contact with the e l e c t r o l y t i c s o l u t i o n allows the separation o f
the various processes o c c u r r i n g during the electrochemical a c t i v a -
t i o n a p a r t from the o x i d a t i o n of i m p u r i t i e s .
However t h e more i m p o r t a n t q u e s t i o n which can b e s o l v e d w i t h such
samples i s r e l a t e d t o c h a r a c t e r i z a t i o n of s u r f a c e s i t e s because each
b a s a l o r i e n t a t i o n shows w e l l - c h a r a c t e r i z e d hydrogen a d s o r p t i o n -
d e s o r p t i o n peaks which might b e h e l p f u l l y used f o r t h i s purpose.
The main f e a t u r e of e l e c t r o s o r b e d h y d r o g e n a t b a s a l o r i e n t a t i o n i s
the presence of s e v e r a l peaks or a d s o r p t i o n s t a t e s f o r s u r f a c e s
c o n t a i n i n g a s i n g l e t y p e of s i t e l i k e P t ( l l l ) and P t ( l O O ) . T h i s
means t h a t the i n f o r m a t i o n a voltammogram c o n t a i n s c o n c e r n s more
than the simple i n t e r a c t i o
surface s i t e (short rang
must b e found p a r t i c u l a r l y b y u s i n g s t e p p e d s u r f a c e s which a l l o w s a
m o d u l a t i o n o f l o n g r a n g e i n t e r a c t i o n s when t h e y a r e s u s p e c t e d t o b e
at t h e o r i g i n of some a d s o r p t i o n s t a t e s .
This p o s s i b l e e f f e c t o f long range i n t e r a c t i o n s on the hydrogen
a d s o r p t i o n s t a t e s i s suggested by the f a c t that platinum e l e c t r o d e s
w i t h (111) and (100) o r i e n t a t i o n s , a f t e r t h e r m a l t r e a t m e n t , showed
a d s o r p t i o n s t a t e s at higher p o t e n t i a l than those observed p r e v i o u s l y
with a l l t y p e s of p l a t i n u m e l e c t r o d e s which were s u b j e c t e d t o
a c t i v a t i o n o r were i n s u f f i c i e n t l y c l e a n .
T h i s p u z z l i n g d i f f e r e n c e s i n c e has been s t u d i e d e x t e n s i v e l y e i t h e r
b y u s i n g p u r e e l e c t r o c h e m i c a l t e c h n i q u e ( 1 0 ) , ( 1 2 , 1 3 ) o r UHV s u r f a c e
s c i e n c e methods (14-17).
I n d e p e n d e n t l y of the t e c h n i q u e used to i n v e s t i g a t e the p r i m e c a u s e
of the e x i s t e n c e of the a d s o r p t i o n s t a t e s at the h i g h e r p o t e n t i a l s
on P t ( l l l ) and P t ( l O O ) , t h e c o n c l u s i o n i s t h e y r e s u l t f r o m t h e
e x i s t e n c e of a t o m i c a l l y f l a t e x t e n d e d s u r f a c e d o m a i n s w i t h t h e
r e s p e c t i v e o r i e n t a t i o n , i . e . e x i s t e n c e of long range s u r f a c e o r d e r .
T h e s e a d s o r p t i o n s t a t e s a p p e a r a s a n i n t r i g u i n g and a u n i q u e
p r o p e r t y of w e l l - o r d e r e d P t ( l l l ) and P t ( l O O ) s u r f a c e s i n c o n t a c t
with various e l e c t r o l y t e s o l u t i o n s because no equivalent e f f e c t s are
known w i t h t h e same o r i e n t a t i o n s i n gas p h a s e e x p e r i m e n t s . Inthis
s e n s e , t h e s e p r o p e r t i e s may b e c o n s i d e r e d a s a s p e c i f i c a s p e c t o f
the e l e c t r o c h e m i s t r y o f surface processes.
The q u e s t i o n of t h e s p e c i e s i n v o l v e d i n t h e s e u n u s u a l adsorption
s t a t e s i s s t i l l c o n t r o v e r s i a l . No d i r e c t i n f o r m a t i o n ( s u c h a s
s p e c t r o s c o p i c d a t a ) o n the n a t u r e of the s p e c i e s i s a v a i l a b l e . Only
e l e c t r o c h e m i c a l d a t a h a v e been o b t a i n e d and t h e s e r e q u i r e s e v e r a l
c r o s s d e t e r m i n a t i o n s and c a r e f u l d i s c u s s i o n t a k i n g i n t o a c c o u n t the
w h o l e e x p e r i m e n t a l d a t a s e t and t h e p a r a l l e l b e h a v i o u r o f t h e (100)
and (111) o r i e n t a t i o n s .
With t h i s i n mind the s p e c i e s which f i t s the best with the
experimental data f o r the anomalous a d s o r p t i o n s t a t e s would b e a
f u l l y r e v e r s i b l y d i s c h a r g e d s p e c i e s i n c l u d i n g t r a n s f e r o f one
e l e c t r o n . It could b e an adsorbed hydrogen-like s p e c i e s under f u l l
c o n t r o l o f the s p e c i f i c a d s o r p t i o n of a n i o n s of the base e l e c t r o l y t e

14. CLAVILIER Surface Characterization ofPlatinum Electrodes 207
( 1 8 ) . T h i s c o u l d a c c o u n t f o r t h e a b s e n c e o f a n y pH d e p e n d e n c e o f t h e
unusual a d s o r p t i o n s t a t e s i n presence of s p e c i f i c a d s o r p t i o n of
s u l p h u r i c a n i o n (13.). R e c e n t r e s u l t s ( K r a u s k o p f , E . K.; R i c e , L . H . j
W i e c k o w s k i , A. J . E l e c t r o a n a l . C h e * . i n p r e s s ) o b t a i n e d w i t h
T
l a b e l e d s u l p h u r i c anions are i n agrement with the hydrogen i n t e r p r e -

t a t i o n . The m a j o r d i f f i c u l t y w i t h t h e h y d r o g e n h y p o t h e s i s i s t h e
p o t e n t i a l of the u n u s u a l a d s o r b e d h y d r o g e n i n a b s e n c e of a n i o n s p e c i -
f i c a d s o r p t i o n c a n n o t be c o r r e l a t e d w i t h e n e r g y f o r h y d r o g e n a d s o r -
bed f r o m gas p h a s e a t t h e same o r i e n t a t i o n . T h e r e i s t o o l a r g e a d i f -
f e r e n c e i n t h e h y d r o g e n b i n d i n g e n e r g y v a l u e s ( 1 5 ) . In t h i s r e s p e c t
i t was f o u n d i n g a s p h a s e f o r P t m ( l l l ) x ( l l l ) t h a t h y d r o g e n i s m o r e
s t r o n g l y b o n d e d on s t e p t h a n o n t e r r a c e (19.). I t w i l l b e s h o w n b e l o w
that the p o t e n t i a l sequence for the r e s p e c t i v e hydrogen s t a t e s gives
the inverse order. This conclusion i s v a l i d for stepped surfaces
w i t h (100) t e r r a c e s . Thus a d i r e c t c o m p a r i s o n b e t w e e n t h e gas p h a s e
b i n d i n g e n e r g y and t h e a d s o r p t i o n p o t e n t i a l d o e s n o t seem p o s s i b l e .
Other hypotheses i n t r o d u c e d i f f i c u l t i e s too the most a p p a r e n t being
either a large differenc
a n i o n s a t P t ( l l l ) and P t ( l O O )
sence or absence of s p e c i f i c a d s o r p t i o n . Whatever the s p e c i e s i n -
v o l v e d t h e s e a n o m a l o u s s t a t e s o b l i g e us t o r e - e x a m i n e c a r e f u l l y ,
c l a s s i c a l i n t e r f a c i a l c o n c e p t s . An e x a m p l e i s g i v e n w i t h t h e new
concept of the r o l e of s u r f a c e long range order i n a d s o r p t i o n
p r o p e r t i e s w h i c h i s now c l e a r l y e s t a b l i s h e d .
As an i l l u s t r a t i o n of the above comments, r e s u l t s o b t a i n e d with
(111) and (100) o r i e n t a t i o n s a r e d i s c u s s e d i n p a r a l l e l .
Surface processes r e l a t e d to electrochemical activation
The u n d e r s t a n d i n g o f a c t i v a t i o n e f f e c t s on t h e e l e c t r o c h e m i c a l
b e h a v i o u r of o r d e r e d p l a t i n u m s u r f a c e s w i l l a l l o w the p o s s i b i l i t y of
c o r r e l a t i n g the c l a s s i c a l knowledge of p l a t i n u m a d s o r p t i o n behaviour
w i t h t h e new observations.
a/ H i g h o x y g e n c o v e r a g e . L e t us c o n s i d e r f i r s t t h e e f f e c t of a h i g h
o x y g e n c o v e r a g e by e l e c t r o s o r b e d o x y g e n a t a c l e a n P t ( l l l ) / 0 . 5 M
H2SO4 i n t e r f a c e . The i n i t i a l voltammogram i s shown i n f i g . 1 . A t such
a s u r f a c e o x y g e n a d s o r p t i o n o c c u r s a b o v e 1.25 V / R . H . E . a s s h o w n i n
2
f i g . 2 A c u r v e 1. I t a m o u n t s t o n e a r l y 5 0 0 p C . c m " a n d t h e b a l a n c e o f
charge i s exact for desorption. This i s a requirement in agreement
with surface c l e a n l i n e s s . Subsequent, hydrogen adsorption-desorption
l o o k s s i m i l a r t o t h a t a t a p o l y c r y s t a l l i n e s u r f a c e and t h e u n u s u a l
b o n d e d s t a t e s h a v e d e c r e a s e d and s h i f t e d p o s i t i v e l y . T h i s e f f e c t i s
r e i n f o r c e d i n the second c y c l e where oxygen a d s o r p t i o n p o t e n t i a l i s
i s decreased. A f t e r t h i r t y c y c l e s between 0.05-1.45 V the r e v e r s i b l e
p e a k s a t 0.110 V/R.H.E. a r e w e l l d e v e l o p e d , and t h e u n u s u a l s t a t e s
a r e s p r e a d i n a w i d e r a n g e of p o t e n t i a l w i t h a low amplitude.
The same t y p e of v o l t a m m o g r a m has been o b t a i n e d w i t h a P t ( l l l ) e l e c -
t r o d e a f t e r i t s o r d e r e d s u r f a c e was s u b j e c t e d t o a r g o n i o n b o m b a r d -
ment, i n t r o d u c i n g s t r u c t u r a l d e f e c t s l i k e randomly d i s t r i b u t e d s t e p s
(14.). T h e s i m i l a r e f f e c t s o f o x y g e n e l e c t r o s o r p t i o n a n d i o n b o m b a r d -
ment show c l e a r l y t h a t t h e f o r m e r p e r t u r b s t h e s u r f a c e o r d e r .
The f i r s t c o n s e q u e n c e of b o t h t r e a t m e n t s i s t h e c o n s i d e r a b l e
d e c r e a s e of t h e a n o m a l o u s a d s o r p t i o n s t a t e s . T h i s i s one of t h e

F i g u r e 2 B. Low o x y g e n c o v e r a g e o n P t ( l l i ) , (i) initial,

(f) l a s t voltammograois.
F i g u r e 2 C. E f f e c t o f a n n e a l i n g o n t h e r e o r d e r i n g o f
p o l i s h e d P t ( l l l ) , a n n e a l i n g t i m e : ( l ) n o a n n e a l i n g j ( 2 ) 1.5
mn ; ( 3 ) 6.5am

14. CLAVILIER Surface Characterization of Platinum 209
p i e c e s of e v i d e n c e f o r the r e s p o n s i b i l i t y of long-range order in the

e x i s t e n c e of t h e s e states.
A s e c o n d c o n s e q u e n c e o f b o t h t r e a t m e n t s i s t h a t a m a j o r i t y o f new
s i t e s a p p e a r s g i v i n g r i s e t o p e a k s a t 0.110 V t h e e x a c t p o t e n t i a l o f
the main peaks observed with Pt(110) f i g . l c o n s e q u e n t l y they are
a s s u m e d of t h e same n a t u r e . The h y d r o g e n a d s o r b e d a t t h i s p o t e n t i a l
c o r r e s p o n d s t o t h e w e a k l y b o n d e d h y d r o g e n on a p o l y o r i e n t e d s u r f a c e .
R e v e r s i b l e peaks corresponding to the c l a s s i c a l s t r o n g l y bonded
h y d r o g e n grow a t t h e f i r s t c y c l e and d i s a p p e a r p r o g r e s s i v e l y w i t h
c y c l i n g m e a n i n g t h a t (100) s i t e s r e a c h a r a t h e r low s u r f a c e d e n s i t y .
The t h i r d c o n s e q u e n c e i s t h a t t h e t r a n s f o r m a t i o n of t h e v o l t a m m o g r a m
i n f i g . 2 A o c c u r s w i t h a c o n s t a n t amount of e l e c t r i c c h a r g e when t h e
c h a r g e i s summed o v e r a l l t h e r e v e r s i b l e a d s o r p t i o n s t a t e s i n c l u d i n g
t h e u n u s u a l o n e s . The d e c r e a s e i n c h a r g e f o r u n u s u a l s t a t e s i s
c o m p e n s a t e d by t h e i n c r e a s e i n c h a r g e f o r t h e n o r m a l s t a t e s ( 1 2 ) ( 2 0 )
Such behaviour i s coheren
adsorbed species for a l
The same b e h a v i o u r i s o b s e r v e d i n p e r c h l o r i c or h y d r o f l u o r i c a c i d s o -
l u t i o n s . U n f o r t u n a t e l y a q u a n t i t a t i v e a n a l y s i s c a n n o t be c a r r i e d o u t
because the unusual adsorption s t a t e current i s merging i n t o the cur-
r e n t of oxygen a d s o r p t i o n at the s u r f a c e d e f e c t s , the former decrea-
ses while the l a t t e r i n c r e a s e s with s u r f a c e d e f e c t s d e n s i t y (17).
In v i e w of t h e l a r g e c o n t r i b u t i o n of (110) s i t e s t o t h e h y d r o g e n
a d s o r p t i o n a t an e l e c t r o c h e m i c a l l y p e r t u r b e d ( 1 1 1 ) o r i e n t a t i o n ,
s t e p p e d s u r f a c e s w i t h (110) s t e p s and (111) t e r r a c e s h a v e b e e n
used f o r the modeling of the main v o l t a m m e t r i c features
of p e r t u r b e d P t ( l l l ) . F i g . 5 shows the voltammogram of a f l a m e -
t r e a t e d Pt(332) e l e c t r o d e otherwise noted 6(111)x(111) or
5 ( l l l ) x ( 1 1 0 ) b e c a u s e t h e s t e p s i t e s h a v e t h e (110) c o n f i g u r a t i o n . As
e x p e c t e d t h e v o l t a m m o g r a m s h o w s t h e r e v e r s i b l e p e a k s a t 0.110 V
c h a r a c t e r i s t i c of h y d r o g e n a d s o r p t i o n - d e s o r p t i o n a t P t ( l l O ) . The
o t h e r s t a t e s a r e due t o t h e h y d r o g e n a d s o r p t i o n - d e s o r p t i o n at
t e r r a c e s . T h i s voltammogram compared t o t h a t of P t ( l l l ) f i g . l shows
c l e a r l y a s m a l l e r amount of the unusual a d s o r p t i o n s t a t e at a more
p o s i t i v e p o t e n t i a l much l i k e a f t e r t h e f i r s t o x y g e n a d s o r p t i o n -
d e s o r p t i o n a t h i g h c o v e r a g e . On t h e o t h e r h a n d , t h e v o l t a m m o g r a m o f
P t ( 3 3 2 ) i n f i g . 5 i s another c o n f i r m a t i o n of the e f f e c t of long-range
o r d e r on t h e u n u s u a l a d s o r p t i o n s t a t e s .
On t h i s v o l t a m m o g r a m t h e h y d r o g e n a d s o r b e d a t s t e p s i t e s
c o r r e s p o n d s to a s t a t e near the lower l i m i t of the p o t e n t i a l r a n g e
i . e . to the weakly bonded s t a t e , a c o n c l u s i o n at v a r i a n c e with gas
p h a s e r e s u l t s (19.).
b / Low o x y g e n c o v e r a g e . L e t u s now c o n s i d e r t h e e f f e c t o f l o w
o x y g e n c o v e r a g e f o r t h e o b s e r v a t i o n of t h e f i r s t s t e p s i n t h e
P t ( l l l ) s u r f a c e t r a n s f o r m a t i o n . The p r o g r e s s i v e t r a n s f o r m a t i o n
o b s e r v e d i n f i g . 2 B i s o b t a i n e d by a p p l y i n g s u c c e s s i v e l y f a s t r e p e -
t i t i v e s e q u e n c e s o f c y c l i n g b e t w e e n 0.05 - 1.2 V. I t c a n b e s e e n
that the f o l l o w i n g changes are simultaneous : i n c r e a s e of the peaks
a t 0 . 1 1 0 V, d e c r e a s e o f t h e u n u s u a l a d s o r p t i o n s t a t e s , i n c r e a s e o f
t h e amount of adsorbed oxygen. These e f f e c t s a l l o w the d e f i n i t i o n

of c r i t e r i a f o r t h e e v a l u a t i o n of the q u a l i t y of a P t ( l l l ) s u r f a c e .
It i s e v i d e n t t h a t t h e s e c h a n g e s a r e due t o a n i n c r e a s e i n
s t r u c t u r a l s u r f a c e d e f e c t d e n s i t y , and o x y g e n a d s o r p t i o n o c c u r s
p a r t i c u l a r l y a t t h e s e d e f e c t s w h i l e s i m u l t a n e o u s l y (110) s i t e s may
be d e t e c t e d b y h y d r o g e n a d s o r p t i o n .
Thermal r e o r d e r i n g of P t ( l l l ) a f t e r p o l i s h i n g
T h e s e c r i t e r i a a r e shown t o b e u s e f u l t o i n v e s t i g a t e t h e r e o r g a -
n i s a t i o n o f t h e s u r f a c e l a y e r s a f t e r t h e p o l i s h i n g o f a (111)
p l a t i n u m s u r f a c e . F i g . 2 C shows the voltammograms of a f r e s h l y
p o l i s h e d P t ( l l l ) s a m p l e . T h e f i r s t c u r v e was r e c o r d e d w i t h t h e
s a m p l e t r e a t e d few s e c o n d s i n t h e r a n g e 4 0 0 - 5 0 0 ° C i n p r e s e n c e o f
a i r f o r s u r f a c e c l e a n i n g . The f i r s t v o l t a m m o g r a m shows t h e s u r f a c e
c l e a n l i n e s s . I t s h o w s c o m m o n f e a t u r e s w i t h t h e c u r v e 1, f i g . 2 A ,
w e l l d e v e l o p e d p e a k s f o r t h e h y d r o g e n a d s o r p t i o n a t (110) s i t e s a t
0.110 V s m a l l r e v e r s i b l e p e a k s a t 0.26 V c o r r e s p o n d i n g t o s t r o n g l y
b o n d e d h y d r o g e n o n (100) s i t e s and a non n e g l i g i b l e c o n t r i b u t i o n
of the unusual a d s o r p t i o
a d s o r p t i o n at s u r f a c e s t r u c t u r a
n e g l i g i b l e amount of unusual a d s o r p t i o n s t a t e s means t h a t wide
d o m a i n s w i t h (111) o r i e n t a t i o n a r e p r e s e n t a t t h e s u r f a c e a f t e r
p o l i s h i n g . A f t e r t h a t t h e e l e c t r o d e was a n n e a l e d f o r l . S mn a t
1 3 0 0 - 1 4 0 0 ° C . T h e n t h e s u b s e q u e n t v o l t a m m o g r a m was r e c o r d e d , c u r v e 2 ,
f i g . 2 C . A s u b s t a n t i a l d e c r e a s e of t h e p e a k s a t 0.110 V i s o b s e r v e d ,
due t o t h e e l i m i n a t i o n of t h e (110) s i t e s w h i l e t h e u n u s u a l
a d s o r p t i o n s t a t e s a r e e n h a n c e d . A t t h e same t i m e o x y g e n i s a d s o r -
bed t o a l e s s e r e x t e n t . A f t e r new a n n e a l i n g i n t h e same t e m p e r a -
t u r e r a n g e f o r 5 mn t h e v o l t a m m o g r a m f o r a w e l l o r d e r e d ( 1 1 1 ) P t
s u r f a c e i s p r a c t i c a l l y a c h i e v e d . P e a k s a t 0.110 V h a v e d i s a p p e a r e d ,
the unusual adsorption s t a t e s are well developed with the sharp
s p i k e at 0.440 V, a d s o r p t i o n o f oxygen has p r a c t i c a l l y disappeared
too. F i g . 3 shows the voltammogram of a P t ( l l l ) e l e c t r o d e with r e -
o r d e r e d s u r f a c e b y a n n e a l i n g at h i g h t e m p e r a t u r e w i t h the minimum
amount o f s u r f a c e d e f e c t s .
Simple model f o r P t ( l l l ) p e r t u r b e d b y oxygen e l e c t r o s o r p t i o n .

It may b e assumed t h a t o x y g e n a d s o r p t i o n a s a r e s u l t o f p l a c e
e x c h a n g e m e c h a n i s m l e a v e s a f t e r d e s o r p t i o n some p l a t i n u m a t o m s i n
a p o s i t i o n of a d a t o m s a t t h e (111) o r d e r e d s u r f a c e .
I f we c o n s i d e r i n a h a r d s p h e r e m o d e l o f f e e c r y s t a l s , a d e n s e r o w
o f a d a t o m s o n t h e (111) s u r f a c e , o n e a c h s i d e o f t h e row new s i t e s
a r e c r e a t e d a t t h e s u r f a c e i n same a m o u n t , (110) o n one s i d e ( f i g .
4a) and (100) ( f i g . 4 b ) o n t h e o t h e r s i d e . The e x p e r i m e n t a l r e s u l t s
show t h a t t h e m a j o r i t y of t h e new s i t e s h a v e t h e (110) symmetry
t h i s i m p l i e s t h a t s u c h a row i s n o t a s t a b l e c o n f i g u r a t i o n f o r t h e
adatoms. More s t a b l e s m a l l t r i a n g u l a r i s l a n d s whose edge s i t e s
h a v e t h e (110) symmetry seem t o b e f o r m e d , f i g . 4 c p o s s i b l y (100)
k i n k s may a p p e a r , f i g . 4 d . T h i s t y p e o f s u r f a c e a r r a n g e m e n t i s n o t
u n u s u a l a t a (111) o r i e n t a t i o n and p r o b a b l y i s a t t h e o r i g i n o f
t h e s h a p e of c o r r o s i o n p i t s o b s e r v e d w i t h o n t h e (111) f a c e o f
many f e e m e t a l s . The mean w i d t h s of (111) o r d e r e d d o m a i n s may b e
e s t i m a t e d from t h e s h a p e and p o s i t i o n of t h e u n u s u a l adsorption
state observed with m ( l l l ) x ( l l l ) surfaces.

CLAVILIER Surface Characterization of Platinum Electrodes 211
1/ lA.cm" 2
- -50
0
1
0.1
I I I
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/1).5
^ ^— 1.0 E/V rhe
F i g u r e 3. V o l t a m m o g r a
defect contribution t
F i g u r e 4. H a r d s p h e r e m o d e l f o r p e r t u r b e d P t ( l l l ) . ( a )
d e n s e row o f P t a d a t o m s f o r m i n g (110) s i t e s , f r o n t v i e w ,
(b) r e a r v i e w s h o w i n g (100) s i t e s . ( c ) i s l a n d f o r m i n g (110)
edge s i t e s , (d) a (100) k i n k s i t e .

Pt(lOO) o r i e n t a t i o n and (100) s i t e s at stepped surfaces.
The P t ( l O O ) o r i e n t a t i o n has a more c o m p l e x e l e c t r o c h e m i c a l b e h a v i -

o u r . The v o l t a m m o g r a m o n f i g . l c o r r e s p o n d s t o a s u r f a c e c o o l e d i n
a i r . C o o l i n g i n t h e p r e s e n c e of h y d r o g e n t h e same a d s o r p t i o n s t a -
t e s a r e o b s e r v e d but w i t h a d i f f e r e n t d i s t r i b u t i o n , the most p o s i -
t i v e b e i n g t h e h i g h e s t one ( 1 U , ( 2 L ) . A s i m i l a r d i s t r i b u t i o n i s
o b t a i n e d i f t h e e l e c t r o d e i s s u b j e c t e d t o f e w c y c l e s i n a IM H C 1
s o l u t i o n p r i o r t o t h e v o l t a m m o g r a m r e c o r d i n g i n a 0.5M H S 0 « s o l u -
2
t i o n (22). F i n a l l y the enhancement o f the r e v e r s i b l e peaks at h i g h -

e s t p o t e n t i a l may b e o b t a i n e d b y a f a s t c y c l i n g i n a 0.5M H2SQ4
s o l u t i o n a s s t u d i e d i n ( 1 2 ) . I t i s shown i n f i g . 5 t h e two l i m i t i n g
v o l t a m m e t r i c p r o f i l e s f o r a (100) o r i e n t a t i o n . E x p e r i m e n t a l re-
s u l t s i n d i c a t e t h a t (100) s u r f a c e w i t h a w e l l - d e v e l o p e d peak a t
high p o t e n t i a l i s probably that with the lowest surface defect
c o n t e n t i n view of the lowest c u r r e n t i n the r e g i o n 0.05-0.2 V a s
a c o n c l u s i o n of the r e s u l t s o b t a i n e d with stepped s u r f a c e s (see
below). Because of i t s a b s e n c
platinum the r e v e r s i b l e s t a t
When t h e P t ( l O O ) o r i e n t a t i o n i s s u b j e c t e d t o o x y g e n a d s o r p t i o n -
d e s o r p t i o n at high coverage, t h i s s t a t e d i s a p p e a r s p r o g r e s s i v e l y
l e s s r a p i d l y than i n the case of P t ( l l l ) w h i l e the a d s o r p t i o n -
d e s o r p t i o n c u r r e n t i n t h e r a n g e 0.05 - 0 . 2 V i n c r e a s e s ( f i g . 5 )
without appearance of d e f i n e d a d s o r p t i o n - d e s o r p t i o n s t a t e s l i k e on
P t ( 1 1 1 ) . C o n t r a r y to the l a t t e r o r i e n t a t i o n , even a f t e r a l a r g e
p e r t u r b a t i o n o f t h e (100) s u r f a c e , t h e u n u s u a l s t a t e may b e
r e s t o r e d b y f a s t c y c l i n g (12.). T h e d i s a p p e a r a n c e o f t h e u n u s u a l
s t a t e with extensive a d s o r p t i o n - d e s o r p t i o n o foxygen suggests that
surface long-range order i s responsible for i t s presence too.
Stepped surfaces with (100) sites
( 1 0 0 ) t e r r a c e s i t e s . Me c o n s i d e r f i r s t s u r f a c e s w i t h (100)
t e r r a c e s . Two t y p e s of s t e p may b e o b t a i n e d e i t h e r w i t h (110)
s i t e s f o r s u r f a c e s c h o s e n i n t h e C0013 z o n e o r w i t h (111) s i t e s
f o r s u r f a c e s chosen i n the [011] zone.
In f i g . 5 t h e v o l t a m m o g r a m of t h e P t ( 3 1 0 ) and P t ( 5 1 1 ) o r i e n t a t i o n s
b o t h c o n t a i n i n g (100) t e r r a c e s w i t h t h r e e a t o m i c rows and (110) o r
(111) s t e p s r e s p e c t i v e l y a r e r e p r e s e n t e d . T h e i r s i m i l a r a d s o r p t i o n
s t a t e s a b o v e 0.2 V may b e u n a m b i g u o u s l y a s c r i b e d t o t h e t e r r a c e
s i t e c o n t r i b u t i o n , while c h a r a c t e r i s t i c s t a t e s at lower p o t e n t i a l s
which are not p r e s e n t on the voltammogram of an o r d e r e d Pt(lOO)
s u r f a c e may b e a s c r i b e d t o s t e p c o n t r i b u t i o n o n b o t h s u r f a c e s .
C o n s i d e r i n g t h e s t a t e s r e l a t e d t o t h e t e r r a c e c o n t r i b u t i o n i t may
be n o t e d t h e a b s e n c e o f t h e r e v e r s i b l e p e a k a t 0.365 V w h i c h c o n -
f i r m s i t s assignment to the bidimensional long-range order. A l l
t h e s t e p c o n t r i b u t i o n s a r e l o c a t e d i n t h e low p o t e n t i a l r a n g e
b e l o w 0.2 V. B o t h (110) and (111) s t e p s i t e s h a v e t h e i r c o n t r i b u -
t i o n t o h y d r o g e n a d s o r p t i o n i n t h e same r a n g e of p o t e n t i a l , t h i s
remark w i l l be u s e f u l i n the i n t e r p r e t a t i o n o fthe weakly bonded
hydrogen p a r t i c u l a r l y on a c t i v a t e d platinum s u r f a c e s . Here the
step c o n t r i b u t i o n s correspond to the s t a t e s i n the lower p o t e n t i a l
range i . e . to the weakly bonded hydrogen.

(100) s t e p s i t e s . T h e a d s o r p t i o n o f h y d r o g e n on (100) s t e p s i t e s
•ay be c h e c k e d by u s i n g s u r f a c e s c h o s e n i n t h e C0113 z o n e . T h i s i s
the case f o r t h e Pt(211) o r i e n t a t i o n which c o n t a i n s (111) t e r r a c e s
with t h r e e atomic rows. F i g . 5 shows t h a t t h e (100) s i t e s c o n t r i b u -
t i o n i s U n i t e d t o a s i n g l e r e v e r s i b l e peak a t t h e p o t e n t i a l of
the l e a s t s t r o n g l y bonded hydrogen on P t ( l O O ) , P M 3 1 0 ) and P t (511),
w h i l e t h e t e r r a c e c o n t r i b u t i o n g i v e s r i s e t o t h e broad peak i n t h e
low p o t e n t i a l r e g i o n . C o n s e q u e n t l y i t may b e c o n c l u d e d f r o * t h e r e -
s u l t s o b t a i n e d with t h e t h r e e o r i e n t a t i o n s t h a t (111) s i t e s i n c l u -
ded i n t o s u r f a c e d o « a i n s w i t h no b i d i « e n s i o n a l l o n g - r a n g e order
(steps, terraces) give a c o n t r i b u t i o n to hydrogen adsorption i n
the low p o t e n t i a l r e g i o n which i s superposed with t h e (110) s i t e
n a r r o w c o n t r i b u t i o n a t 0 . 1 1 0 V. N e v e r t h e l e s s t h e p r e s e n c e o f ( 1 1 1 )
t e r r a c e s * a y be d e t e c t e d by t h e p r e s e n c e o f r e s i d u a l u n u s u a l
s t a t e s a b o v e 0.4 V .
Volta**etric surface analysi f platinized olatinu*
Recently i n this laborator

p l a t i n u * surfaces the conditions f o r the observation of the va-
r i o u s adsorption s t a t e s as a consequence of the existence of o r -
dered do«ains with basal o r i e n t a t i o n s at t h e surface of the c r y s -
t a l l i t e s . N h e n we c o n s i d e r c l a s s i c a l r e s u l t s w i t h p l a t i n i z e d p l a -
t i n u * e l e c t r o d e a v o l t a « * o g r a « s i Hilar t o t h a t r e p o r t e d on F i g . 6a
i s o b s e r v e d . T h i s t y p e o f v o l t a « * o g r a * was o b t a i n e d a f t e r c y c l i n g
t h e e l e c t r o d e b e t w e e n 0 . 0 2 - 1.6 V, i n o t h e r w o r d s f o r p e r t u r b e d
c r y s t a l l i t e s . It i s i n t e r e s t i n g to investigate these electrodes
f r o * the point of view of the unavoidable presence of s * a l l orde-
red domains at the surface of the unperturbed c r y s t a l l i t e s . If
s u c h d o m a i n s e x i s t t h e y h a v e t o y i e l d a d s o r p t i o n s t a t e s w h i c h were
not o b s e r v e on t h e c o n v e n t i o n a l voltammogram o f p l a t i n i z e d p l a t i -
num. T h e i r o b s e r v a t i o n r e q u i r e s t h e p r e p a r a t i o n o f c l e a n s a m p l e s
a v o i d i n g t h e u s e o f c y c l i n g u p t o 1.5 V. D e p o s i t s o f p l a t i n u *
b l a c k w i t h a s u r f a c e e x p a n s i o n c o e f f i c i e n t o f a b o u t 110 w e r e p r e -
pared and s t u d i e d i n a narrow range of p o t e n t i a l . A t y p i c a l v o l -
tammogram i s g i v e n i n f i g . 6 b . T h i s voltammogram shows t h e p r e s e n c e
o f a d s o r p t i o n s t a t e s i n t h e r a n g e 0 . 3 - 0.4 V c o r r e s p o n d i n g t o h y -
drogen adsorbed a t (100) t e r r a c e s with v a r i o u s widths and t h e low
a n d w i d e s t a t e f r o m 0.4 t o 0 . 6 V w h i c h i s c h a r a c t e r i s t i c o f ( 1 1 1 )
narrow t e r r a c e s .
Contrary t o the conventional d i s t r i b u t i o n of hydrogen at a c t i v a t e d
p l a t i n u m t h e p e a k a t 0 . 2 6 V i s h i g h e r t h a n t h e p e a k a t 0 . 1 1 0 V.
The r e g i o n o f t h e w e a k l y b o n d e d h y d r o g e n s h o w s t h e n a r r o w peak
corresponding t o (110) s i t e s superposed t o a broader adsorption
s t a t e as expected from (111) s t e p s and t e r r a c e s c o n t r i b u t i o n s .
A f t e r a p p l y i n g c y c l e s b e t w e e n 0 . 0 2 a n d 1.6 V t h e v o l t a m m o g r a m i s
changed t o that reported i n f i g . 6 a , the surface expansion decrea-
s e s down t o 86 a n d t h e u n u s u a l s t a t e s d i s a p p e a r w i t h a d r a m a t i c
d e c r e a s e o f t h e c u r r e n t i n t h e d o u b l e l a y e r r e g i o n a b o v e 0.4 V.
These r e s u l t s with p l a t i n u * black f i t well with data f r o * stepped
s u r f a c e s and c o n f i r m t h a t v o l t a m m e t r y o f a d s o r b e d h y d r o g e n c a n be
used a s a t o o l l e a d i n g t o an i n t e r e s t i n g l e v e l o f d e s c r i p t i o n of
the c r y s t a l l i n e surface s t r u c t u r e of a c a t a l y s t l i k e platinum.

F i g u r e 5. V o l t a m m o g r a m s o f P t ( l O O ) (two p r o f i l e s , S.6. Sun,

T h e s i s ) and s t e p p e d s u r f a c e s .
F i g u r e 6. V o l t a m m o g r a m s o f p l a t i n u m b l a c k ( a ) a f t e r c y c l e s
b e t w e e n 0 . 0 2 - 1.6 V ( b ) f r e s h l y e l e c t r o d e p o s i t e d p l a t i n u m
b l a c k c y c l e d w i t h o u t o x y g e n a d s o r p t i o n ( a f t e r Sun and
Clavilier).

The u s e o f a n u m e r i c a l a n a l y s i s o f v o l t a m m o g r a m s w i t h a p r e c i s e
deconvolution technique of t h e adsorption s t a t e s (23 24) andt h e T
comparison of r e s u l t i n g data with hard sphere models oft h e

s t e p p e d s u r f a c e s i n number o f c a s e s a l l o w s an u n d e r s t a n d i n g o f t h e
i n t e r f a c i a l processes a t t h e atomic level of t h e working s u r f a c e ,
in t h e presence of t h e e l e c t r o l y t e .
Acknowledgments
The a u t h o r i s g r a t e f u l t o D r s O.Armand, M . P e t i t , S.6.Sun,
T. V a n d e r n o o t a n d times A . P l a z a a n d Y. R o d i e r f o r t h e i r a s s i s t a n c e
i n v a r i o u s ways d u r i n g t h e p r e p a r a t i o n o f t h i s m a n u s c r i p t .
Literature Cited
1. Hammett, V. W. J.Am.Chem.Soc 1924, 46, 7.
2. James, S. D. J.Electrochem.Soc. 1967, 114, 1113.
3. Will, F. G. J.Electrochem.Soc 1965 112 451
4. Ishikawa, R. M.; Hubbard
317.
5. O'Grady, W. E.; Woo, M. Y. C . ; Hagans, P. L.; Yeager, E.
J.Vac. Sci.Technol. 1977, 14, 365.
6. Yeager, E; O'Grady, W. E.; Woo, M. Y. C . ; Hagans, P. L.
J. Electrochem.Soc. 1978, 125, 348.
7. Yamamoto, K.; Kolb, D.M.; Kotz, R; Lehmpfuhl, G.
J.Electroanal. Chem. 1979, 96, 233.
8. Hubbard, A. T.; Ishikawa, R. M.; Katekaru, J . J. Electroanal.
Chem.1978, 86, 271.
9. C l a v i l i e r , J.; Faure, R.; Guinet G.; Durand, R. J.Electroanal.
Chem. 1980, 107, 205.
10. C l a v i l i e r , J.; Armand, D.; Sun, S. G.; Petit, M.
11. C l a v i l i e r , J.; Armand, D.; Wu, B. L. J.Electroanal.Chem. 1982,
135,159.
12. Clavilier, J.; Armand, D. J.Electroanal.Chem. 1986, 199, 187.
13. Al-Jaaf-Golze, K.; Kolb, D.; Scherson, D. J.Electroanal. Chem.
1986, 200, 353.
14. Aberdam, D.; Corotte, C.; Dufayard, D.; Durand, R.; Faure R.;
th
Guinet, G. Proceedings of the 4 Conference on Solid Surfaces,
September 22-26(1980), Cannes, France, Supplément à "Le Vide,
Les Couches Minces" 1980, 201, 622.
15. Wagner, F. T.; Ross, P. N. J r . J.Electroanal.Chem. 1985, 150,
141.
16. Wagner, F. T.; Ross, P. N. J r . Surface Science 1985, 160, 305.
17. Aberdam, D.; Durand, R.; Faure, R.; El-Omar, F. Surface
Science 1986, 171, 303.
18. C l a v i l i e r , J. J.Electroanal.Chem. 1980, 107, 211.
19. Christmann, K.; Ertl, G. Surface Science 1976, 60, 365.
20. Furuya, N.; Motoo, S.; Kunimatsu, K. J.Electroanal.Chem. 1988,
239, 347.
21. Motoo, S.; Furuya, N. J.Electroanal.Chem. 1984, 167, 309.
22. Scortichini, C. L.; Reilley, C. N. J.Electroanal.Chem. 1982,
139, 233.
23. Armand, D., Clavilier, J. J.Electroanal.Chem. 1987, 225, 205.
24. Armand, D., C l a v i l i e r , J . J.Electroanal.Chem. 1987, 233, 251.
R E C E I V E D May 17, 1988

Chapter 15
In Situ Surface Extended X-ray Absorption

Fine Structure at Chemically
Modified Electrodes
M . J . Albarelli, J . H. White, M . McMillan, G. M . Bommarito, and

H D Abruña
Department of Chemistry, Bake Laboratory, Cornel University, Ithaca,

NY 14853
The surface EXAFS and near edge structure of
+2
electropolymerized films of [M(v-bpy)3] (v-bpy
i s 4-vinyl-4'-methyl,-2,2'-bipyrdine and M = Ru,
2+
Os) and [Os(v-bpy)2(phen)] (phen i s 4-methyl-
1,10-phenanthroline) on platinum electrodes have
been studied as a function of surface coverage
and a p p l i e d p o t e n t i a l by measuring the
c h a r a c t e r i s t i c RuK and OsL
a a fluorescence
intensity. For [Ru(v-bpy)3]+2 spectra for
electrodes modified with 1, 5, 12, 25 and 50
monolayers were obtained. Analysis and
comparison of EXAFS and XANES features for these
films showed s i m i l a r morphological and
e l e c t r o n i c c h a r a c t e r i s t i c s in agreement with
previous electrochemical studies showing that
solution redox properties of monomer complexes
can be transferred to electrode surfaces by
electrodeposition as polymer films of varying
thickness. Electrochemical oxidation of the
films resulted in a shift of 2.0 eV in the edge
position towards higher energy, consistent with
the higher charge on the ruthenium centers.
Other s p e c t r a l features, however, remained
e s s e n t i a l l y unchanged. Similar studies were
performed on the osmium complexes but, in
addition, changes in the edge position and near
edge features could be correlated with the
coordination environment. The a p p l i c a b i l i t y of
these studies to the i n - s i t u investigation of
electrocatalytic systems is discussed.
0097-6156/88/0378-0216$06.00/0
c

15. ALBARELLI ET AL. EXAFS at Modified Electrodes 217
Among t h e m a i n g o a l s o f e l e c t r o c h e m i c a l r e s e a r c h a r e t h e
design, characterization and understanding of
e l e c t r o c a t a l y t i c systems, (1-2) b o t h i n s o l u t i o n a n d on
electrode surfaces. Q ) Of p a r t i c u l a r i m p o r t a n c e a r e t h e
nature and s t r u c t u r e o f r e a c t i v e intermediates involved
i n t h e e l e c t r o c a t a l y t i c r e a c t i o n s . (4.) The n a t u r e o f an
electrocatalytic s y s t e m c a n be q u i t e v a r i e d a n d c a n
i n c l u d e a c t i v a t i o n o f t h e e l e c t r o d e s u r f a c e by s p e c i f i c
p r e t r e a t m e n t s (5-9) t o g e n e r a t e a c t i v e s i t e s , deposition
or adsorption o f m e t a l l i c adlayers (10-11) o r t r a n s i t i o n
metal complexes. (12-16) I n a d d i t i o n t h e e l e c t r o d e can
act as a simple e l e c t r o n s h u t t l e t o an a c t i v e s p e c i e s i n
s o l u t i o n such as a m e t a l l o - p o r p h y r i n o r phthalocyanine.
O v e r t h e y e a r s , many s y s t e m s h a v e b e e n i n v e s t i g a t e d
and a variety of experimental probes, both
electrochemical and s p e c t r o s c o p i c , have been used i n
t h e i r study and c h a r a c t e r i z a t i o n Thus electrochemical
techniques such as r o t a t e d - r i n
spectroscopic technique
numerous v a r i a n t s ) h a v e p r o v i d e d much i n s i g h t i n t o t h e
m e c h a n i s m s o f many o f t h e s e p r o c e s s e s , however, in-situ
s t r u c t u r a l s t u d i e s o f such systems have, t o date, proved
very elusive t o d i r e c t experimental probing.
The application of ultra-high vacuum surface
spectroscopic methods coupled to electrochemical
techniques (21-24) have p r o v i d e d v a l u a b l e i n f o r m a t i o n on
surface structure/reactivity correlations. These
determinations, however, a r e performed e x - s i t u and thus
r a i s e important concerns as t o t h e i r a p p l i c a b i l i t y t o
electrocatalytic s y s t e m s , e s p e c i a l l y when v e r y active
intermediates are involved.
An added difficulty that arises i n the in-situ
spectroscopic study of electrocatalytic systems i n
s o l u t i o n i s t h a t t h e a c t i v e s p e c i e s w i l l be l o c a t e d i n
the v i c i n i t y o f t h e e l e c t r o d e so that t h e m a t e r i a l i n
solution will generally represent a large background
s i g n a l making t h e d e t e c t i o n and i d e n t i f i c a t i o n o f r e l a t e d
s p e c i e s d i f f i c u l t . Thus, i t would be i d e a l t o be a b l e t o
probe only that region proximal t o t h e electrode surface
and furthermore t o be able to obtain structural
information of the species involved.
A way t o c i r c u m v e n t t h e f i r s t p r o b l e m i s t o e n s u r e
that a l lof the a c t i v e m a t e r i a l i s present at the
e l e c t r o d e s u r f a c e . That i s , employ a c h e m i c a l l y modified
e l e c t r o d e where a p r e c u r s o r t o t h e a c t i v e e l e c t r o c a t a l y s t
is incorporated. The field of chemically modified
electrodes Q) i s a p p r o a c h i n g a more mature s t a t e a n d
there are now numerous methodologies f o r the
incorporation of materials that exhibit electrocatalytic
a c t i v i t y . F u r t h e r m o r e , some o f t h e s e s y n t h e t i c p r o c e d u r e s
a l l o w f o r t h e p r e c i s e c o n t r o l o f t h e coverage so that
e l e c t r o d e s m o d i f i e d w i t h a few monolayers o f redox a c t i v e
m a t e r i a l c a n b e r e p r o d u c i b l y p r e p a r e d . (2L)
The s e c o n d p r o b l e m o f c o n c e r n i s b e i n g a b l e t o p e r f o r m
an in-situ structural c h a r a c t e r i z a t i o n of the redox

a c t i v e c a t a l y s t i n c o r p o r a t e d on t h e e l e c t r o d e surface.
S u r f a c e E X A F S a n d X - r a y S t a n d i n g W a v e s (XSW) a r e p e r h a p s
the only techniques capable of yielding in-situ (the
e l e c t r o d e i n contact w i t h an e l e c t r o l y t e s o l u t i o n and
under p o t e n t i o s t a t i c c o n t r o l ) s t r u c t u r a l i n f o r m a t i o n on
electrodeposited layers.
We h a v e p r e v i o u s l y e m p l o y e d s u c h t e c h n i q u e s i nt h e
study o f i o d i d e adsorption onto P t ( l l l ) e l e c t r o d e s (2JL)
as w e l l a s i n t h e i n - s i t u s t r u c t u r a l c h a r a c t e r i z a t i o n o f
u n d e r p o t e n t i a l l y d e p o s i t e d copper and s i l v e r on A u ( l l l )
electrodes. (26)
W i t h t h e e x c e p t i o n o f E l d e r e t . a l . , who u s e d E X A F S t o
look a t redox p r o p e r t i e s o f copper complexes d i f f u s e d i n
N a f i o n f i l m m o d i f i e d e l e c t r o d e s (27.) , n o i n - s i t u s t u d i e s
have been r e p o r t e d on m o d i f i e d e l e c t r o d e s u s i n g EXAFS.
We n o w p r e s e n t an i n - s i t u surface EXAFS s t u d y o f
2 +
electropolymerized film f [M(v-bpy)3] (v-bp i 4
1
vinyl, 4 -methyl, 2,
[Os(phen)(v-bpy)2] (phen i s 4-methyl phenanthroline)
and on t h e a p p l i c a b i l i t y of this technique to follow the
course o f redox transformations.
These systems have been t h e o b j e c t o f c o n s i d e r a b l e
study s i n c e t h e monomer c o m p l e x e s a n d t h e i r analogues
h a v e b e e n w i d e l y s t u d i e d (2.8.) a n d e l e c t r o p o l y m e r i z a t i o n
i s r e a d i l y a c c o m p l i s h e d a t t h e v i n y l s u b s t i t u e n t on t h e
bipyridinyl ligand. (2 9-31) There a r e v a r i o u s aspects
t h a t we w i s h t o a d d r e s s a n d t h e s e a r e t h e d e p e n d e n c e o f
the s t r u c t u r e o f e l e c t r o d e p o s i t e d l a y e r s on coverage and
the ability to follow redox transformations. The
dependence of structure on s u r f a c e coverage should
i n d i c a t e 1) t h e n a t u r e a n d s t r e n g t h o f i n t e r a c t i o n o f t h e
e l e c t r o d e p o s i t e d f i l m w i t h t h e e l e c t r o d e s u r f a c e a n d 2)
the a p p l i c a b l e range o f surface coverages over which
polymer local structure i s similar t o that of the
monomeric parent complex i n s o l u t i o n (and by i n f e r e n c e ,
the range over which redox behavior i s similar). In
addition, the ability t o f o l l o w redox transformations
w i l l be of great u t i l i t y i n i n v e s t i g a t i n g
electrocatalytic systems. We a r e a l s o interested i n
correlating changes i n spectral features with
coordination environment.
The i n f o r m a t i o n o b t a i n e d f r o m t h e p r e v i o u s l y d e s c r i b e d
studies may b e u s e d t o e s t a b l i s h g u i d e p o s t s f o r the
rational design and synthesis of electrochemical
interfaces ( i n particular, of polymer modified
electrodes) with high c a t a l y t i c a c t i v i t y .
Experimental
2 +
Reagents . [M(v-bpy)3] (M = R u , O s ) w e r e prepared as
9+
previously described.(32-33) [Os(phen)(v-bpy)2] was
prepared following procedures previously described f o r

15. ALBARELLIETAK EXAFS at Modified Electrodes 219
inalogous c o m p l e x e s . (3A) Ace tonitrile (Burdick and

J a c k s o n d i s t i l l e d i n g l a s s ) was d r i e d o v e r 4Â molecular
s i e v e s . T e t r a η-butyl ammonium perchlorate (TBAP) (G.F.
S m i t h ) was r e c r y s t a l l i z e d t h r e e times from e t h y l acetate
ind d r i e d under vacuum a t 7 0 ° C f o r 72 h o u r s .
Electrochemical Instrumentation. F o r t h e Ru c o m p l e x e s , a
1 cm d i a m e t e r p l a t i n u m d i s k b r a z e d o n t o a b r a s s holder
was u s e d as a w o r k i n g e l e c t r o d e . I t was masked with
ChemGrip (a t e f l o n b a s e d e p o x y ) e x c e p t f o r t h e upper
f a c e . P r i o r t o u s e , i t was p o l i s h e d w i t h 1 m i c r o n d i a m o n d
paste (Buehler) and rinsed with water, acetone and
m e t h a n o l . The w o r k i n g e l e c t r o d e f o r e a c h Os c o m p l e x was
the uppermost p l a t i n u m l a y e r of a platinum/carbon layered
synthetic microstructure (LSM) (Energy Conversion
D e v i c e s ) . The LSM c o n s i s t e d o f 200 l a y e r p a i r s o f c a r b o n
and platinum whose t h i c k n e s s e 24. 17.0 Â
r e s p e c t i v e l y and wher
The LSM was place
e l e c t r o c h e m i c a l y b y h o l d i n g t h e p o t e n t i a l a t +1.7 volts
f o r 5 m i n u t e s , t h e n c y c l i n g t h e p o t e n t i a l f r o m +1.2 to -
0.4 v o l t s f o r 10 m i n . A f t e r w a r d s , t h e LSM was r i n s e d w i t h
w a t e r and d r i e d . The counter and reference electrodes
were a p l a t i n u m c o i l and s i l v e r w i r e , r e s p e c t i v e l y .
Electropolymerization was carried out in
a c e t o n i t r i l e / 0 . 1 M TBAP s o l u t i o n i n a c o n v e n t i o n a l three
compartment e l e c t r o c h e m i c a l c e l l a c c o r d i n g t o p r e v i o u s l y
described procedures. (29-31)
The electrochemical cell f o r t h e EXAFS experiments
( F i g u r e 1) was m a c h i n e d f r o m a t e f l o n c y l i n d e r (6 cm
d i a m e t e r χ β cm h i g h ) a n d was p r o v i d e d w i t h c o n t a c t s f o r
all electrodes as w e l l as teflon fittings for the
i n j e c t i o n o f e l e c t r o l y t e . The e l e c t r o d e was placed flat
on t h e t o p o f t h e c e l l a n d c o v e r e d w i t h a t h i n T e f z e l ( E .
I . D u P o n t de N e m o u r s I n c . ) f i l m (12μπ\) w h i c h was h e l d i n
p l a c e w i t h a v i t o n o - r i n g p l a c e d 1 cm b e l o w t h e t o p and
around the circumference o f t h e c e l l . The s u r f a c e o f t h e
p l a t i n u m e l e c t r o d e was r a i s e d a b o u t 1 mm a b o v e t h e e d g e
o f t h e c e l l so as t o a l l o w n e a r g r a z i n g i n c i d e n c e o f t h e
x-ray beam. The tefzel cover made e f f e c t i v e l y a thin
l a y e r c e l l w h o s e t h i c k n e s s we e s t i m a t e t o b e o f t h e order
o f 20 μπι. The c e l l was mounted i n s i d e a p l e x i g l a s box
w i t h K a p t o n ( p o l y i m i d e ) windows (not shown i n F i g u r e 1 ) .
The t o p o f t h e b o x was provided with entrance and exit
p o r t s s o t h a t i t c o u l d b e c o n s t a n t l y f l u s h e d w i t h He to
eliminate contamination from oxygen and minimize a i r
s c a t t e r i n g . The b o x a s s e m b l y was b o l t e d on a H u b e r 410
goniometer stage providing very f i n e and reproducible
r o t a t i o n and t r a n s l a t i o n . ( T y p i c a l l y 4,000 s t e p s / d e g r e e
of rotation and 100 steps/μιη translation.) A l l
e x p e r i m e n t s were p e r f o r m e d a t g r a z i n g i n c i d e n c e i n o r d e r
to enhance t h e s u r f a c e s i g n a l and decrease background
scatter.

F i g u r e 1. Electrochemical c e l l for in situ surface
EXAFS a t c h e m i c a l l y m o d i f i e d electrodes.

X - r a y I n s t r u m e n t a t i o n . A l l e x p e r i m e n t s were p e r f o r m e d a t
the Cornell High Energy Synchrotron Source (CHESS)
operated at 5.8 GeV (Stations A-3, B and C-2).
Monochromatic r a d i a t i o n was obtained with a S i (220)
double crystal monochromator. In o r d e r t o eliminate
h i g h e r h a r m o n i c s , 50% d e t u n n i n g was t y p i c a l l y employed .
A P r i n c e t o n Gamma T e c h S i ( L i ) s o l i d s t a t e d e t e c t o r i n
c o n j u n c t i o n w i t h an EG&G O r t e c M o d e l 673 S p e c t r o s c o p y
Amplifier and a Tennelec Model 450 Single Channel
a n a l y z e r were employed t o d e t e c t t h e c h a r a c t e r i s t i c Ru K a
and Os L a fluorescence at 19.2 keV and 8.9 keV

r e s p e c t i v e l y . D a t a were a n a l y z e d u s i n g a m o d i f i e d v e r s i o n
o f t h e EXAFS a n a l y s i s program by B.M. K i n c a i d (AT&T B e l l
Labs) .
2 +
Bulk samples of [M(v-bpy)3] (M = Ru, Os) , and [Os
2 +
(phen)(v-bpy) ] 2 (employe
e v a p o r a t e d from a c e t o n i t r i l
s i g n a l o b t a i n e d . In t h i s c a s e t h e complexes were not in
s o l u t i o n b u t i n a He atmosphere.
Procedure
The p l a t i n u m e l e c t r o d e and LSM's were m o d i f i e d w i t h Ru

and Os polymers respectively as described in the
e x p e r i m e n t a l s e c t i o n . E a c h sample was r i n s e d w i t h a c e t o n e
and p l a c e d i n an a c e t o n i t r i l e / 0 . I M TBAP s o l u t i o n and a
cyclic voltammogram of the Ru ( o r Os) 2 + /3+ e w a v
o b t a i n e d . From t h e c h a r g e consumed ( i . e . by i n t e g r a t i o n
o f t h e a r e a u n d e r t h e v o l t a m m e t r i c wave) t h e surface
coverage (in equivalent number of monolayers) was
d e t e r m i n e d . Samples w i t h 1, 5, 12, 25, and 50 m o n o l a y e r s
2 +
were p r e p a r e d f o r t h e [Ru(v-bpy)3] , 1 and 3 monolayers
2 +
for [Os(v-bpy)3] , and 2 monolayers for [Os(phen)(v-
> + A
t py)2^ * monolayer of complex (diameter of 14.2 A)
- 1 2
r e p r e s e n t s about l X l O ^ moles/cm . S i n c e d e t e c t i o n i s
b a s e d on t h e c h a r a c t e r i s t i c f l u o r e s c e n c e a r i s i n g f r o m t h e
m e t a l c e n t e r s , a more r e l e v a n t f i g u r e i s t h e amount o f
1 2
metal present (SXIO ^ atoms/cm ) which represents about
5% o f a m e t a l m o n o l a y e r .
E a c h e l e c t r o d e i n t u r n was mounted on t h e EXAFS c e l l
and t h e s p e c t r u m o f t h e r e d u c e d f o r m o f t h e p o l y m e r i c
f i l m was p e r f o r m e d w h i l e t h e p o t e n t i a l was h e l d a t 0.0 V.
A f t e r w a r d s , t h e p o t e n t i a l was s c a n n e d t o 300 mV p o s i t i v e
o f t h e o x i d a t i o n wave o f t h e complex (+1.6 V f o r Ru and
+1.1 V f o r Os) and h e l d f o r 5 m i n u t e s t o e n s u r e c o m p l e t e
o x i d a t i o n p r i o r t o o b t a i n i n g the spectrum of the o x i d i z e d
form. After spectroscopic investigations, the

voltammetric behavior o f each modified electrode i n

a c e t o n i t r i l e / O . I M TBAP was p e r f o r m e d t o c o n f i r m t h e r e w a s
no l o s s o f m a t e r i a l .
2 +
TRu(v-bpy)31 . Figure 2 presents EXAFS spectra for bulk
2 +
[Ru ( v - b p y ) 3 ] (A) a s w e l l as f o relectrodes modified
with 5 (B) a n d 1 (C) m o n o l a y e r s of poly-[Ru(v-bpy)3]^ .

2 +
The spectrum for bulk [Ru(v-bpy)3] shows a w e l l defined
edge a t 22.18 keV w i t h t h r e e w e l l d e f i n e d oscillations
beyond t h e edge. Qualitatively similar spectra are
o b t a i n e d f o re l e c t r o d e s m o d i f i e d w i t h 1 and 5 monolayers
of t h e polymer. Again
oscillation are clearl
second and e s p e c i a l l
d i f f i c u l t t o d i s c e r n i n t h e spectrum f o rt h e electrode
modified with a single monolayer whereas, f o rt h e
electrode modified with 5 monolayers o f polymer, these
oscillations are well defined. The a p p e a r a n c e of
oscillations at higher energies i s more d i f f i c u l t t o
detect because of the rapid decrease i n the
backscattering amplitude f o rlow Z scatterers (nitrogen
in this case) , i n a d d i t i o n t o t h e s m a l l amounts o f
m a t e r i a l p r e s e n t on t h e m o d i f i e d e l e c t r o d e . ( R e c a l l t h a t
a m o n o l a y e r o f c o m p l e x r e p r e s e n t s a b o u t 5% o f a m e t a l
monolayer.) Thus, even f o r rather low coverages of
ruthenium, c l e a r s i g n a l s c a n be o b t a i n e d . F o r samples
c o n t a i n i n g 25 o r more m o n o l a y e r s , t h e s p e c t r u m o b t a i n e d
was i n d i s t i n g u i s h a b l e f r o m t h a t o f t h e b u l k m a t e r i a l .
Figure 3 shows t h e phase uncorrected radial
distribution functions (solid line) f o r bulk [Ru(v-
p _1_
bpy>3] (A) a n d a n e l e c t r o d e m o d i f i e d w i t h 50 m o n o l a y e r s
of poly-[Ru(v-bpy)3]^ (B) a n d b o t h s h o w a v e r y p r o m i n e n t
peak a t a d i s t a n c e o f about 1.5 A. T h e s e p e a k s were
fourier f i l t e r e d i n the indicated regions (dashed line)
and b a c k t r a n s f o r m e d i n t o k space where t h e y were f i t t e d
for amplitude a n d p h a s e . P h a s e c o r r e c t i o n s w e r e made
employing t h e Ru-N d i s t a n c e r e p o r t e d b y R i l l e m a e t a l
(34) f o r an x-ray diffraction study of [Ru(bpy)3]^ .
F i g u r e 4 shows t h e k w e i g h t e d experimental data (solid
l i n e ) , f i l t e r e d data (dashed l i n e ) and f i t (squares) f o r
a n e l e c t r o d e m o d i f i e d w i t h 50 m o n o l a y e r s o f p o l y - [ R u ( v -
2 - 1
bpy^] " • A very good f i t i s obtained f o rthe first
t h r e e o s c i l l a t i o n s a l t h o u g h a t h i g h e r wave v e c t o r t h e f i t
d e g r a d e s somewhat due t o t h e l o w e r s i g n a l t o n o i s e ratio
in t h i s r e g i o n o f t h e spectrum.
Virtually identical results were o b t a i n e d f o r bulk

4 0 0 0 0 I • • • • | • • • . | • • • • | • • • i | • • • • | • • • • | • • • • | • • • • 1
i
0 I i i i • I • i i i 1 1 i i i i I i i i i I i i i i I
21.9 22.0 22.1 22.2 22.3 22.4 22.5 22.6 22.7 22.8
Energy (keV)
Figure 2. Normalized EXAFS s p e c t r a f o r (A) b u l k [Ru(v-
+ 2
bpy)3] / (B) platinum electrode modified with 5
+ 2
monolayers o f p o l y - [ R u ( v - b p y ) 3 ] , (C) same as B except
the coverage is one monolayer. Spectra have been
shifted vertically for clarity.

F i g u r e 3 A . Phase u n c o r r e c t e d r a d i a l d i s t r i b u t i o n
f u n c t i o n s ( s o l i d l i n e ) and f o u r i e r f i l t e r window
(dashed l i n e ) f o r b u l k [ R u ( v - b p y ) 3 ] + 2 u

ALBARELLI ET AL. EXAFS at Modified Electrodes

0.6 -
7 9 13
F i g u r e 4. EXAFS as a f u n c t i o n o f wave v e c t o r f o r an
e l e c t r o d e m o d i f i e d w i t h 50 m o n o l a y e r s o f p o l y - [ R u ( v -
bpy) ] +2 3 experimental data (solid line), fourier
filtered data (dashed line), theoretical f i t (squares).

2 +
[Ru ( v - b p y ) 3 ] . Upon f i t t i n g t h e d a t a t o t h e o r e t i c a l
a m p l i t u d e s and phase s h i f t s , bond lengths o f 1.9, 2.0,
and 2.1 a n g s t r o m s a n d c o o r d i n a t i o n n u m b e r s o f a b o u t 6
w e r e f o u n d f o r 1, 5, a n d 50 m o n o l a y e r s r e s p e c t i v e l y .
There i s d o u b t f u l s t a t i s t i c a l s i g n i f i c a n c e i n t h e t r e n d
o b s e r v e d i n t h e b o n d l e n g t h s . However, i t a p p e a r s t h a t t h e
s i m i l a r i t y i n t h e data f o r t h e samples i s i n d i c a t i v e o f
similar local structure at a l lstages of polymer
deposition. These values c o r r e l a t e very well with the
known c o o r d i n a t i o n number o f s i x a n d a Ru-N d i s t a n c e o f
2.056 A. (2A)
In a d d i t i o n t o t h e s i m i l a r i t i e s aforementioned, i t i s
also clear that there i s l i t t l e d i f f e r e n c e between t h e
2 +
electrodeposited polymer and bulk compound [Ru(v-bpy)3]
i n t e r m s o f t h e n e a r edge s p e c t r a l f e a t u r e s p o i n t i n g t o a
s i m i l a r geometric d i s p o s i t i o
The results presente
the l o c a l order abou
i s e s s e n t i a l l y u n c h a n g e d f r o m t h a t i n t h e monomer c o m p l e x
and 2) t h a t t h e i n t e r a c t i o n w i t h t h e e l e c t r o d e surface
occurs without appreciable e l e c t r o n i c and s t r u c t u r a l
change. This spectroscopic information corroborates
previous e l e c t r o c h e m i c a l r e s u l t s w h i c h showed t h a t r e d o x
properties ( e . g . as measured by formal potentials) of
d i s s o l v e d s p e c i e s c o u l d be t r a n s f e r r e d from s o l u t i o n t o
the e l e c t r o d e surface by e l e c t r o d e p o s i t i o n s as polymer
f i l m s on t h e e l e c t r o d e . F u r t h e r m o r e , i t i s a p p a r e n t t h a t
the i n i t i a t i o n o f p o l y m e r i z a t i o n a t these surfaces ( i . e .
g r o w t h o f up t o one m o n o l a y e r o f p o l y m e r ) i n v o l v e s no
g r o s s s t r u c t u r a l change.
The r e s u l t s p r e s e n t e d t o t h i s p o i n t were f o r f i l m s
w h e r e t h e r u t h e n i u m was p r e s e n t i n t h e 2+ oxidation
state. I d e n t i c a l r e s u l t s were o b t a i n e d f o r electrodes
p o t e n t i o s t a t e d a t 0.0 V o r a t o p e n c i r c u i t .
Having established that there were no significant
structural perturbations i n t h e coordination spheres of
the ruthenium centers i n the polymer films we
investigated the e f f e c t of oxidation of the ruthenium t o
the 3+ s t a t e . T h i s was p e r f o r m e d i n a c e t o n i t r i l e / 0 . IM
TBAP b y h o l d i n g t h e p o t e n t i a l a t +1.6 V f o r 5 m i n u t e s t o
ensure o x i d a t i o n o f t h e f i l m . A change i n t h e c o l o r o f
2 +
the film from orange (typical of [Ru(v-bpy)3] ) t o green
+
(typical of [Ru(v-bpy)3]^ ) was a clear indication of
complete oxidation.
2 + +
Upon o x i d a t i o n from R u to Ru^ there was a w e l l
defined shift towards higher energies i n t h e edge
p o s i t i o n . F i g u r e 5 shows t h e edge r e g i o n s f o rthe films
present i n the reduced (A) a n d o x i d i z e d (B) f o r m s . T h e
shift, taken at half t h e edge jump, i s 2 eV a n d
consistent with t h e change i n o x i d a t i o n state of the
metal c e n t e r s . Consequent r e d u c t i o n o f t h e f i l m r e s u l t e d


-400 1
• • ' i | 1
10.850 10.875 10.900 10.925 10.950 10.975 11.000 11.025
Energy (keV)
Figure 6. EXAFS spectra for electrodes modified with
2 + 2 +
[Os(v-bpy)3] (solid line) and [Os(phen)(v-bpy)2]
(dotted l i n e ) .

i n a r e v e r s i b l e s h i f t o f t h e edge back t o l o w e r e n e r g y .
The spectral features obtained i n this case were
e s s e n t i a l l y i d e n t i c a l t o those obtained f o rt h e f i l m i n
its reduced form. This i s not surprising, since the
difference i n m e t a l / l i g a n d (Ru/N) bond distance i s
e s t i m a t e d t o b e l e s s t h a n 0.01 A.
2+ 12 +
rOs ( v - b p y ) 1
3 a n d ros (phen) (v-bpy) 2 • Similar results
w e r e o b t a i n e d f o r t h e Os c o m p l e x e s i n t e r m s o f t h e l o c a l
s t r u c t u r e around t h e metal c e n t e r and changes i nt h e
p o s i t i o n o f t h e edge a s a f u n c t i o n o f o x i d a t i o n s t a t e . I n
addition, we w e r e a b l e t o c o r r e l a t e changes i n the
p o s i t i o n o f t h e edge a n d n e a r edge f e a t u r e s w i t h t h e
c o o r d i n a t i o n environment around t h e metal c e n t e r . F i g u r e
2+
6 presents spectra f o r [Os(v-bpy)3] ,and [Os(phen) ( v -
a n c i t n e
bpy) ] 2 differenc
and a r e a under t h
These changes can be a s c r i b e d t o t h e presence of the
p h e n a n t h r o l i n e l i g a n d whose h i g h e r p i a c i d i t y r e l a t i v e t o
b i p y r i d i n e r e s u l t s i n a h i g h e r degree o f p i backbonding.
S i n c e a h i g h e r degree o f backbonding e f f e c t i v e l y removes
e l e c t r o n d e n s i t y away f r o m t h e m e t a l c e n t e r t h e s h i f t i n
t h e edge p o s i t i o n t o h i g h e r e n e r g i e s i s c o n s i s t e n t w i t h
t h i s e f f e c t . T h i s i s a l s o c o n s i s t e n t w i t h t h e change i n
t h e a r e a u n d e r t h e s h a r p t r a n s i t i o n n e a r t h e edge a s h a s
been previously demonstrated f o r P t , Rh a n d o t h e r
m e t a l s . (3J1)
T h e r e a r e some p o i n t s f r o m t h i s s t u d y t h a t n e e d t o b e
emphasized. F i r s t , i t i s p o s s i b l e t o o b t a i n good q u a l i t y
in-situ s u r f a c e EXAFS s p e c t r a f o r e l e c t r o d e s m o d i f i e d
w i t h one t o f i v e monolayers o f a t r a n s i t i o n m e t a l complex
(depending on t h e m e t a l of interest) and changes i n
o x i d a t i o n s t a t e c a n a l s o be m o n i t o r e d . I n a d d i t i o n , t h e
n e a r edge s p e c t r a l f e a t u r e s a n d edge p o s i t i o n changes c a n
a l s o be c o r r e l a t e d with the coordination environment
around a metal center. These aspects should a i d
significantly i n t h e study and i d e n t i f i c a t i o n of
electrocatalytic intermediates in-situ a n d we a r e
c u r r e n t l y p u r s u i n g such studies. In addition, we a r e
c u r r e n t l y i n v o l v e d i n a x - r a y s t a n d i n g wave s t u d y o f t h e
same L S M s a m p l e s ( w i t h t h e d e p o s i t e d o s m i u m p o l y m e r s ) t o
determine t h e degree o f o r d e r i n t h e e l e c t r o p o l y m e r i z e d
layer.
Acknowledgments
T h i s w o r k was s u p p o r t e d b y t h e M a t e r i a l s S c i e n c e C e n t e r
at C o r n e l l U n i v e r s i t y , t h e N a t i o n a l Science Foundation,
t h e Army R e s e a r c h O f f i c e , t h e O f f i c e o f N a v a l Research
a n d t h e Dow C h e m i c a l C o . HDA a c k n o w l e d g e s s u p p o r t b y t h e
Presidential Young I n v e s t i g a t o r Award Program o f t h e
National Science Foundation and t h e A l f r e d P. S l o a n
Foundation.

15. ALBARELLI ET AL. EXAFS at Modified Electrodes
Literature Cited
1. O'Grady, W. E . ; Ross, P. N . ; Wiull, F. G., Eds.; Proc.
Symp. Electrocat.; The Electrochemical Society, Inc.:
New Jersey, 1982; Vol. 82-2.
2. McIntyre, J . D. E . ; Weaver, M. J.; Yeager, E. B . ,
Eds.; Symposium of the chemistry and Physics of
Electrocatalysis; The Electrochemical Society, Inc.:
New Jersey, 1983.
3. Murray, R. W. in Electroanalytical Chemistry; Bard, A.
J., Ed.; Marcel Dekker: New York, 1983; Vol. 13, pp.
191-368.
4. Meyer, T. J . J . Electrochem. Soc. 1984, 131, 221C.
5. Hance, G. W.; Kuwana, T. Anal. Chem. 1987, 59, 131.
6. Poon, M.; McCreery, R. L. Anal. Chem 1986, 58, 2745.
7. Kak, J.; Kuwana, T. J . Am. Chem. Soc. 1982,104,5515.
8. Ergstrom, R. C Anal Chem 1982 54, 2310
9. Cabaniss, G. E .
Linton, R. W.;Meyer
107, 1845.
10. Kolb, D. M. In Advances in Electrochemistry and
Electrochemical Engineering; Gerischer, H . ; Tobias,
C., Eds.; Pergamon Press: New York, 1978, Vol. 11, p.
125.
11. Adzic, R. R. In Advances in Electrochemistry and
Electrochemical Engineering; Gerischer, H . ; Tobias,
C., Eds.; Wiley Interscience: New York, 1984, Vol. 13,
p. 159.
12. Collman, J . P.;Marrocco, M.;Denisevich, P.; Koval, C.;
Anson, F. C. J . Electroanal. Chem. 1979, 101, 117.
13. Collman, J . P.; Kim, K. J. Am. Chem. Soc. 1986, 108,
7847.
14. Lieber, C. M.; Lewis, N. S. J . Am. Chem. Soc. 1984,
106, 5033.
15. Abruña, H. D.; Walsh, J . L.; Meyer, T. J.; Murray, R.
W. J . Am. Chem. Soc. 1980, 102, 3272.
16. Abruña, H. D.; Calvert, J . M.; Denisevich, P.; Ellis,
C. D.; Meyer, T. J.; Murphy, W. R.; Murray, R. W.;
Sullivan, B. P.; Walsh, J . L. In Chemically Modified
Electrodes in Catalysis and Electrocatalysis; Miller,
J . S., Ed.; ACS Symposium Series No. 192, ACS Press:
Washington, D. C., 1982.
17. Bard, A., J.; Faulkner, L. R. Electrochemical Methods;
Wiley & Sons: New York, 1980.
18. Fleischmann, M.; Hendra, P. J.; McQuillan, A. J. Chem.
Phys. Lett. 1974, 26, 173.
19. Fleischmann, M.; Hendra, P. J.; McQuillan, A. J. J.
20. Jeanmarie, D. J.; Van Duyne, R. P. J . Electroanal.
Chem. 1977, 84, 1.
21. Hubbard, A. T. Accts. Chem. Res. 1980, 13, 177.
22. Yeager, E. J. Electroanal. Chem. 1981, 128, 1600.

23. Ross, P. N. Surf. S c i . 1981, 102, 463.

24. Bange, K.; Grider, D. E.; Madey, T. E.; Sass, J . K.
Surf. S c i . 1984, 136, 381.
25. Gordon, J . G.; Melroy, O. R.; Borges, G. L.; Reisner,
D. L.; Abruña, H. D.; Chandrasekhar, P.; A l b a r e l l i , M.
J . ; Blum, L. J . E l e c t r o a n a l . Chem. 1986, 210, 311.
26. Blum, L.; Abruña, H. D.; White, J . H.; Albarelli, M.
J . ; Gordon, J . G.;Borges, G. L.; Samant, M. G.;
Melroy, O. R. J . Chem. Phys. 1986, 85, 6732.
27. E l d e r , R. C.; Lunte, C. E.; Rahman, A. F. M. M.;
K i r c h h o f f , J . R.; Dewald, H. D.; Heineman, W. R. J .
E l e c t r o a n a l . Chem., 1988, 240., 361.
28. Meyer, T. J . Accts. Chem. Res. 1978, 11, 94.
29. Abruña, H. D.; Denisevich, P.; Umaña, M.; Meyer, T.
J.; Murray, R. W. J . Am. Chem. Soc. 1981, 103, 1.
30. Denisevich, P.; Abruña, H. D.; Leidner, C. R.; Meyer,
T. J.; Murray, R W Inorg Chem 1982 21 2153
31. Ghosh, P. K.; Spiro
128, 1281.
32. Abruña, H. D. J . E l e c t r o a n a l . Chem. 1984, 175, 321.
33. Abruña, H. D. J . Electrochem. Soc. 1985, 132, 842.
34. Rillema,D. P.; Jones, D. S.; Levy, H. A. J . Chem. Soc.
Chem. Commun. 1979, 849.
35. Bart, J . C. J . Adv. i n Cat. 1986, 34, 203.
R E C E I V E D May 17, 1988

Chapter 16
Charge-Transfer Reaction Inverse
Photoemission at Gold(111) and
Polycrystalline Silver Electrodes
R. McIntyre, D. K. Roe, J. K. Sass, and H. Gerischer

Emission spectra have been recorded f o r electron
i n j e c t i o n i n t o Au and Ag s p h e r i c a l e l e c t r o d e s and hole
injection i n t o Au(111) planar electrodes. These
processes were brough
a c e t o n i t r i l e containin
phosphate (TBAHP), u s i n g t h e t r a n s - s t i l b e n e r a d i c a l
anion as the e l e c t r o n i n j e c t o r and t h e thianthrene
r a d i c a l c a t i o n as hole i n j e c t o r . The spectrum f o r the
hole i n j e c t i o n process i n t o p l a n a r Au(111) e l e c t r o d e s
has been r e s o l v e d i n t o the P & S - p o l a r i s e d components o f
the emitted light. A comparison o f t h e s p e c t r a l
d i s t r i b u t i o n o f emitted l i g h t f o r t h e above e l e c t r o n
injection process, occurring a t both Au and Ag
e l e c t r o d e s , with t h a t obtained f o r t h e emission process
occurring a t the e q u i v a l e n t A1/A1 O /metal2 3 tunnel
j u n c t i o n is reported.
The emission o f l i g h t from metal and semi-metal s u r f a c e s
i n contact with a condensed phase c o n t a i n i n g charge
acceptors o r donors has r e c e n t l y been t h e s u b j e c t o f
s e v e r a l papers /1-5/. In t h i s work, we a r e going t o
d e a l with three new aspects which have r e c e n t l y emerged.
F i r s t , an experimental m o d i f i c a t i o n t o the o r i g i n a l c e l l
geometry has been made, t o avoid an unusual edge e f f e c t
caused by a lower c e l l r e s i s t a n c e a t t h e edge o f t h e
e l e c t r o d e than a t the centre. The consequence i s a non-
uniformity o f p o t e n t i a l which i s enhanced during
transient changes of potential with electronic
compensation f o r the IR drop i n s o l u t i o n . Second, with
t h i s new modified c e l l geometry and hence b e t t e r d e f i n e d
c o n d i t i o n s , we have r e s o l v e d the emitted l i g h t from t h e
Au(lll) planar surface into P and S-polarised
components. The enhanced emission o f P - p o l a r i s e d l i g h t
has been a t t r i b u t e d t o d i r e c t sp t o d-band t r a n s i t i o n s
o c c u r r i n g i n the 1-L d i r e c t i o n f o r p l a n a r A u ( l l l )
electrodes. Third, by comparing the s p e c t r a l
d i s t r i b u t i o n of the emitted l i g h t f o r the electron
injection process from e l e c t r o n i c donor states i n
s o l u t i o n i n t o p o l y c r y s t a l l i n e g o l d and s i l v e r e l e c t r o d e s
with the spectrum f o r the analogous process o c c u r r i n g a t
0097-6156/88/0378-0233$06.00/0
* 1988 American Chemical Society

the A l / A l 0 3 / m e t a l tunnel j u n c t i o n /6/, we propose t h a t

2
information concerning the shape of the d i s t r i b u t i o n

curve which d e s c r i b e s the e l e c t r o n i c s t a t e s i n s o l u t i o n
can be obtained.
EXPERIMENTAL
Experiments were performed with a conventional three

e l e c t r o d e e l e c t r o c h e m i c a l system c o n t r o l l e d by a PG-
p o t e n t i o s t a t (HEKA E l e c t r o n i k ) modified t o g i v e +25V
output with a maximum c u r r e n t of 2A. The s i n g l e c r y s t a l
A u ( l l l ) e l e c t r o d e was mechanically p o l i s h e d , o r i e n t a t e d
and f i n a l l y e l e c t r o c h e m i c a l l y p o l i s h e d u s i n g a procedure
d e s c r i b e d i n d e t a i l elsewhere /7/. The g o l d and s i l v e r
spherical electrodes were produced by heating the
r e s p e c t i v e wires i n a reducing flame. To a v o i d exposing
the wire t o the charge i n j e c t i o n process i t was s e a l e d
i n t o g l a s s a t the p o i n
A u ( l l l ) c r y s t a l was
s i l i c o n rubber gasket m a t e r i a l . The p l a t i n i s e d Pt mesh
counter e l e c t r o d e was then h e l d f i r m l y i n p l a c e , a g a i n s t
the Kel-F holder, d i r e c t l y opposite the A u ( l l l ) working
e l e c t r o d e such t h a t the volume of e l e c t r o l y t e between
the working and counter e l e c t r o d e s could be d e s c r i b e d as
2
a cone with the counter e l e c t r o d e as base (A = 0.64cm )
2
and the working e l e c t r o d e as top (A = 0.125cm ). The
s e p a r a t i o n between the two e l e c t r o d e s was ^3mm. This
h o l d e r s u b s t a n t i a l l y decreases the edge e f f e c t . The
Kel-F holder was l o c a t e d i n the g l a s s c e l l such t h a t the
A u ( l l l ) e l e c t r o d e was i n l i n e with the r o t a t i o n a x i s .
The Luggin c a p i l l a r y was p o s i t i o n e d between the working
and counter e l e c t r o d e s by means of a 0.5mm diameter hole
i n the Kel-F holder.
The s o l v e n t a c e t o n i t r i l e , the supporting electrolyte,

TBAHP, and the r e a c t a n t thianthrene were p u r i f i e d by
well-known procedures d e s c r i b e d i n d e t a i l elsewhere /8/.
The r e a c t a n t t - s t i l b e n e (Fluka Gmbh) was r e c r y s t a l l i s e d
twice from a methanol water mixture. The optical
arrangement consisted of focusing lenses, a high
efficiency Bausch and Lomb monochromator and a
polarising f i l t e r . The e l e c t r o c h e m i c a l c e l l was mounted
on an X, Y, Z manipulator with c a l i b r a t e d r o t a t i o n
facilities (Fritz-Haber-Institut). The detection
equipment has been d e s c r i b e d i n d e t a i l elsewhere /1,2/.
RESULTS
It has previously been shown that the trans-stilbene

16. McINTYRE ET AL. Charge- Transfer Reaction Inverse Photoemission 235
r a d i c a l anion i s a very s u i t a b l e s p e c i e s f o r i n j e c t i n g
e l e c t r o n s i n t o Pt e l e c t r o d e s , i n a c e t o n i t r i l e s o l u t i o n s ,
with excess energies of up t o 2.2eV /5/. F i g 1 shows
the voltaitimogram f o r the r e v e r s i b l e r e d u c t i o n of t -
3
stilbene (10 M) a t a Au surface (the reversible
+
potential U r = -2.5V vs Ag/Ag ). The p o t e n t i a l range
p o s i t i v e of the wave i s shown t o be almost p e r f e c t l y
p o l a r i s a b l e t o +1.0V.
To c r e a t e the e x c i t e d s t a t e s we employed square-wave

p o t e n t i a l modulation from -2.6V where the r a d i c a l anion
i s produced t o v a r i o u s p o s i t i v e p o t e n t i a l s w i t h i n the
p o l a r i s a b l e region. The o s c i l l o s c o p e t r a c e of the
current-time and photon-time data are shown i n F i g 2,
u s i n g e l e c t r o n i c compensation f o r about 90% of the c e l l
r e s i s t a n c e and a modulation amplitude of 3.1V ( i e . -2.6V
to 0.5V). We see c l e a r l y t h a t l i g h t i s produced only
during the half-cycl
oxidised. During th
the t-stilbene radical anion occurs, on stepping
p o s i t i v e t h e r e i s i n i t i a l l y no l i g h t s i n c e the time
constant of the c e l l i s about 20/AS due t o the r e s i d u a l
uncompensated r e s i s t a n c e . A f t e r 30-50 s, the d e s i r e d
p o t e n t i a l change i s s u f f i c i e n t and we observe emission
throughout the remaining p e r i o d of the p o s i t i v e c y c l e .
On r e t u r n i n g t o the negative h a l f - c y c l e , the e x c i t a t i o n
energy i s reduced and the photon p u l s e s disappear. The
s p i k e s observed on the current-time curves are an
unfortunate a b e r r a t i o n due t o the high impedance of the
junction between reference and working electrode
compartments. The curvature of the photon s p i k e s i s
simply due t o the f i n i t e time constant a s s o c i a t e d with
the inherent capacitance of the coax c a b l e and the l a r g e
load resistor (10k Q ) necessary to register the
p h o t o m u l t i p l i e r c u r r e n t on the o s c i l l o s c o p e .
The s p e c t r a recorded f o r the e l e c t r o n i n j e c t i o n process

by the t - s t i l b e n e r a d i c a l anion i n t o both Au and Ag
s p h e r i c a l e l e c t r o d e s are shown i n F i g 3. The e x c i t a t i o n
energy E e x i s d e f i n e d as ( U - U ) / e where Up i s the
p r
positive potential limit. For the s i l v e r e l e c t r o d e s U R
was l i m i t e d t o -0.1V t o avoid a p p r e c i a b l e d i s s o l u t i o n ox

the e l e c t r o d e . Two observations can be made, both of
which have p r e v i o u s l y been i d e n t i f i e d with the CTRIPS
process /1-4/. F i r s t , s p e c t r a l peak v a l u e s ( E ) ands p
the high energy t h r e s h o l d values ( E ) are observed t o t h
shift t o lower energies with decreasing excitation

energy. Second, the emission i n t e n s i t y i s observed t o
f a l l with decreasing values of In t h i s case,
however, we no longer observe the high energy l i g h t ( i e .
photons with energies>0.5eV higher than expected from

Current/pA
\ \ Ja
1 1
1 1**—— ' r • —
1 /z.s -1.0
1 / P o t e n t i a l / V v s Ag/Ag+
Figure 1. The c u r r e n t - v o l t a g e curve f o r t h e

3
r e v e r s i b l e reduction of t - s t i l b e n e (10~ M) a t a Au
2
sphere e l e c t r o d e (area = 0.125cm ) i n acetonitrile
1
c o n t a i n i n g TBAHP (0.2M) f o r a sweep r a t e = O.IVs"" .

16. McINTYRE ET AL. Charge-Transfer Reaction Inverse Photoemission 237
(e-injectlon) Positive half cycle — | 20|is —

I
20«A
Negative half-cycle (anion production)
F i g u r e 2. Current-time and photon-time data f o r

the e l e c t r o n i n j e c t i o n process by t - s t i l b e n e i n t o a
Au sphere e l e c t r o d e . These data were obtained u s i n g
e l e c t r o n i c compensation f o r the r e s i d u a l IR drop i n
s o l u t i o n , with a modulation amplitude o f 3.1V ( i e .
-2.6V t o 0.5V).

100
Inoise level
a 1x0.125)
1.85 2.05 2.25 2.45 2.65 2.85 3.05

Photon Energy lev)
F i g u r e 3. CTRIPS s p e c t r a recorded f o r t h e system,
metal/MeCN, TBAHP (0.2M) t - s t i l b e n e (0.07M) f o r t h e
e l e c t r o n i n j e c t i o n process by the r a d i c a l anion
i n t o a s p h e r i c a l Au e l e c t r o d e (dashed l i n e ) , area =
2
0.22cm , a) E = 2.6eV; b) E =2.6eV; c) E = e
2
2.4eV and a s p h e r i c a l Ag e l e c t r o d e area = 0.125cm ;
d) e x
E = 2
* 2 e V a
) n
Ed e
= 2.0eV. e x

16. McINTYRE ET AL. Charge-Transfer Reaction Inverse Photoemission 239
the maximum excitation energy) when compensating

electronically for the I R drop in solution, as
p r e v i o u s l y reported /3,4/. Furthermore, with this
p a r t i c u l a r geometry, the p r e c i s i o n with which E and t n
E s p move as a f u n c t i o n of E i s much c l o s e r t o t h a t
e x
expected from simple energetic considerations, than

p r e v i o u s l y observed /1-4/.
As a consequence of having performed the above

experiments with s p h e r i c a l e l e c t r o d e s we suspected t h a t
the o r i g i n of the high energy l i g h t , p r e v i o u s l y observed
with p l a n a r e l e c t r o d e s , was a r e s u l t of a non-uniform
p o t e n t i a l d i s t r i b u t i o n at the p l a n a r e l e c t r o d e due t o
the lower s o l u t i o n r e s i s t a n c e at the unshielded edge
compared t o the c e n t r a l area of the e l e c t r o d e . We
t e s t e d t h i s hypothesis with a p l a n a r g o l d d i s c e l e c t r o d e
evaporated onto a mica s u b s t r a t e s i m i l a r t o t h a t used
previously /2-4/. B
benzophenone ( U = -2.0 r
+
= +0.95V vs Ag~/Ag ) present i n s o l u t i o n and then
s e t t i n g the modulation l i m i t s t o -1.5V and +0.4V ( i e .
500mV away from the r e v e r s i b l e p o t e n t i a l of e i t h e r
couple) we c o u l d not expect t o observe l i g h t from e i t h e r
the electrogenerated chemiluminescence or inverse
photoemission processes. However, by applying
e l e c t r o n i c compensation we were able t o observe orange
l i g h t o r i g i n a t i n g from the edges of the g o l d e l e c t r o d e .
T h i s observation can be explained i f we c o n s i d e r t h a t
f o r a given volume element at the edge of the e l e c t r o d e ,
the r e s i s t a n c e between working and counter e l e c t r o d e s i s
s l i g h t l y l e s s than f o r the same volume element a t the
centre, simply because more c u r r e n t paths e x i s t a t the
edge than i n the c e n t r e . Therefore, d u r i n g the p o s i t i v e
feedback process, used t o compensate f o r the I R drop, i t
i s p o s s i b l e t o s u s t a i n higher p o t e n t i a l s a t the edge
than i n the centre, thus exceeding the s e t p o t e n t i a l
limits at the edge and hence giving rise to
e l e c t r o g e n e r a t e d chemiluminescence a t the edges only. A
q u a n t i t a t i v e a n a l y s i s which attempts t o e x p l a i n the high
energy l i g h t reported e a r l i e r /3,4/ will be given
elsewhere /9/. To avoid t h i s s i t u a t i o n with p l a n a r
e l e c t r o d e s , i t i s necessary t o e l i m i n a t e the e x t r a
c u r r e n t paths a v a i l a b l e at the edges of the e l e c t r o d e s .
T h i s was achieved f o r the A u ( l l l ) e l e c t r o d e u s i n g the
Kel-F holder d e s c r i b e d i n S e c t i o n 2.
The s p e c t r a recorded f o r the hole i n j e c t i o n process by

the thianthrene radical cation into the Au(lll)
e l e c t r o d e are shown i n F i g 4, f o r three different
e x c i t a t i o n energies. Once again, square wave modulation
was employed with a f i x e d p o s i t i v e value of +1.0V where
the c a t i o n r a d i c a l i s produced /4/ t o negative values

.23
5
Photon Energy lev)

F i g u r e 4. CTRIPS s p e c t r a recorded f o r the system
2
A u ( l l l ) / MeCN, TBAHP (0.2M), t h i a n t h r e n e (10" M)
f o r the h o l e i n j e c t i o n process with excitation
energies, a) E = 2.6eV; b)
e x = 8e a n d C ) E
= 3.0eV f o r an e l e c t r o d e area ex = 2; Y
= 0.125cm' ex

16. McINTYRE E T AL. Charge- Transfer Reaction Inverse Photoemission 241
chosen t o g i v e the r e q u i r e d e x c i t a t i o n energy. The

c h a r a c t e r i s t i c s h i f t s of E ^ and E t lt o lower energies
x
with d e c r e a s i n g values of E e x are observed. Also, i n

c o n t r a s t t o the e l e c t r o n i n j e c t i o n process, where l i g h t
p u l s e s are observed i n the p o s i t i v e h a l f - c y c l e (see F i g
2) , we observed emission only d u r i n g the negative h a l f -
cycle i n accordance with expectations f o r a hole
i n j e c t i o n process. F i g 5 shows an emission peak f o r P-
p o l a r i s e d l i g h t from the A u ( l l l ) s u r f a c e . T h i s spectrum
was obtained by r e s o l v i n g the emitted l i g h t i n t o P and
S - p o l a r i s e d components f o r an emission angle = 30°. The
P and S s p e c t r a were then normalised t o account f o r the
wavelength dependent t r a n s m i s s i o n of the monochromator
and the photo-response of the p h o t o m u l t i p l i e r tube, then
s u b t r a c t e d t o g i v e the P - p o l a r i s e d emission spectrum.
The emission peak i s centred a t about 2.1eV f o r an
e x c i t a t i o n energy E = 3.0eV
DISCUSSION
With t h i s new c e l l geometry f o r p l a n a r e l e c t r o d e s the

t h r e s h o l d energy i s no longer dependent on the degree of
e l e c t r o n i c compensation f o r the IR drop and always
coincides closely with the excitation energy.
Therefore, these s p e c t r a are more l i k e l y t o represent
the t r u e j o i n t o p t i c a l d e n s i t y of s t a t e s f o r the system
than those r e p o r t e d p r e v i o u s l y /1-4/. Consequently,
t h i s data does merit more r i g o r o u s i n t e r p r e t a t i o n with
r e s p e c t t o the s p e c t r a l d i s t r i b u t i o n of the emitted
l i g h t and the p o l a r i s a t i o n dependence of the emission.
The emission of P - p o l a r i s e d l i g h t , f o r h o l e i n j e c t i o n
i n t o A u ( l l l ) e l e c t r o d e s , occurs predominantly i n the
energy range 1.7 t o 2.5eV. I f we c o n s i d e r t h a t f o r
o r i e n t a t i o n P the t r a n s m i t t i n g a x i s of the f i l t e r was
p a r a l l e l t o the plane of the e l e c t r o d e but r o t a t e d 90°
about the l i n e of o b s e r v a t i o n , then by r o t a t i n g the
e l e c t r o d e t o make a f i n i t e angle ( i n our case 30°) with
the normal, the emission of P - p o l a r i s e d l i g h t would be
enhanced i f the source were a dipole radiating
p e r p e n d i c u l a r t o the s u r f a c e of the g o l d e l e c t r o d e .
I n s p e c t i o n of the bulk band s t r u c t u r e f o r Au /10/ shows
t h a t d i r e c t sp t o d-band t r a n s i t i o n s , f u l f i l l i n g the
above requirements, are p o s s i b l e i n the *1-L d i r e c t i o n
with energies s i m i l a r t o those observed above.
The p r i n c i p l e of the l i g h t - e m i t t i n g t u n n e l j u n c t i o n
warrants p a r t i c u l a r mention because of the s i m i l a r i t i e s
which e x i s t between the CTRIPS process f o r e l e c t r o n
i n j e c t i o n and the emission process which occurs i n
tunnel j u n c t i o n s / l l , 1 2 / . In the f i r s t case e l e c t r o n s

eiission angle -30° Au(lll)
.7
P - polarised
.5
.4
.3
_L _L _L
1.55 1.75 1.95 2.15 2.35 2.55 2.75 2.95 3.15
Photon Energy (ev)
Figure 5. The P - p o l a r i s e d emission spectrum
obtained f o r hole i n j e c t i o n by the t h i a n t h r e n e
r a d i c a l c a t i o n i n t o A u ( l l l ) f o r emission angle =
30° and e x c i t a t i o n energy = 3.0eV. (NB.
electrochemical c o n d i t i o n s as f o r spectrum C, F i g
4).

16. McINTYRE ET AL. Charge- Transfer Reaction Inverse Photoemission 243
are i n j e c t e d from a d i s t r i b u t i o n o f e l e c t r o n i c s t a t e s i n
s o l u t i o n i n t o a metal e l e c t r o d e with t y p i c a l e x c i t a t i o n
energies o f 2.0-3.0eV and c u r r e n t s o f t h e order o f
100mA. In the second case e l e c t r o n s t u n n e l from one
metal t o another with e x c i t a t i o n energies o f 2.0-3.7eV
and t y p i c a l c u r r e n t values between 8-100mA. Data e x i s t s
f o r A1-A1 0 tunnel j u n c t i o n s with top Au and Ag f i l m s
2 3
/6/. The s p e c t r a obtained from these j u n c t i o n s , f o r t h e

top e l e c t r o d e s b i a s e d 3.5V p o s i t i v e with r e s p e c t t o t h e
aluminium, show high energy t h r e s h o l d v a l u e s a t about
3.5eV, which i s c o n s i s t e n t with t h e maximum e x c i t a t i o n
energy. The spectrum f o r the Ag top e l e c t r o d e shows
almost constant emission intensity down t o 1.5eV.
S i m i l a r behaviour i s observed f o r the Au t o p e l e c t r o d e
with t h e exception o f a s l i g h t d i p a t 2.5eV which i s
r e p o r t e d l y due t o a Au interband t r a n s i t i o n . The CTRIPS
spectra f o r electron injection shown i n F i g 3 f o r both
Au and Ag, have hig
compare favourably wit
however, the emission i n t e n s i t y i n both cases peaks and
f a l l s o f f quite rapidly. T h i s i s expected s i n c e the
e l e c t r o n i c s t a t e s i n s o l u t i o n a r e not continuous as they
are f o r t h e metal injector. However, t h e exact
d i s t r i b u t i o n f u n c t i o n which d e s c r i b e s t h e s t a t e s i n
s o l u t i o n has been t h e s u b j e c t o f controversy f o r a
number o f years. U n f o r t u n a t e l y , the e x i s t i n g t u n n e l
j u n c t i o n data i s not d i r e c t l y comparable w i t h e x i s t i n g
CTRIPS data because o f a miss-match o f t h e e x c i t a t i o n
energies. However, by c a r r y i n g out CTRIPS and t u n n e l
j u n c t i o n experiments, experimental i n f o r m a t i o n c o u l d be
obtained t o compare with t h e o r e t i c a l d e s c r i p t i o n s o f t h e
distribution function f o r the e l e c t r o n i c states i n
solution.
REFERENCES
1. R McIntyre and J K Sass, J E l e c t r o a n a l . Chem.,

196,199 (1985)
2. R McIntyre and J K Sass, Phys. Rev. L e t t . 56,651

(1986)
3. R McIntyre, D K Roe, J K Sass and H G e r i s c h e r ,

Ber.Bunsenges. Phys. Chem. 91,488 (1987)
4. R McIntyre, D K Roe, J K Sass and W Storck, J

E l e c t r o a n a l Chem. 228,293 (1987)
5. J Ouyang and A J Bard, J Phys. Chem. 91,4058 (1987)
6. A Adams and P K Hansma, Phys. Rev. B, 23,3597

(1981)

7. H Laucht, J K Sass, E Piltz and H Neff Surface Sci.

80,141 (1979)
8. R McIntyre, B Smandek and H G e r i s c h e r , Ber.

Bunsenges. Phys. Chem. 89, 78 (1985)
9. D K Roe, R McIntyre, J K Sass and H G e r i s c h e r , t o

be p u b l i s h e d
10. N E Christensen and B O Seraphin, Phys. Rev. B

4,3321 (1971)
11. J Lambe and S J McCarthy, Phys. Rev. L e t t . 37,923

(1976)
12. T i e n - L a i Hwany, S E Schwarz and R K J a i n , Phys.

Rev. L e t t . 36,379 (1976)
R E C E I V E D May 17, 1988

Chapter 17
Radioelectrochemistry at Well-Defined
Electrodes
Andrzej Wieckowski
Department of Chemistry, University of Illinois, Urbana, IL 61801
Radiochemical measurement
c r y s t a l , well-define reporte
the method of the measurements i s described.
Adsorption of acetic acid on Pt(111) surface was
studied: the surface concentration data were
correlated with voltammetric p r o f i l e s of the
Pt(111) electrode i n perchloric acid e l e c t r o l y t e
containing 0.5 mM of CH3COOH. I t i s concluded that
acetic acid adsorption i s associative and occurs
without a s i g n i f i c a n t charge transfer across the
interface. Instead, the recorded currents are due
to adsorption/desorption processes of hydrogen,
processes which are much better resolved on Pt(111)
than on p o l y c r y s t a l l i n e platinum. A c l a s s i f i c a t i o n
of adsorption processes on c a t a l y t i c electrodes and
atmospheric methods of preparation of single
c r y s t a l electrodes are discussed.
The methodology of surface electrochemistry i s at present

s u f f i c i e n t l y broad to perform molecular-level research as
required by the standards of modern surface science (.1). While
ultra-high vacuum electron, atom, and ion spectroscopies connect
electrochemistry and the state-of-the-art gas-phase surface
science most d i r e c t l y (1-11), their application i s appropriate
for systems which can be transferred from solution to the vacuum
environment without desorption or rearrangement. That this
usually occurs has been v e r i f i e d by several groups (see r e f . 11
for the recent discussion of this issue). However, for the
characterization of weakly interacting i n t e r f a c i a l species, the
vacuum methods may not be able to provide information d i r e c t l y
relevant to the surface composition of electrodes i n contact with
the e l e c t r o l y t e phase. In such a case, jln s i t u methods are
preferred. Such techniques are also unique for the nonelectro-
chemical characterization of i n t e r f a c i a l k i n e t i c s and for the
measurements of surface concentrations of reagents involved i n
0097-6156/88/0378-0245$06.00/0

steady-state processes. Many iri s i t u t e c h n i q u e s have r e c e n t l y

emerged and some o f them can p r o v i d e v a l u a b l e i n f o r m a t i o n as t o
the c o m p o s i t i o n and s t r u c t u r e o f t h e "wet" s o l i d - l i q u i d
i n t e r f a c e . V i b r a t i o n a l a n a l y s i s by SERS (12) and s u r f a c e IR
(12,13)t i n s i t u X-ray d i f f r a c t i o n ( 1 2 ) , Raman second harmonic
g e n e r a t i o n (IM, 15) and s c a n n i n g t u n n e l i n g microscopy (_16) a r e t h e
best examples o f p r o b i n g t h e s o l i d / l i q u i d i n t e r f a c e w i t h o u t
system emersion.
We have r e c e n t l y m o d i f i e d one o f the s e v e r a l r a d i o -
c h e m i c a l methods (_18) which have been used f o r s u r f a c e
e l e c t r o c h e m i s t r y i n v e s t i g a t i o n s i n order t o c h a r a c t e r i z e
a d s o r p t i o n on w e l l - d e f i n e d , s i n g l e c r y s t a l e l e c t r o d e s . Below, we
w i l l d e s c r i b e t h e t e c h n i q u e and i d e n t i f y some c h a l l e n g i n g i s s u e s
which we w i l l be a b l e t o address. The proposed method i s
s e n s i t i v e t o a few p e r c e n t o f a monolayer a t smooth s u r f a c e s , i s
n o n d e s t r u c t i v e and s i m p l e t o use. The r a d i o c h e m i c a l measurements
can be made w i t h a l l compound which b l a b e l l e d with
reasonably l o n g - l i v e d
b e l i e v e t h i s technique
i n s i t u s u r f a c e a n a l y s i s as Auger s p e c t r o s c o p y c u r r e n t l y does i n
vacuum, ex s i t u c h a r a c t e r i z a t i o n o f e l e c t r o d e s .
The Method. The s k e t c h o f the r a d i o - e l e c t r o c h e m i c a l c e l l (17)

used i n our l a b o r a t o r y i s shown i n F i g u r e 1. F i g u r e 2
i l l u s t r a t e s the e s s e n t i a l element o f t h e c e l l : the s i n g l e c r y s t a l
e l e c t r o d e and t h e d e t e c t o r o f the n u c l e a r r a d i a t i o n , i . e . , t h e
g l a s s s c i n t i l l a t o r . Two p o s i t i o n s o f t h e e l e c t r o d e a g a i n s t t h e
s c i n t i l l a t o r are d e p i c t e d : i n p o s i t i o n A the e l e c t r o d e i s
s i t u a t e d s u f f i c i e n t l y away from the d e t e c t o r t o a l l o w f o r a
complete a t t e n u a t i o n , i n t h e bulk e l e c t r o l y t e , o f the r a d i a t i o n
e m i t t e d from the e l e c t r o d e s u r f a c e . I n t h i s p o s i t i o n t h e
c o u n t i n g e f f i c i e n c y o f t h e system i s d e t e r m i n e d . I n p o s i t i o n B,
the e l e c t r o d e i s pressed a g a i n s t the g l a s s s c i n t i l l a t o r and t h e
amount o f a d s o r p t i o n i s measured. The c o u n t i n g c o n t r i b u t i o n due
t o the r a d i o a c t i v i t y i n t h e trapped f i l m can, i n some i n s t a n c e s ,
be n e g l i g i b l e , o r can e a s i l y be c a l i b r a t e d i n the "squeeze" (B)
p o s i t i o n when the a d s o r p t i o n i s not o c c u r r i n g . A s u i t a b l e
e l e c t r o d e p o t e n t i a l can v e r y o f t e n be found t o perform such
calibration.
S u r f a c e c o n c e n t r a t i o n and c o u n t i n g r a t e data are connected by
E q u a t i o n 1:
N N x 1 0 3 c
ads A "
r = (1)
N R f e x x
backg n b P(~n )
where: N a d s i s t h e s i g n a l measured i n t h e "squeezed" p o s i t i o n ,
F i g u r e 2-B, N i s t h e Avogadro c o n s t a n t , c i s t h e bulk
A
c o n c e n t r a t i o n o f t h e a d s o r b a t e (M), N i s the counting r a t e

b a c k g
measured i n t h e "open" p o s i t i o n , F i g u r e 2-A, y i s the a b s o r p t i o n

c o e f f i c i e n t o f t h e B~ r a d i a t i o n i n s o l u t i o n , R i s the roughness
f a c t o r , f i s t h e b a c k s c a t t e r i n g f a c t o r , and x i s t h e t h i c k n e s s
f e
of t h e t r a p p e d s o l u t i o n , F i g u r e 2-B.

17. W I E C K O W S K I Radioekctrochemistry at Well-Defined Electrodes 247
JPMTJ
F i g u r e 1. Diagram of T e f l o n c e l l : (1) p l a t i n u m e l e c t r o d e ; (2)
g l a s s s c i n t i l l a t o r ; (3) Macor ceramic d i s k c e l l bottom; (H)
T e f l o n O - r i n g ; (5) f l e x i b l e elbow (see i n s e r t ) ; (6) c e l l p o r t s
( s i x of them around c e l l body); (7) l i g h t p i p e . I n s e t shows
the d e t a i l s of the f l e x i b l e elbow: (8) s t a i n l e s s s t e e l sphere;
(9) concave T e f l o n s p a c e r ; (10) p l a t i n u m w i r e f o r e l e c t r i c a l
c o n n e c t i o n a c r o s s elbow; (11) l o c k nut.
A Β ©
TO PMT TO PMT
F i g u r e 2. Diagram o f e l e c t r o d e i n a d s o r p t i o n p o s i t i o n and
"squeezed" p o s i t i o n f o r a d s o r b a t e measurement: (1) smooth,
p o l y c r y s t a l l i n e p l a t i n u m e l e c t r o d e ; (2) p o l i s h e d g l a s s
s c i n t i l l a t o r d e t e c t o r ; (3) Macor ceramic d i s k , which forms c e l l
bottom; (4) r e s i n ; (5) e l e c t r o d e s h a f t .

I n t h e squeezed p o s i t i o n , t h e 3~ r a d i a t i o n i s t r a p p e d i n t h e
gap between t h e two s u r f a c e s and the e l e c t r o n s a r e b a c k s c a t t e r e d
from both o f them (J_9). The l a r g e r c o n t r i b u t i o n comes from t h e
s c a t t e r i n g from the h i g h d e n s i t y m a t e r i a l o f the metal e l e c t r o d e
(due t o the Z-dependence o f t h e b a c k s c a t t e r i n g power). The f ^
c o r r e c t i o n which a c c o u n t s f o r t h e b a c k s c a t t e r i n g i s i n c l u d e d i n
E q u a t i o n 1.
A p o w e r f u l c h a r a c t e r i z a t i o n o f e l e c t r o d e s u r f a c e s can be
a c h i e v e d by t h e combined r a d i o c h e m i s t r y and e l e c t r o c h e m i s t r y
p r o c e d u r e s ; w i t h p o l y c r y s t a l l i n e m a t e r i a l s many measurements o f
t h i s type have been r e p o r t e d (18,20,21). A s u c c e s s f u l study o f
a d s o r p t i o n a t w e l l - d e f i n e d s u r f a c e s has r e c e n t l y been conducted
i n our l a b o r a t o r y and i t i s r e p o r t e d below (22,23).
Electrochemical Adsorption a t C a t a l y t i c Electrodes. A

c l a s s i f i c a t i o n o f adsorption processes a t c a t a l y t i c e l e c t r o d e s ,
such as p l a t i n u m o r rhodium f i r s t d b H o r a n y i (,24) d
f u r t h e r developed by Wieckowsk
adsorption processes i n t
1) s u r f a c e complexing p r o c e s s e s ;
2) p r o c e s s e s l e a d i n g t o f o r m a t i o n o f CO-type p r o d u c t s ;
3) a d s o r p t i o n p r o c e s s e s o f weakly i n t e r a c t i n g s p e c i e s .
Two f i r s t two groups c a n b e s t be u n d e r s t o o d i n terms o f
c h e m i s o r p t i o n w i t h e n e r g e t i c s , i r r e v e r s i b i l i t y and s u r f a c e
d i f f u s i o n c h a r a c t e r i s t i c s analogous t o those known from
c h e m i s o r p t i o n r e s e a r c h i n the gas phase ( 2 ) . They encompass both
d i s s o c i a t i v e and n o n d i s s o c i a t i v e a d s o r p t i o n p r o c e s s e s . The
d i s c r i m i n a t i o n between the f i r s t and t h e second group was
p o s s i b l e (21,25,26) due t o t h e i d e n t i f i c a t i o n o f two s e p a r a t e
p o t e n t i a l ranges f o r t h e v o l t a m m e t r i c e l e c t r o o x i d a t i o n o f
r e s p e c t i v e chemisorption products. This i s , i n turn, r e l a t e d t o
the d i f f e r e n c e s i n a d s o r p t i o n e n e r g i e s : f o r t h e f i r s t group
between 30 and 40 k c a l / m o l e and f o r the second group, h i g h e r than
40 k c a l / m o l e . The h i g h a d s o r p t i o n energy a s s o c i a t e d w i t h these
s u r f a c e r e a c t i o n s makes t h e c h e m i c a l c o n t r i b u t i o n t o t h e t h e i r
o v e r a l l e n e r g e t i c s much more pronounced than the e l e c t r i c a l
c o n t r i b u t i o n . Such systems, i n t h e i r c o m p o s i t i o n a l and
s t r u c t u r a l a s p e c t s , c a n s a f e l y be s t u d i e d by t h e vacuum methods:
any d e s o r p t i o n (or rearrangement) from the s u r f a c e d u r i n g
s o l u t i o n / v a c u u m t r a n s f e r a t room t e m p e r a t u r e c a n be r u l e d out
from e n e r g e t i c r e a s o n s .
The p r o c e s s e s c l a s s i f i e d i n t h e t h i r d group a r e o f primary
importance i n e l u c i d a t i n g the s i g n i f i c a n c e o f e l e c t r i c v a r i a b l e s
i n e l e c t r o s o r p t i o n and i n the double l a y e r s t r u c t u r e a t s o l i d
e l e c t r o d e s . These p r o c e s s e s encompass i n t e r a c t i o n s o f i o n i c
components o f s u p p o r t i n g e l e c t r o l y t e s w i t h e l e c t r o d e s u r f a c e s and
a d s o r p t i o n o f some o r g a n i c m o l e c u l e s such as s a t u r a t e d c a r b o x y l i c
a c i d s and t h e i r d e r i v a t i v e s ( e x c e p t f o r f o r m i c a c i d ) . The
s p e c i e s t h a t a r e concerned here are weakly adsorbed on p l a t i n u m
and rhodium e l e c t r o d e s and t h e i r heat o f a d s o r p t i o n i s w e l l below
20 k c a l / m o l e ( 2 5 ) . Due t o the r e v e r s i b i l i t y and s i g n i f i c a n t
m o b i l i t y o f such weakly adsorbed i o n s o r m o l e c u l e s , t h e
a p p l i c a t i o n o f t h e in s i t u methods f o r t h e s u r f a c e c o n c e n t r a t i o n
measurements i s more a p p r o p r i a t e than t h a t o f the vacuum

17. WIECKOWSKI Radioekctrochemistry at Well-Defined Electrodes 249
t e c h n i q u e s . The primary measurements t h a t can be done by the use

of the r a d i o - e l e c t r o c h e m i s t r y r e g a r d i n g t h i s group o f processes
are as f o l l o w s :
- p o t e n t i a l dependence o f a d s o r p t i o n a t v a r i o u s metals and a t
d i f f e r e n t c r y s t a l l o g r a p h i c planes o f a g i v e n m e t a l ;
- a d s o r p t i o n isotherms and i s o t h e r m - r e l a t e d parameters such as
f r e e energy o f a d s o r p t i o n and i n t e r a c t i o n parameters ( a g a i n
related to surface crystallography);
- dynamics o f t h e i n t e r f a c i a l processes i n c l u d i n g k i n e t i c s o f
a d s o r p t i o n and d e s o r p t i o n and those o f m o l e c u l a r and atomic
exchanges between the s p e c i e s i n the s u r f a c e a t t a c h e d and
dissolved states;
- steady-state c h a r a c t e r i s t i c s ;
- m o l e c u l a r o r i e n t a t i o n o f molecules t h a t have more than one
p o s s i b l e modes o f s u r f a c e attachment.
To implement t h i s program o f measurements on w e l l - d e f i n e d
e l e c t r o d e s , the method f preparatio f clea d well-ordered
single c r y s t a l surface
o b t a i n e d e i t h e r by the
procedures, the l a t t e r methods w i l l b r i e f l y be d e s c r i b e d below.
P r e p a r a t i o n o f W e l l - D e f i n e d E l e c t r o d e s f o r I n S i t u Measurements
i n S u r f a c e E l e c t r o c h e m i s t r y . There are t h r e e methods o f
p r e p a r a t i o n o f c a t a l y t i c , s i n g l e c r y s t a l e l e c t r o d e s t h a t do n o t
r e q u i r e an u l t r a - h i g h vacuum environment: ( i ) c r y s t a l flame
a n n e a l i n g f o l l o w e d by water quenching (27); ( i i ) c r y s t a l flame
a n n e a l i n g f o l l o w e d by c o o l i n g i n gaseous hydrogen (£8) and ( i i i )
c r y s t a l e l e c t r i c a l a n n e a l i n g and c o o l i n g i n an i n e r t gas
atmosphere c o n t a i n i n g i o d i n e vapor (29,30). To c r e a t e an
i o d i n e - f r e e s u r f a c e , t h i s t h i r d method r e q u i r e s some a d d i t i o n a l
s t e p s developed i n our l a b o r a t o r y : a replacement o f i o d i n e by
carbon monoxide and anodic s t r i p p i n g o f chemisorbed CO has been
proposed (3J_). C o n t r a r y t o the e l e c t r o o x i d a t i o n o f i o d i n e , t h e
e l e c t r o o x i d a t i o n o f carbon monoxide does not cause s u r f a c e
disorder.
A voltammetric c h a r a c t e r i z a t i o n o f platinum s i n g l e c r y s t a l
s u r f a c e s produced by these t h r e e methods shows t h a t a v e r y
s i m i l a r s u r f a c e order and c l e a n l i n e s s are o b t a i n e d i n each case.
The f e a t u r e s embodied by the t h i r d method which we use f o r t h e
r a d i o - e l e c t r o c h e m i s t r y work, are as f o l l o w s :
- up t o the stage o f I/CO r e p l a c e m e n t , the s i n g l e c r y s t a l
p r e p a r a t i o n procedure was s t r i c t l y v e r i f i e d by LEED and Auger
s p e c t r o s c o p y (29,30). A c l o s e correspondence between t h e
s u r f a c e e l e c t r o c h e m i s t r y and the gas-phase s u r f a c e s c i e n c e o f
p l a t i n u m has r e s u l t e d due t o t h i s e a r l i e r work.
- slow c o o l i n g i n the i o d i n e atmosphere does n o t cause
p o l y g o n i z a t i o n o f p l a t i n u m c r y s t a l r e p o r t e d by some a u t h o r s
to t r o u b l e the quenching technique (32). F o r the a p p l i c a -
t i o n s r e q u i r i n g h i g h l e v e l o f s u r f a c e smoothness (as i n t h e
case o f r a d i o - e l e c t r o c h e m i s t r y ) deformations o f the e l e c t r o d e
m a t e r i a l must be a v o i d e d .
- the c l e a n , i o d i n e - f r e e s i n g l e c r y s t a l s u r f a c e i s c r e a t e d i n
the e l e c t r o l y t i c s o l u t i o n thus m i n i m i z i n g p o s s i b l e

c o n t a m i n a t i o n s from the gaseous atmosphere b e f o r e the

e l e c t r o c h e m i c a l steps are executed.
- e x t e n s i o n o f the p r e p a r a t i o n o f s i n g l e c r y s t a l s u r f a c e s to
rhodium has become p o s s i b l e (J33). Aqueous quenching o f hot
rhodium causes a f o r m a t i o n o f b l a c k s u r f a c e d e p o s i t and makes
f u r t h e r w e l l - d e f i n e d work w i t h t h i s m e t a l d i f f i c u l t , i f not
impossible.
Case S t u d i e s ; A d s o r p t i o n o f A c e t i c A c i d on P t ( 1 1 1 ) S i n g l e
C r y s t a l E l e c t r o d e s . A c e t i c a c i d i s one o f a very few o r g a n i c
compounds which i s r e v e r s i b l y adsorbed on p l a t i n u m a t room
temperature (20,25). We r e p o r t below our r a d i o c h e m i c a l r e s u l t s
on a d s o r p t i o n of t h i s compound on Pt(111) and on p o l y c r y s t a l l i n e
Pt.
The Pt(111) e l e c t r o d e was c h a r a c t e r i z e d by the low e l e c t r o n
energy d i f f r a c t i o n i n the u l t r a - h i g h vacuum i n s t r u m e n t t o be
d e s c r i b e d s h o r t l y . A prope hexagonal LEED p a t t e r d it
l o w - i n t e n s i t y backgroun
surface order. The c r y s t a
and t r a n s f e r r e d v i a a i r t o the r a d i o c h e m i c a l c e l l , F i g u r e 1 (17).
The c l e a n i n g and o r d e r i n g o f the s u r f a c e was performed a c c o r d i n g
to the I/CO method d e s c r i b e d above and i n r e f . 31. Addition of
0.5 mM a c e t i c a c i d t o the p e r c h l o r i c a c i d s o l u t i o n produced the
voltammogram shown i n F i g u r e 4. The f o r m a t i o n o f some new
v o l t a m m e t r i c f e a t u r e s between 0.1 and 0.4 V and the s u p p r e s s i o n
of the peaks between 0.3 and 0.6 V, c h a r a c t e r i s t i c f o r c l e a n
p e r c h l o r i c a c i d e l e c t r o l y t e s h o u l d be n o t e d . S i m i l a r voltammet-
r i c behavior o f the P t ( l l l ) e l e c t r o d e has p r e v i o u s l y been
observed a f t e r a d d i t i o n t o p e r c h l o r i c a c i d e l e c t r o l y t e of
s u l f u r i c a c i d i n the m i l l i m o l a r range o f i t s bulk c o n c e n t r a t i o n
(27).
The r a d i o c h e m i c a l r e s u l t s o b t a i n e d w i t h the P t ( l l l ) e l e c t r o d e
i n the e l e c t r o l y t e c o n t a i n i n g C-14 l a b e l e d a c e t i c a c i d a r e shown
in Figure 4 ( c i r c l e s ) . The a d s o r p t i o n i s n e g l i g i b l e at 0.15 V,
s m a l l a t more n e g a t i v e p o t e n t i a l s and v e r y pronounced a t
p o t e n t i a l s more p o s i t i v e than 0.15 V. I n the p o t e n t i a l range
between 0.3 and 0.85 V, the r a d i o c h e m i c a l s i g n a l from the
s u r f a c e , i . e . , the s u r f a c e c o n c e n t r a t i o n o f a c e t i c a c i d , e q u a t i o n
1, i s p o t e n t i a l independent. T h i s r e s u l t i s i n t e r e s t i n g s i n c e
v e r y s t r o n g p o t e n t i a l e f f e c t s i n t h i s p o t e n t i a l range were found
i n the case o f CH^COOH a d s o r p t i o n on p o l y c r y s t a l l i n e p l a t i n u m
(see r e f s . 20, 25, 34 and F i g u r e 5 o f t h i s w o r k ) . I f the
p r o d u c t s on both e l e c t r o d e s are the same, t h i s o b s e r v a t i o n would
be i n d i c a t i v e o f an i n c r e a s e d s t a b i l i t y o f adsorbed a c e t i c a c i d
on the w e l l - o r d e r e d , s i n g l e c r y s t a l e l e c t r o d e v s . the p o l y -
c r y s t a l l i n e s u b s t r a t e . I n g e n e r a l , such b e h a v i o r r e f l e c t s the
p r o p e r t i e s o f i n t e r f a c i a l atoms and m o l e c u l e s which, when
adsorbed on w e l l - d e f i n e d s u b s t r a t e s , tend t o c r e a t e s t a b l e and
d i s t i n c t phases o f t w o - d i m e n s i o n a l p e r i o d i c i t y and order ( 3 5 ) .
As shown i n F i g u r e 4, the i n c r e a s e i n a d s o r p t i o n o f a c e t i c
a c i d on P t ( l l l ) o c c u r s i n the p o t e n t i a l range o f 0.15 t o 0.3 V,
w h i c h r o u g h l y c o i n c i d e s w i t h p o s i t i o n o f the c u r r e n t - p o t e n t i a l
peak of the voltammogram r e c o r d e d i n the same s o l u t i o n . An
i n t e r d e p e n d e n c e can thus be sought between a c e t i c a c i d a d s o r p t i o n

WIECKOWSKI Radioelectrochemistry at Well-Defined Electrodes
F i g u r e 3. LEED p a t t e r n o f the P t ( l l l ) e l e c t r o d e used f o r t h e

r e p o r t e d r e s e a r c h . The beam energy was 65 eV.

-i 1 1 1 1 r
_2_}o.5mM CH3COOH
'S 2
o
E
'O
X
0.2 0.4
E/V (Ag/AgCI)
Figure 4. A combined figure representing the following
r e l a t i o n s h i p s : c y c l i c voltammogram of the P t ( l l l ) electrode
i n 0.1 M HCIO^ ( s o l i d l i n e ) ; c y c l i c voltammogram following
addition of 0.5. mM CH3COOH to the 0.1 M HC10 e l e c t r o l y t e
4
(broken l i n e ) ; surface concentration of adsorbed acetic acid

plotted as a function of the electrode p o t e n t i a l ( s o l i d l i n e
and c i r c l e s ) . (Reprinted with permission from r e f . 23.
Copyright 1988 Elsevier.)

17. WIECKOWSKI Radioelectrochemistry at Well-Defined Electrodes 253
0.0 0.4 0.8 L2

—i 1 1 —• r
_°-} ImM CH3COOH
I I I I U
0.0 0.4 0,8 1.2
E/V vs. SCE
Figure 5. A combined figure representing the following

r e l a t i o n s h i p s : c y c l i c voltammogram of the p o l y c r y s t a l l i n e
Pt electrode i n 0.1 M HCIO^ ( s o l i d l i n e ) ; c y c l i c voltam-
mogram following addition of 1 mM CH C00H to the 0.1 M 3
HCIO^ e l e c t r o l y t e (broken l i n e ) ; surface concentration

of adsorbed acetic acid plotted as a function of the
electrode p o t e n t i a l ( s o l i d l i n e and c i r c l e s ) . (Reprinted
with permission from r e f . 23. Copyright 1988 E l s e v i e r . )

and t h e r e s p e c t i v e c u r r e n t - g e n e r a t i n g p r o c e s s . The s i m p l e s t
explanation i s that adsorption of a c e t i c a c i d i s d i s s o c i a t i v e
(36) and f o l l o w e d by t h e e l e c t r o n charge t r a n s f e r p r o c e s s ,
a c c o r d i n g t o e q u a t i o n 2:
+
CH COOH
3 > CH COO
3 ads + H + e" (2)
C o n t r a r y t o t h e s i n g l e - c r y s t a l r e s u l t s d i s c u s s e d above, t h e
e f f e c t of a d d i t i o n of a c e t i c acid t o the p e r c h l o r i c acid
e l e c t r o l y t e on t h e voltammograms o f the p o l y c r y s t a l l i n e Pt (34)
was i n s i g n i f i c a n t ( F i g u r e 5 ) . Only a s m a l l e x t r a charge i n t h e
hydrogen range and an i n i t i a l s u p p r e s s i o n o f p l a t i n u m o x i d a t i o n
were observed ( d o t t e d c u r v e ) v e r s u s t h e base voltammogram
o b t a i n e d i n pure HClOj^ e l e c t r o l y t e ( s o l i d voltammogram).
N o t i c e a b l y , t h e c u r r e n t - p o t e n t i a l curve i n t h e double l a y e r
r e g i o n (from 0.1 t o 0.4 V) was u n a f f e c t e d by a c e t i c a c i d p r e s e n t
in the e l e c t r o l y t e . I n t h e same p o t e n t i a l range t h e s u r f a c e
concentration of aceti
shown by the r a d i o c h e m i c a
t h e r e f o r e conclude that accumulation o f a c e t i c a c i d molecules a t
the e l e c t r o d e s u r f a c e between 0.1 and 0.4 V was n o t a s s o c i a t e d
w i t h a measurable e l e c t r o n charge t r a n s f e r p r o c e s s a c r o s s t h e
interface. I n o t h e r words, a d s o r p t i o n o f a c e t i c a c i d on t h e
p o l y c r y s t a l l i n e substrate i s associative.
Comparison o f R e s u l t s O b t a i n e d w i t h P t ( l l l ) and P o l y c r y s t a l l i n e
E l e c t r o d e s . We have shown above t h a t p o t e n t i a l dependence o f
a d s o r p t i o n o f a c e t i c a c i d on P t ( l l l ) and on p o l y c r y s t a l l i n e P t i s
d i f f e r e n t . However, t h e c e n t r a l q u e s t i o n whether a d s o r p t i o n o f
CH^COOH can be d i s s o c i a t i v e on P t ( l l l ) ( e q u a t i o n 2) and
a s s o c i a t i v e on t h e p o l y c r y s t a l l i n e Pt c a n n o t unambiguously be
answered by t h e r a d i o c h e m i c a l and e l e c t r o c h e m i c a l s t u d i e s a l o n e
(23). To a d d r e s s t h e i s s u e o f t h e "anomalous" s i n g l e - c r y s t a l
voltammetry (£7), we have r e c e n t l y s t u d i e d a d s o r p t i o n o f s u l f a t e
( b i s u l f a t e ) a n i o n s on P t ( l l l ) (37). We found t h a t t h e s p e c i f i c
a d s o r p t i o n model o f t h e anomalous b e h a v i o r (_38) would r e q u i r e an
exchange o f t h r e e e l e c t r o n s between adsorbed a n i o n and the m e t a l .
S i n c e t h i s appeared u n l i k e l y , we concluded t h a t t h e anomalous
charge i s due t o a d s o r p t i o n o f h i g h - e n e r g y hydrogen, as
o r i g i n a l l y proposed by C l a v i l i e r (2J). We have a l s o i n d i c a t e d
the p o s s i b i l i t y t h a t t h e p o t e n t i a l range o f a d s o r p t i o n / d e s o r p t i o n
o f t h i s h i g h - e n e r g y hydrogen can be c o n t r o l l e d by t h e e x t e n t o f
c o a d s o r p t i o n w i t h hydrogen o f a n i o n s o r o t h e r e l e c t r o n - r i c h
molecules. S i n c e t h e voltammetry o f the P t ( l l l ) e l e c t r o d e i n
s o l u t i o n s c o n t a i n i n g a c e t i c a c i d and s u l f u r i c a c i d i s v e r y
s i m i l a r , we c o n s e q u e n t l y c o n c l u d e t h a t d e s o r p t i o n o f h i g h - e n e r g y
hydrogen i s a more p r o b a b l e s o u r c e o f e l e c t r i c c u r r e n t than t h e
a c e t i c a c i d d i s c h a r g e r e p r e s e n t e d by e q u a t i o n 2.
Whether such s t r o n g l y - b o u n d hydrogen i s p r e s e n t on t h e
P t ( 1 1 1 ) s u r f a c e has been a s u b j e c t o f debate f o r some time. By
a n a l y z i n g then e x i s t i n g d a t a on a d s o r p t i o n energy o f gas phase
hydrogen on P t ( 1 1 1 ) , Wagner and Ross (39) concluded t h a t
e l e c t r o c h e m i c a l a d s o r p t i o n o f hydrogen i s n o t e n e r g e t i c a l l y
a l l o w e d t o occur i n t h e h i g h p o t e n t i a l range c l o s e l y p r e c e d i n g

17. W I E C K O W S K I Radioelectrochemistry at Well-Defined Electrodes 255
p l a t i n u m e l e c t r o o x i d a t i o n . However, some newer data i n d i c a t e

t h a t a t l e a s t 10 - 15% o f a monolayer o f hydrogen desorbs a t a
temperature o f 100 Κ h i g h e r than t h a t where most o f t h e monolayer
hydrogen desorbs (^0). We b e l i e v e t h a t t h i s o b s e r v a t i o n g i v e s an
a d d i t i o n a l support t o t h e o r i g i n a l i n t e r p r e t a t i o n o f t h e P t ( l l l )
voltammetry i n a c i d i c media ( 2 7 ) . We would a l s o l i k e t o note
t h a t more d a t a r e g a r d i n g a d s o r p t i o n o f hydrogen on s i n g l e - c r y s t a l
s u r f a c e s may soon be p r o v i d e d by t h e i n s i t u s p e c t r o s c o p i e s o f
e l e c t r o c h e m i c a l s u r f a c e s c i e n c e . Recent p r o g r e s s i n s u r f a c e IR
(13,41,42) and i n Raman second harmonic g e n e r a t i o n (15,43) i s
p a r t i c u l a r l y p r o m i s i n g here.
Acknowledgments
T h i s work was supported by t h e N a t i o n a l S c i e n c e Foundation under

Grant NSF DMR-86-12860 ( a d m i n i s t e r e d by the M a t e r i a l s Research
L a b o r a t o r y o f the U n i v e r s i t
U.S.A.
Literature Cited
1. Hubbard, A. T. Acc. Chem. Res. 1980, 13, 177.

Cornell University Press: Ithaca, 1981.
3. Ishikawa, R. M.; Hubbard, A. T.; J. Electroanal. Chem. 1976,
69, 317.
4. Ross, R. Ν. J . Electroanal. Chem. 1977, 78, 139.
5. Yeager, E . ; O'Grady, E. W.; Woo, M. Y. C.; Hagans, P. J.
Electrochem. Soc. 1978, 125, 346.
6. Hubbard, A. T. J . Vac. S c i . Technol. 1980, 17, 49.
7. Yeager, E. J . Electrochem. Soc. 1981, 128, 160c.
8. Ross, P. Ν.; Wagner, F. T. Adv. in Electrochem. and
Electrochem. Eng; Gerisher, H . , Ed.; Wiley-Interscience, New
York, 1984; Vol. 31, p. 69.
9. D'Agostino, A. T.; Hansen, W. N. Surf. S c i . 1986, 165, 268.
10. Kotz, E. R.; Neff, H.; Muller, K. J . Electroanal. Chem.
1986, 215, 331.
11. Kolb, D. M. Z. Phys. Chem. 1987, 154, 179.
12. Fleischmann, M. Advances in Electrochemistry; The Robert A.
Welch Foundation Conferences on Chemical Research, 1986; No.
3-5, p. 91.
13. Bewick, Α.; Pons, S. Adv. in Infrared, Raman Spectr.;
Clark, R. J. H.; Hester, R. E . , Ed.; Wiley Heyden: New
York, 1985; Vol. 12, p. 1.
14. Chen, C. K.; Heinz, T. F.; Ricard, D; Shen, Y. R. Phys.
Rev. Β 1983, 27, 1965.
15. Richmond, G. L. Langmuir 1986, 2, 132.
16. Sonnenfeld, R.; Hansma, P. K. Science 1986, 232, 211.
17. Krauskopf, Ε. K.; Chan, K.; Wieckowski, A. J . Phys. Chem.
1987, 91, 2327.
18. Kazarinov, V. E.; Andreev, V. N. Comprehensive Treatise of
Electrochemistry; Yeager, E.; Bockris, J. O'M.; Conway, B.
E.; Sarangapani, S., Ed.; Plenum: New York, 1984; Vol. 9,
p. 393.

19. Price, W. J. McGraw-Hill Series in Nuclear Engineering;

Zinn, W. H . ; Luntz, J. D., Ed.; McGraw-Hill: New York,
1958; p. 131.
20. Horanyi, G. Electrochimica Acta 1980, 25, 43.
21. Krauskopf, E. K.; Wieckowski, A. Modern Aspects of
Electrochemistry; submitted.
22. Wieckowski, A.; Krauskopf, E. K. Presented at the 194th
National Meeting of the ACS, August 30-September 4, 1987,
New Orleans, LA.
23. Rice, L . ; Krauskopf, E. K.; Wieckowski, A. J . Electroanal.
Chem. in press.
24. Horanyi, G. J . Electroanal. Chem. 1974, 51, 163.
25. Wieckowski, A. Electrochimica Acta 1981, 26, 1121.
Wieckowski, A.; Sobkowski, J.; Zelenay, P.; Franaszczuk, K.
Electrochimica Acta 1981, 26, 1111.
26. Wieckowski, A. The Analysis of Electrochemical Adsorption
Processes on Platinum; P W U . Warsaw Poland 1984
27. Clavilier, J . J .
28. Motoo, S.; Furuya
29. Wieckowski, A.; Rosasco, S. D.; Schardt, B. C.; Stickney, J .
L . ; Hubbard, A. T. Inorg. Chem. 1984, 23, 565.
30. Wieckowski, A.; Schardt, B.C.; Rosasco, S. D.; Stickney, J .
L . ; Hubbard, A. T. Surf. S c i . 1984, 146, 115.
31. Zurawski, D.; Rice, L . ; Hourani, M.; Wieckowski, A. J .
32. Aberdam, D.; Durand, R.; Faure, R.; El-Omar, F. Surf. S c i .
1986, 171, 303.
33. Hourani, M.; Wieckowski, A. J . Electroanal. Chem. 1987,
227, 259.
34. Corrigan, D. S.; Krauskopf, E. K.; Rice, L. M.; Wieckowski,
A.; Weaver, M. J. J. Phys. Chem. in press.
35. Roelofs, L. D.; Estrup, P. J. Surf. S c i . 1983, 125, 51.
36. Avery, N. R. J . Vac. S c i . Technol. 1982, 20, 3.
37. Krauskopf, E. K., Rice, L. M., and Wieckowski, A. J .
Electroanal. Chem., in press.
38. Al Jaaf-Golze, K.; Kolb, D. M.; Scherson, D. J . Electro-
anal. Chem. 1986, 200, 353.
39. Wagner, F. T.; Ross, P. N . , Jr. J . Electroanal. Chem. 1983,
150, 141.
40. Zhou, X . - L . ; White, J. M. Surf. S c i . 1987, 185, 450.
41. Leung, L-W. H. and Weaver, M. J. J . Electroanal. Chem.,
1988, 240, 341.
42. Sun, S. G., Clavilier, J., and Bewick, A. J . Electroanal.
Chem., 1988, 240, 147.
43. Campbell, D. J. and Corn, R. M. J . Phys. Chem., 1987, 91,
4668.
R E C E I V E D May 17, 1988

Chapter 18
Applications of In Situ Mössbauer

Spectroscopy to the Study
of Transition Metal Oxides
1 2 1
Daniel A. Scherson , Dennis A. Corrigan , Cristian Fierro ,
1
and Raul Carbonio
1
Case Center for Electrochemical Sciences and the Department of
Chemistry, Case Wester
2
Physical Chemistry Department
Warren, MI 48090-9055
A d e t a i l e d understanding of the electrochemistry of t r a n s i t i o n
metal oxides i s of importance to the f i e l d s of energy storage,
corrosion protection, and electrocatalysis.(1) Itisthus not
s u r p r i s i n g that much research has been devoted to the ex situ and
i n s i t u spectroscopic c h a r a c t e r i z a t i o n of such materials i n an
e f f o r t to elucidate t h e i r structure and o v e r a l l physicochemical
properties. Although ex situ techniques o f f e r s i g n i f i c a n t advan-
tages in terms of s e n s i t i v i t y and s p e c i f i c i t y , considerable care
must be exercised i n the analysis o f information derived from
t h e i r use. This is due p r i m a r i l y to the f a c t that the transfer of
electrodes from electrochemical to other environments often r e -
s u l t s i n a loss of p o t e n t i a l c o n t r o l , s t r u c t u r a l rearrangements,
such as those induced by the exposure of specimens to air or
vacuum, and/or actual chemical transformations associated with the
i r r a d i a t i o n of specimens with UV, X-rays and electrons, asisthe
case with the electron-based surface science a n a l y t i c a l methods.
I t i s p r e c i s e l y because of these uncertainties that much a t t e n t i o n
has been focused over the l a s t ten to f i f t e e n years towards the
development of techniques capable of providing in situ microscopic
l e v e l information regarding the structure and properties of metal
electrolyte interfaces.
This work summarizes some applications of in situ Mossbauer
spectroscopy to the study of c e r t a i n aspects of the electrochemis-
t r y of i r o n and i r o n containing t r a n s i t i o n metal oxides. A number
of i l l u s t r a t i o n s of the use of t h i s technique to the i n v e s t i g a t i o n
of a wide v a r i e t y of i n t e r f a c i a l phenomena may be found i n two
recent monographs.(2)
THE IRON 0XYHYDR0XIDE SYSTEM
One of the f i r s t i n s i t u Mossbauer investigations of the behavior

of i r o n oxides i n electrochemical enviroments was the r e s u l t of a
f o r t u i t o u s incident i n which a specimen containing i r o n phthalo-
0097-6156/88/0378-0257$06.00/0

cyanine, FePc, dispersed on a high area carbon was a c c i d e n t a l l y

decomposed during a rather mild heat treatment to y i e l d a very
f i n e dispersion of some form of f e r r i c oxide.(3) FePc i s a h i g h l y
conjugated t r a n s i t i o n metal macrocycle which has been found to
e x h i b i t high a c t i v i t y f o r the electrochemical reduction of dioxy-
gen when supported on a host e l e c t r o n i c a l l y conducting sub-
s t r a t e . (4)
F i g . 1 shows the c y c l i c voltammetry of an FePc/XC-72 disper-
sion, heated at 280°C i n an i n e r t atmosphere, i n the form a t h i n
porous Teflon bonded coating electrode i n a 1 M NaOH s o l u t i o n . A
d e s c r i p t i o n of the methodology involved i n the preparation of t h i s
type of electrode may be found i n Ref. 3. As can be c l e a r l y seen,
the voltammetry of t h i s 'specimen e x h i b i t s two sharply defined
peaks separated by about 330 mV. The p o t e n t i a l s associated with
these features are e s s e n t i a l l y i d e n t i c a l to those found by other
workers f o r the reduction and oxidation of f i l m s of i r o n oxy-
hydroxide formed on a number of host surfaces i n c l u d i n g i r o n and
carbon.(5)
A 10% w/w highly enriche
i n exactly the same fashion, was used i n the Mossbauer measure-
ments. (The isomer s h i f t s , 5, are r e f e r r e d to the a-Fe standard,
and 6. the quadrupole s p l i t t i n g s A, and widths T, are a l l given i n
mm•s"1, throughout the text.)
The i n s i t u Mossbauer spectra obtained at 0.0 V i s given i n
curve A, F i g . 2. The parameters associated with t h i s doublet
(Table I) are s i m i l a r to those reported by various groups f o r high
spin f e r r i c oxyhydroxides (Table I I ) . Also, they appear i n agree-
ment with those observed for c e r t a i n magnetically ordered oxides
for which the c h a r a c t e r i s t i c s i x l i n e spectra collapses i n t o a
doublet as the p a r t i c l e s become smaller i n s i z e . This phenomenon
known as superparamagnetism,(6) i s a t t r i b u t e d to the f l i p p i n g of
the magnetic moment of each microcrystal between easy d i r e c t i o n s .
This occurs i n a shorter time than e i t h e r the Larmor precessional
period of the nucleus or the l i f e t i m e of the excited 3/2 state of
5 7
the F e nucleus or both, when the temperature i s s u f f i c i e n t l y
high. Such behavior has been observed, f o r example, by Hassett et
al.(7) for magnetite dispersed i n lignosulfonate.
The quadrupole s p l i t t i n g of the heat treated FePc/XC-72
electrode measured ex s i t u , p r i o r to the electrochemical experi-
ments, was larger than that found i n s i t u . Smaller values f o r A
have been reported for c e r t a i n f e r r i c hydroxide gels and f o r small
p a r t i c l e s of FeOOH (Table I I ) , and thus the e f f e c t associated with
the immersion of the specimen i n the e l e c t r o l y t e i s most probably
r e l a t e d to the incorporation of water i n t o the oxide structure.
For t h i s reason, the material observed i n s i t u at t h i s p o t e n t i a l
w i l l be r e f e r r e d to hereafter as FeOOH(hydrated), without implying
any s p e c i f i c stoichiometry.
The i n s i t u spectra obtained at -1.0 V, shown i n curve B, F i g
2, y i e l d e d a doublet with values of 6 and A i n e x c e l l e n t agreement
with those of c r y s t a l l i n e Fe(0H)2 (Table I ) . This provides rather
d e f i n i t e evidence that the redox process associated with the
voltammetric peaks i s given by:
+
FeOOH (hydrated) + e" + H > Fe(0H) 2 ( c r y s t a l l i n e ) (1)

SCHERSON ET AL. Mossbauer Spectroscopy and Transition Metal Oxides 259
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2
POTENTIAL/V vs. Hg/HgO,OH*
F i g . 1. C y c l i c voltammetry of 7% w/w i r o n phthalocyanine,

FePc dispersed on Vulcan XC-72 carbon, after a heat treatment
at 280°C i n a flowing inert atmosphere. The measurement was
conducted with the material i n the form a t h i n porous Teflon
bonded coating i n 1 M NaOH at 25°. Sweep rate: 5 mV/s. (Repro-
duced with permission from r e f . 3. Copyright 1985 Elsevier.)

H
2
or
<
Q:
CD
Q:
<
-5.0 -3.0 -L0 1.0 3.0 5.0
VELOCITY (mm/s)
2
>-
or
<
CD
cr
<
-4.0 -2.0 00 2.0
VELOCITY (mm/s)
F i g . 2. I n s i t u Mossbauer spectra f o r ^ F e P c dispersed i n

Vulcan XC-72 carbon and subsequently heat treated a t 300°C
obtained a t 0.0 V (Curve A), and -1.05 V v s . Hg/Hg0,0H"
(Curve B). (Reproduced with permission from r e f . 3. Copyright
1985 Elsevier.)

TABLE I
In s i t u Mossbauer parameters f o r small p a r t i c l e s of a hydrated f e r r i c

oxyhydroxide, FeOOH(hydrated), dispersed on high area Vulcan XC-72 carbon *
Potential Isomer S h i f t Quadrupole S p l i t t i n g Width Figure

1
V vs. Hg/HgO,OH" 5/mm- " vs . a - Fe A/mm-s"•1 r/mm•s"1
0.0 0.37 0.76 0.62 2A
-0.4 0.37 0.74 0.65 --

-0.75 0.37 0.66 0.57 --
-0.85 0.35 0.63 0.60 --
-1.05 1 0.41 0.65 0.77 2B
2 1.14 2.85 0.32

* This material was prepared by the heat treatment of i r o n phthalocyanine
dispersed on the carbon i n an i n e r t atmosphere a t 280°C.

TABLE II
Ex s i t u Mossbauer parameters of various iron oxides and oxyhydroxides

at room temperature *
Specimen Isomer Shift Quadrupole S p l i t t i n g Width H ff

e
"1 vs. a-Fe A/mm-s"l r/mrn-s"^- kOe
a-FeOOH 0.44 0.16 0.86 367

(goethite)
a
a-Fe203 0.32 0.98
(diam.< 10 nm)
P-FeOOH 0.38 (61.4) 0.53 0.26

0.39 (38.6) 0.88 0.30
7-FeOOH 0.38 0.59 0.27

(lepidocrocite)
a-Fe203 0.38
(hematite)
7-Fe203 0.43 0.06 0.45 506

(maghemite)
Fe304 0.39 (49.6) 0.11 0.53 506

non- 0.78 (50.4) 0.28 0.38 465
stoichiometric
7-Fe 04
3 0.37 ( 4.8)° 0.59 0.43
stoichiometric 0.34 (34.4) 0.12 0.29 491
(magnetite) 0.72 (59.8) 0.10 0.31 461
D
7-Fe304 0.37 0.89
(diam.< 5 nm)
Fe(0H) 2
c
1.18 2.92
d
F e r r i c oxide 0.33 0.70
(small p a r t i c l e s )
e
F e r r i c oxide 0.35 0.62
(hydrated)
f
Fe00H 0.39 0.62
(small particles)
* Data from S. Music, I. Czako-Nagy, S. Popovic, A. Vertes and M. Tonkovic,

Croat. Chem. Acta, 59,833(1986), except where otherwise indicated,
o This feature i s due to FeOOH.
a. W. Kundig, H. Bommel, C. Constabaris and H. Lindquist, Phys. Rev.,142,

327(1966);
b. S. Aharoni and M. L i t t , J . AppI. Phys.,42,352(1971);
c. A. M. Pritchard and B. T. Mould, Corros. Sci.,11,1(1971);
d. D. G. Rethwisch and J . A. Dumesic, J . Phys. Chem.,90,1863(1986);
e. P. P. Bakare, M. P. Gupta and A. P. B. Sinha, Indian J . Pure AppI.
Phys.,18,473(1980);
f. P. 0. Vozniuk, V. N. Dubinin, Sov. Phys.-Solid State,15,1265(1973).

18. SCHERSON ET AL. Mossbauer Spectroscopy and Transition Metal Oxides 263
I t may thus be concluded that the s p e c i f i c methodology i n -

volved i n the dispersion of FePc on high area carbon leads to the
thermal decomposition of the macrocycle at temperatures much below
those expected f o r the bulk material, generating small p a r t i c l e s
of hydrated FeOOH upon exposure to an a l k a l i n e s o l u t i o n .
More recently, F i e r r o e t al.(8) have reported a series of i n
s i t u Mossbauer experiments aimed at i n v e s t i g a t i n g the e l e c t r o -
chemical behavior of the i r o n oxyhydroxide system i n strongly
a l k a l i n e media. For these measurements, a hydrated form of a
f e r r i c oxyhydroxide p r e c i p i t a t e d by chemical means on a high area
carbon was used. This material was prepared by f i r s t d i s s o l v i n g a
mixture of h i g h l y enriched m e t a l l i c ->7p j
e a n c appropriate amount
a n
of natural i r o n i n concentrated n i t r i c a c i d to achieve about one-

t h i r d isotope enrichment i n the f i n a l product. This s o l u t i o n was
then added to an u l t r a s o n i c a l l y agitated water suspension of
Shawinigan black, a high area carbon of about 60 m^-g'l, and the
i r o n subsequently p r e c i p i t a t e d by the a d d i t i o n of 4 M KOH A
Teflon bonded electrod
the same procedure a
heat treatment was performed to remove the Teflon e m u l s i f i e r . The
57
Fe/XC-72 w/w r a t i o was i n t h i s case 50% and thus much higher
than that involved i n the heat treated FePc experiments described
e a r l i e r . The electrochemical c e l l f o r the i n s i t u Mossbauer
measurements i s shown i n F i g . 3.
The ex s i t u Mossbauer spectrum f o r the p a r t i a l l y d r i e d
electrode y i e l d e d a doublet with 6 - 0.34 and A - 0.70 M - S " . A 1
decrease i n the value of A was found i n the i n s i t u spectra of the

same electrode immersed i n 4 M KOH at -0.3 V vs Hg/HgO,OH" ( see
Table I I I , and Curve a, F i g . 4 ), i n d i r e c t analogy with the
behavior observed f o r the heat treated FePc. I t i s thus conceiv-
able that t h i s material i s the same as that found a f t e r the ther-
mal decomposition of FePc dispersed on carbon and that reported by
other workers, and that the v a r i a t i o n s i n the value of A are
simply due to differences i n the degree of hydration of the
lattice.
No s i g n i f i c a n t changes i n the spectra were found when the
electrode was p o l a r i z e d sequentially at -0.5 and -0.7 V, by scan-
ning the p o t e n t i a l to these values at 10 mV'S'l. This i s not
s u r p r i s i n g since the c y c l i c voltammetry f o r an i d e n t i c a l , although
non-enriched, iron/carbon mixture, shown i n the Inset, F i g . 4,
indicated no s i g n i f i c a n t faradaic currents over t h i s voltage
region f o r the sweep i n the negative d i r e c t i o n .
In a subsequent measurement at a p o t e n t i a l of -0.9 V, the
resonant absorption of the doublet underwent a marked drop, an
e f f e c t that may be due to an increase i n the s o l u b i l i t y of the
oxide, and thus i n a loss of s o l i d i n the electrode, and/or to a
modification i n the r e c o i l l e s s f r a c t i o n of the s o l i d induced by
the hydration of the l a t t i c e .
The electrode was then swept further negative to -1.1 V, a
p o t e n t i a l more negative than the onset of the faradaic current i n
the voltammogram, y i e l d i n g a f t e r about two hours of measurement, a
strong, c l e a r l y defined doublet (Curve b, F i g . 4 ) , with parameters
i n excellent agreement with those of Fe(0H)2 ( see Tables I I and
I I I ) . The p o t e n t i a l was then stepped to -0.3 V. I n contrast to the

nickel wire reference
nickel wire ^ , „
V - c o l l a p s i b l e cell
plunge
source
detector
a c r y l i c cell
working e l e c t r o d e
F i g . 3. Electrochemical c e l l f o r i n s i t u Mossbauer spectros-

copy measurements. (Reproduced with permission from r e f . 3.
Copyright 1985 Elsevier.)
TABLE i l l
In s i t u Mossbauer parameters f o r iron oxides and oxyhydroxides dispersed on

high area Schawinigan Black carbon electrode
Potential Isomer Shift Quadrupole S p l i t t i n g H ff

e Figure
1
V vs. Hg/HgO.OH" fi/mm-" vs. a-Fe A/mm-s-J- kOe
-0.3 0.33(0.34)* 0.58(0.70) 3A

(initial)
-1.1 1.10 2.89 3B
-0.3 0.37 0.04 406 4A

(step)
-0.3 0.33 0.57 4B

(sweep) 0.28 463
0.56 0.15 437
0.24
-1.2 0.00 330 4C

1.15 2.90
* Values i n parenthesis are those obtained for the same electrode dry.

CC -4.0 -2.0 0.0 2.0 4.0

<
or
CD
CC
<
-8.0 -4.0 0.0 4.0 8.0

VELOCITY ( m m / s )
Fig. 4. In s i t u Mossbauer spectra of a Teflon bonded 50%
5 7
w/w F e enriched hydrated f e r r i c oxide p r e c i p i t a t e d on
Schawinigan black high area carbon electrode i n 4 M KOH at -
0.3 V (Curve a ) , and -1.1 V vs Hg/Hg0,0H" (Curve b ) . Inset:
C y c l i c voltammogram of the same, although non enriched,
material f e r r i c oxide on carbon material i n the form of a t h i n
porous Teflon bonded coating electrode deposited on an
ordinary p y r o l y t i c graphite electrode, i n 4 M KOH. Scan rate:
10 mV/s.

doublet obtained o r i g i n a l l y at t h i s voltage, a magnetically s p l i t

s i x - l i n e spectrum was obtained i n t h i s case ( Curve a, F i g . 5).
The Zeeman e f f e c t and the value of S are consistent with those of
a magnetically ordered f e r r i c oxide species (see Table I I ) . Un-
fortunately, the strength of the i n t e r n a l f i e l d , H f f , cannot be
e
used as a d e f i n i t e i d e n t i f y i n g parameter as the c a l c u l a t e d value

seems s i g n i f i c a n t l y smaller than that expected f o r a bulk i r o n
oxide, a behavior often a t t r i b u t e d to superparamagnetism (vide
supra). Furthermore, the asymmetric broadening of the peaks may be
ascribed to a d i s t r i b u t i o n of e f f e c t i v e magnetic f i e l d s , providing
evidence f o r the presence of an ensemble of small p a r t i c l e s of
varying s i z e s . From a s t a t i s t i c a l viewpoint t h i s i s accounted for
i n the f i t t i n g by a Gaussian d i s t r i b u t i o n of Lorentzians. I t may
be noted that Hassett et al.(7) have reported a s t r i k i n g l y s i m i l a r
s i x - l i n e spectrum for small p a r t i c l e s of magnetite dispersed i n a
lignosulfonate matrix.
In a subsequent measurement the p o t e n t i a l was swept i n the
negative d i r e c t i o n t
spectrum c h a r a c t e r i s t i
rather than stepped p o s i t i v e to -0.3 V. As shown i n curve b, F i g .
5, the r e s u l t i n g spectrum was d i f f e r e n t than e i t h e r that asso-
c i a t e d with the o r i g i n a l material or that obtained a f t e r a voltage
step. The apparent s p l i t t i n g observed f o r two of the absorption
l i n e s located at negative v e l o c i t i e s i s t y p i c a l of magnetite
(Fe304) i n bulk form at room temperature (Table I I ) . This i s due
to the superposition of spectra a r i s i n g from f e r r i c cations i n
tetrahedral s i t e s and ferrous and f e r r i c cations i n octahedral
sites. The broad background centered at 0.24 nun-s"^- may be the
r e s u l t of several e f f e c t s including p a r t i c l e s i z e and s t r u c t u r a l
disorder among magnetite c r y s t a l s which would d i s t o r t the
Mossbauer spectra. The sharp doublet i n the center of the spec-
trum, as judged by the parameter values given i n Table I I I , can be
a t t r i b u t e d to the same hydrated f e r r i c oxyhydroxide observed
originally.
The r e s u l t s of these experiments may be explained i n terms of
differences i n the nature of the p a r t i c l e s generated by the speci-
f i c way i n which the ferrous oxide i s electrochemically oxidized.
In p a r t i c u l a r , a p o t e n t i a l step i s expected to promote the forma-
t i o n of multitude of n u c l e i large enough to e x h i b i t a Zeeman
s p l i t t i n g but on the average smaller than that required to y i e l d a
spectra c h a r a c t e r i s t i c of bulk magnetite. When the oxidation i s
performed by sweeping the p o t e n t i a l , however, a few magnetite
n u c l e i are generated which grow to a s i z e s u f f i c i e n t l y large to
show bulk l i k e behavior.
At the end of these measurements, the electrode was p o l a r i z e d
by sweeping the p o t e n t i a l to -1.2 V, y i e l d i n g a s i x - l i n e spectrum
corresponding to m e t a l l i c i r o n with some c o n t r i b u t i o n from Fe(0H)2
(curve c, F i g . 5). The p o t e n t i a l was then scanned up to -0.3 V
and a spectrum e s s e n t i a l l y i d e n t i c a l to that recorded at -1.2 V
was observed. This r e s u l t c l e a r l y indicates that the i r o n metal
p a r t i c l e s formed by the electrochemical reduction are large enough
f o r the contributions a r i s i n g from the passivation layer to be too
small to be c l e a r l y resolved. A f t e r scanning the p o t e n t i a l several

-10.0 -5.0 0.0 5.0 10.0

VELOCITY (mm/s)
Fig. 5. In s i t u Mossbauer spectra of the same electrode as
i n a) F i g . 4 at -0.3 V, a f t e r a p o t e n t i a l step (Curve a),
and a f t e r a p o t e n t i a l sweep (Curve b), from -1.1 V. Curve c
was obtained at a p o t e n t i a l of -1.2 V.

times between -0.3 and -1.2 V, however, the doublet associated

with the Fe(0H>2 disappeared.
I t may be i n t e r e s t i n g to note that Geronov et a l . ( 9 ) i n much
e a r l i e r studies investigated the s p e c t r a l changes induced by the
charge and discharge of high area iron-carbon polymer bonded
electrodes i n strongly a l k a l i n e media. Despite the f a c t that the
experiments were not conducted under s t r i c t p o t e n t i a l c o n t r o l , as
the c i r c u i t was opened during data a c q u i s i t i o n , these authors made
a number o f i n t e r e s t i n g observations regarding the behavior o f
i r o n electrodes i n 5 M KOH. In p a r t i c u l a r , electrodes i n the f u l l y
charged state (-0.9 V vs. Hg/Hg0,0H") were found t o e x h i b i t fea-
tures associated with m e t a l l i c i r o n and Fe(0H>2, whereas two
a d d i t i o n a l peaks, a t t r i b u t e d to 0-FeOOH, were observed upon d i s -
charge o f these electrodes under galvanostatic conditions (-0.5 V
vs. Hg/Hg0,0H"). S i m i l a r experiments conducted i n the presence of
LiOH i n the same s o l u t i o n lead to a conversion o f the fi-FeOOH i n t o
bulk magnetite (Fe203> as evidenced by the appeareance of the
c h a r a c t e r i s t i c strong f i e l
MIXED NICKEL-IRON OXYHYDROXIDES
The presence of i r o n i n n i c k e l oxyhydroxide electrodes has been

found to reduce considerably the overpotential f o r oxygen evolu-
t i o n i n a l k a l i n e media associated with the otherwise i r o n free
material.(10) An i n s i t u Mossbauer study of a composite Ni/Fe
oxyhydroxide was undertaken i n order to gain i n s i g h t i n t o the
nature o f the species responsible f o r the e l e c t r o c a t a l y t i c
activity.(11) This s p e c i f i c system appeared particularly
i n t e r e s t i n g as i t offered a unique opportunity f o r determining
whether redox reactions i n v o l v i n g the host l a t t i c e s i t e s can a l t e r
the s t r u c t u r a l and/or e l e c t r o n i c c h a r a c t e r i s t i c s of other species
present i n the material.
Thin f i l m s of a composite n i c k e l - i r o n (9:1 Ni/Fe r a t i o ) and
i r o n - f r e e oxyhydroxides were deposited from metal n i t r a t e solu-
tions onto N i f o i l s by e l e c t r o p r e c i p i t a t i o n at constant current
density. A comparison of the c y c l i c voltammetry o f such f i l m s i n
IM KOH a t room temperature (see F i g . 6) shows that the incorpora-
t i o n o f i r o n i n the l a t t i c e s h i f t s the p o t e n t i a l s associated
formally with the Ni00H/Ni(0H)2 redox processes towards negative
p o t e n t i a l s , and decreases considerably the onset p o t e n t i a l f o r
oxygen evolution. The o x i d a t i o n peak, as shown i n the voltammo-
gram, i s much l a r g e r than the reduction counterpart, providing
evidence that w i t h i n the time scale of the c y c l i c voltammetry, a
f r a c t i o n of the n i c k e l s i t e s remains i n the o x i d i z e d state a t
p o t e n t i a l s more negative than the reduction peak.
The i n s i t u Mossbauer experiments were conducted with 90%
5 7 enriched 9:1 Ni/Fe oxyhydroxide f i l m s which were deposited i n
F e
the fashion described above onto a gold on Melinex support(12) i n

a conventional electrochemical c e l l . P r i o r to t h e i r t r a n s f e r i n t o
the i n s i t u Mossbauer c e l l , the electrodes were cycled twice
between 0 and 0.6 V vs. Hg/Hg0,0H" i n 1 M KOH. Two such f i l m s were
used i n the a c t u a l Mossbauer measurements i n order to reduce the
counting time. The i n s i t u Mossbauer c e l l involved i n these
experiments was previously described.

18. SCHERSONETAL. Mossbauer Spectroscopy and Transition Meted Oxides 269
0.0 0.2 0.4 0.6 0.8
POTENTIAL/V vs.Hg/Hg0,0H~
Fig. 6. C y c l i c voltammograms f o r a composite Fe/Ni oxyhyd-
roxide (Fe/Ni 1:9) on a Ni f o i l substrate i n 1 M KOH (solid
curve). Scan rate: 10 mV/s. The dashed curve was obtained f o r
an iron-free Ni oxyhydroxide f i l m under the same experimental
conditions.

The i n s i t u spectrum obtained at 0.5 V vs. Hg/HgO,OH" (oxi-

dized state) i s shown i n curve a, F i g . 7. Following t h i s measure-
ment, the p o t e n t i a l was swept to 0.0 V (reduced s t a t e ) , and a new
i n s i t u spectrum recorded a f t e r the current had dropped to a very
small value (curve b, F i g . 7). E s s e n t i a l l y i d e n t i c a l r e s u l t s were
obtained when the films were examined f i r s t i n the reduced and
then i n the oxidized state.
The spectrum of the oxidized form was successfully f i t t e d
with a s i n g l e t y i e l d i n g an isomer s h i f t of 0.22. For the spectrum
i n the reduced state, a s a t i s f a c t o r y f i t could be achieved with
two s i n g l e t s , which when regarded as the components of an asymmet-
r i c doublet yielded S - 0.34 and A - 0.43. In view of the f a c t
that the c y c l i c voltammetry indicated a slow reduction of the
oxidized state, a s t a t i s t i c a l analysis of the data i n curve b,
F i g . 7 was attempted with a symmetric doublet and a s i n g l e t to
account f o r a possible contribution due to the oxidized phase.
This approach afforded excellent r e s u l t s y i e l d i n g an isomer s h i f t
f o r the s i n g l e t very
curve a, F i g . 7. Furthermore
symmetric doublet were found to be nearly the same as those i n the
f i t i n v o l v i n g the asymmetric doublet. These are l i s t e d i n Table
IV.
The isomer s h i f t of 0.32 associated with the reduced state of
the composite material i s s i m i l a r to that reported f o r various
Fe(III) oxyhydroxides (see Table I I ) and indicates that i r o n i s
present i n the f e r r i c form. The much smaller quadrupole s p l i t t i n g ,
however, provides evidence that the c r y s t a l environment of such
f e r r i c s i t e s i s d i f f e r e n t than that i n common forms of f e r r i c
oxyhydroxides. The lower value of the isomer s h i f t observed upon
oxidation of the composite f i l m indicates a p a r t i a l transfer of
e l e c t r o n density away from the Fe(III) s i t e s , which could r e s u l t
i n d i r e c t l y from the oxidation of the N i ( I I ) s i t e s to y i e l d a
h i g h l y oxidized i r o n species. I t i s i n t e r e s t i n g to note that
recent Raman measurements have provided evidence f o r the presence
of highly symmetrical Ni s i t e s i n oxidized n i c k e l hydroxide
films.(13) Based on such information, i t was postulated that the
f i l m structure could be better represented as Ni02 rather than as
NiOOH. I t seems thus reasonable that the oxidized composite oxy-
hydroxide could contain symmetrical s i t e s which might be occupied
by Fe ions. This would be consistent with the presence of a sing-
l e t , rather than a doublet, i n the spectra shown i n curve a, F i g .
7. Based on these arguments, Corrigan et a l . H concluded that the
composite metal oxyhydroxide may be regarded as a single phase
i n v o l v i n g d i s t i n c t i r o n and n i c k e l s i t e s as opposed to a physical
mixture of Ni(0H)2 and FeOOH p a r t i c l e s . This i s not s u r p r i s i n g
since the composite hydroxide i s a better c a t a l y s t than e i t h e r of
the i n d i v i d u a l hydroxides.
In summary, the r e s u l t s of t h i s i n v e s t i g a t i o n indicated that
the formal oxidation of the n i c k e l s i t e s i n a composite n i c k e l -
i r o n oxyhydroxide modifies the e l e c t r o n i c and s t r u c t u r a l proper-
t i e s of the f e r r i c s i t e s y i e l d i n g a more d-electron d e f i c i e n t i r o n
species. Although i t may be reasonable to suggest that the elec-
t r o c a t a l y t i c a c t i v i t y of t h i s composite oxide f o r oxygen evolution
may be r e l a t e d to the presence of such highly oxidized i r o n s i t e s ,

CO
H
z
-3.0 -2.0 -1.0 0.0 1.0 2.0 3.0 4.0

VELOCITY (mm/s)
-3.0 -2.0 -1.0 0.0 1.0 2.0 3.0 4.0
V E L O C I T Y (mm/s )
F i g . 7. In s i t u Mossbauer spectrum of a composite Fe/Ni oxy-
hydroxide (Fe/Ni 1:9) p o l a r i z e d at 0.5 V (oxidized s t a t e ) ,
curve A, and at 0.0 V vs Hg/HgO,OH" (reduced s t a t e ) , curve B,
i n 1 M KOH.

TABLE IV
In s i t u Mossbauer parameters for an iron-nickel mixed oxyhydroxide

i n 1 M KOH
Potential Isomer S h i f t Quadrupole S p l i t t i n g Width Figure

1 1
V vs. Hg/HgO,OH" 5/mm-s" vs. a-Fe A/mm-s"l r/mm-s"
0.5 0.22 0.97 6A
0.0 0.32(95)t 0.44 0.47 6B

0.19(5) 0.19
f Values i n parentheses represent the f r a c t i o n of the t o t a l resonant

absorption associated with each peak assuming a common r e c o i l l e s s
f r a c t i o n f o r both species.

18. SCHERSON ETAL. Mossbauer Spectroscopy and Transition Metal Oxides 273
a d d i t i o n a l i n s i t u spectroscopic measurements such as EXAFS may be

necessary i n order to support t h i s view.
CONCLUDING REMARKS
Although important information can be derived from an analysis of

i n s i t u data of the type described i n t h i s work, considerable
i n s i g h t into the nature of these electrochemically formed mate-
r i a l s could be obtained by examining t h e i r s p e c t r a l behavior as a
function of temperature and the strength of an e x t e r n a l l y applied
magnetic f i e l d . Unfortunately, the range of temperatures i n which
electrochemical measurements can be c a r r i e d out i s rather narrow.
An approach that could to a c e r t a i n extent circumvent some of
these d i f f i c u l t i e s , however, currently being implemented i n t h i s
laboratory, involves the f a s t quenching of p o l a r i z e d electrodes at
cryogenic temperatures with the electrochemical c e l l placed i n the
c a v i t y of the superconducting magnet Should t h i s quasi i n s i t u
technique prove successfu
acquiring informatio
afforded by present i n s i t u techniques.
ACKNOWLEDGMENTS
F i n a n c i a l support f o r t h i s work was provided by NASA Lewis

Research Center, and by IBM through a Faculty Development Award to
one of the authors (D.A.S.).
LITERATURE CITED
1. For a recent review in t h i s area see: E.J.M. O'Sullivan and

E. J. Calvo Reactions at Metal Oxide Electrodes, i n
Comprehensive Chemical K i n e t i c s , V o l . 27, Chapter 4.
2. a. Vertes, A. and Czako-Nagy, I . Izv. Khim., 1988, 19, 380.
b. Scherson, D. i n Spectroelectrochemistry: Theory and Prac-
t i c e , R. Gale, Ed. Plenum Press, New York, 1988.
3. Scherson, D.; F i e r r o , C.; Tryk, D.; Gupta, S. L.; Yeager, E.
B.; Eldridge, J . ; Hoffman, R. W. J . Electroanal. Chem.
1985 184, 419.
4. Tanaka, A.; F i e r r o , C.; Scherson, D.; Yeager, E. B. J . Phys.
Chem. 1987, 91, 3799.
5. a. Burke, L. D.; Murphy, O. J . J . Electroanal.Chem. 1980
109, 379.
b. Macagno, V. A.; V i l c h e , J . R.; A r v i a , A. J . J . Appl.
Electrochem. 1981, 11, 417.
6. a. Simpson, A. W. J . Appl. Phys. 1962, 33, 1203.
b. Kunding, W.; Bommel, H.; Constabari, G.; Lindquist, R. H.
Phys. Rev. 1966, 142, 327.
c. McNab, T. K.; Fox, R. A.; Boyle, A. J . F. J . Appl. Phys.
1968 39, 5703.
7. Hassett, K. L.; Stecher, L. C.; Hendrickson, D. N. Inorg.
Chem. 1980, 19, 416.
8. F i e r r o , C.; Carbonio, R.; Scherson, D.; Yeager, E. B.

J . Phys. Chem. 1987, 91, 6597.

9. Geronov, Y.; Tomov, T.; Georgiev, S. J . Appl. Electrochem.

1975, 5, 351.
10. a. Cordoba, S.I.; Carbonio, R.; Lopez-Teijelo, M.; Macagno,
V. A. Electrochim. Acta 1986, 31, 1321.
b. Corrigan, D.; J . Electrochem. Soc. 1987, 134, 377.
11. Corrigan, D.; Conell, R. S.; F i e r r o , C.; Scherson, D. J .
Phys. Chem. 1987, 91, 5009.
12. Kordesch, M. E.; Hoffman, R. W. Thin S o l i d Films 1983, 107,
365.
13. Desilvestro, J . ; Corrigan, D.; Weaver, M. J . J . Phys. Chem.
1986, 90, 6408.
R E C E I V E D May 17, 1988

Chapter 19
Use of the Frozen Electrolyte Electrochemical

Technique for the Investigation
of Electrochemical Behavior
Ulrich Stimming
Electrochemistry Laboratory, Department of Chemical Engineering and

Applied Chemistry, Columbia University, New York, NY 10027
The background
results using th
Properties of liquid and frozen HClO4*5.5H O) 2
with respect to e l e c t r i c a l conductivity and

deuteron NMR are discussed. Electrochemical
behavior of the metal-(1iquid or frozen)
electrolyte interface as observed in capacity
measurements and charge transfer reactions is
described. In the case of hydrogen evolution on
copper, s i l v e r and gold, temperature dependent
transfer coefficients are found. For copper and
silver, straight Tafel lines with a slope of 85mV
independent of temperature result in a transfer
coefficient that is proportional to temperature.
Some implications of the results for the under-
standing of electrochemical processes on a
molecular level are discussed. The importance of
UHV work on water-ion coadsorption on metal
surfaces for the understanding of electrochemical
processes on a molecular level is emphasized.
In s t u d y i n g i n t e r f a c i a l e l e c t r o c h e m i c a l b e h a v i o r , e s p e c i a l l y i n
aqueous e l e c t r o l y t e s , a v a r i a t i o n o f t h e temperature i s n o t a
common means o f e x p e r i m e n t a t i o n . When a temperature dependence
i s i n v e s t i g a t e d , the temperature range i s u s u a l l y l i m i t e d t o 0-
80°C. T h i s c o r r e s p o n d s t o a t e m p e r a t u r e v a r i a t i o n on t h e
a b s o l u t e temperature s c a l e of l e s s t h a n 30%, a v a l u e t h a t
compares p o o r l y w i t h o t h e r areas o f i n t e r f a c i a l s t u d i e s such as
s u r f a c e s c i e n c e where t h e temperature can e a s i l y be changed by
s e v e r a l hundred K. T h i s " d e f i c i e n c y " i n e l e c t r o c h e m i c a l s t u d i e s
i s commonly b e l i e v e d t o be compensated by t h e unique a b i l i t y o f
e l e c t r o c h e m i s t r y t o v a r y t h e e l e c t r o d e p o t e n t i a l and thus, i n
case o f a charge t r a n s f e r c o n t r o l l e d r e a c t i o n , t o v a r y the
energy b a r r i e r a t t h e i n t e r f a c e . There e x i s t , however, a number
of examples where t h i s s i t u a t i o n i s o b v i o u s l y n o t so.
0097-6156/88/0378-0275$06.00/0

There a r e c u r r e n t l y a number o f attempts t o overcome the

l i m i t a t i o n s of the l i m i t e d t e m p e r a t u r e a c c e s s i b l e i n aqueous
electrolytes:
(i) To u s e o r g a n i c s o l v e n t s t h a t a l l o w one t o work a t much
lower temperatures (1-5);
( i i ) To u s e an e l e c t r o l y t e w i t h a h i g h b o i l i n g p o i n t s u c h as
c o n c e n t r a t e d p h o s p h o r i c a c i d (6);
( i i i ) To work i n an aqueous e l e c t r o l y t e under h i g h p r e s s u r e i n
order t o extend the a v a i l a b l e temperature range t o h i g h e r
t e m p e r a t u r e s (7 8);
y
(iv) To work i n aqueous e l e c t r o l y t e s below the f r e e z i n g p o i n t

of the e l e c t r o l y t e thus i n c r e a s i n g t h e a v a i l a b l e t e m p e r a t u r e
range t o lower temperatures (9).
The l a t t e r a p p r o a c h t e r m e d FREECE (FRozen E l e c t r o l y t e
E l e c t r o C h E m i s t r y ) h a s been p u r s u e d i n o u r l a b o r a t o r y . I n
a d d i t i o n t o i n c r e a s i n g t h e a v a i l a b l e t e m p e r a t u r e down t o
a p p r o x . 120K w h i c h a l lows one t o v a r y t h e t e m p e r a t u r e by more
t h a n a f a c t o r o f two
these t e c h n i q u e :
- One can study s p e c i f i c low temperature e f f e c t s , such as
p o s s i b l e quantum e f f e c t s ;
- One can study the i n f l u e n c e o f s o l i d i f i c a t i o n , i . e . the
development o f a l o n g range o r d e r o r a p o s s i b l e g l a s s f o r m a t i o n
of the e l e c t r o l y t e on e l e c t r o c h e m i c a l b e h a v i o r ;
- One i s i n a b e t t e r p o s i t i o n t o compare r e s u l t s i n
electrochemistry with r e s u l t s i n surface science i n v o l v i n g
water ad- o r c o a d s o r p t i o n on metal s u r f a c e s which a r e u s u a l l y
i n v e s t i g a t e d i n the temperature range 100-250K as done by Sass
and co-workers (10,11), Wagner (12) and Madey (13).
In t h i s paper, some o f the p o s s i b i l i t i e s a s s o c i a t e d w i t h
t h e FREECE t e c h n i q u e w i l l be d e s c r i b e d . R e s u l t s r e f e r r i n g t o
the charge d i s t r i b u t i o n a t the e l e c t r o d e - e l e c t r o l y t e i n t e r f a c e
and t o c h a r g e ^ t r a n s f e r r e a c t i o n s w i l l be p r e s e n t e d and b r i e f l y
discussed.
Experimental
Design of E x p e r i m e n t a l Set-up. In performing electrochemical

m e a s u r e m e n t s a t c r y o g e n i c t e m p e r a t u r e s , two different
a p p r o a c h e s c a n be c h o s e n : E i t h e r t o a d a p t an e l e c t r o c h e m i c a l
c e l l t o a c o m m e r c i a l l y a v a i l a b l e c r y o s t a t o r t o adapt a c o o l i n g
system t o an o p t i m i z e d e l e c t r o c h e m i c a l c e l l .
W h i l e i t i s c o n v e n i e n t t o use a s t a n d a r d c r y o s t a t , the
c e l l has t o be f i t t e d i n t h e s a m p l e s p a c e o f t h e c r y o s t a t and
the leads t o the c e l l are u s u a l l y f a i r l y long - a s p e c i f i c
draw-back f o r impedance measurements. Another d i s a d v a n t a g e i s
the l o n g cool-down times o f these systems which may not a l l o w
one t o r a p i d l y f r e e z e the e l e c t r o l y t e . However, f o r experiments
not r e q u i r i n g s o p h i s t i c a t e d e l e c t r o c h e m i c a l e x p e r i m e n t a t i o n
t h i s may be the most c o n v e n i e n t e x p e r i m e n t a l set-up.
M o s t o f t h e work i n o u r l a b o r a t o r y h a s b e e n done u s i n g
s p e c i a l l y designed c e l l s that are incorporated i n a rather
s i m p l e c o o l i n g d e v i c e . In working w i t h p o l y c r y s t a l l i n e metal
f o i l s , a c e l l d e s i g n as p i c t u r e d i n F i g . l has been used. M e t a l

SUMMING FREECE Technique and Electrochemical Behavior
F i g u r e 1. E l e c t r o c h e m i c a l c e l l f o r cryogenic measurements.

f o i l s f o r w o r k i n g and c o u n t e r e l e c t r o d e a r e s e p a r a t e d by
a p p r o x . 1mm, w i t h a r e f e r e n c e e l e c t r o d e made o f w i r e c l o s e t o
t h e gap between t h e two f o i l s . The r e f e r e n c e e l e c t r o d e c a n be
e i t h e r a h y d r o g e n l o a d e d Pd w i r e o r , i n c a s e o f a r e d o x
e l e c t r o l y t e , a p l a t i n u m w i r e o r any o t h e r m e t a l that
e s t a b l i s h e s the e q u i l i b r i u m p o t e n t i a l of the i n v e s t i g a t e d
r e a c t i o n . For the l a t t e r s i t u a t i o n , o v e r p o t e n t i a l s a t a l l
t e m p e r a t u r e s a r e d i r e c t l y g i v e n by t h e d i f f e r e n c e between
working and r e f e r e n c e e l e c t r o d e . The c e l l f u r t h e r c o n t a i n s two
p l a t i n u m r e s i s t a n c e elements s e a l e d i n g l a s s f o r the
temperature c o n t r o l and an independent temperature measurement.
3
The e l e c t r o l y t e v o l u m e i s a p p r o x . 1cm . A heating wire i s
wrapped around the c e l l which i s connected t o the temperature
c o n t r o l l e r . The c e l l i s p l a c e d i n an o u t e r j a c k e t w h i c h i s
hooked up t o a vacuum r e g u l a t i o n system and, i n i t s lower p a r t ,
i s c o n n e c t e d w i t h a l i q u i d n i t r o g e n r e s e r v o i r . By r e g u l a t i n g
t h e vacuum, a v a r i a b l e s t r e a m o f e v a p o r a t i n g n i t r o g e n p a s s e s
the c e l l and c o o l s i t
constant temperature
a c c u r a c y o f t h e t e m p e r a t u r e r e g u l a t i o n i s a b o u t J+1K and t h e
c e l l has been operated down t o 100K. C e l l s made e i t h e r o f g l a s s
or o f K e l - F have been used.
In o r d e r t o i n v e s t i g a t e s p e c i f i c c r y s t a l f a c e s , a c e l l
d e s i g n has been chosen t h a t i s based on the i d e a o f the hanging
drop t e c h n i q u e o f t e n used i n s i n g l e c r y s t a l s t u d i e s . A
s c h e m a t i c p i c t u r e i s shown i n F i g . 2 . The c e n t r a l p a r t i s a
g l a s s b l o c k t h a t extends i n t o the lower p a r t where c o o l i n g i s
p r o v i d e d by e v a p o r a t i n g l i q u i d n i t r o g e n , w h i l e h e a t i n g w i r e s
connected t o the temperature c o n t r o l l e r and wrapped around the
glass block e s t a b l i s h a constant temperature i n a comparable
way as d e s c r i b e d above. On top o f the g l a s s b l o c k , a g o l d d i s k
which forms the c o u n t e r e l e c t r o d e s i t s i n a d e p r e s s i o n . A drop
3
of e l e c t r o l y t e o f 50-100 mm can be s u p p l i e d onto the Au d i s k .
A c r y s t a l rod w i t h the d e s i r e d c r y s t a l f a c e p o i n t e d down can be
lowered by means o f a micrometer t o c o n t a c t the e l e c t r o l y t e . A
Pd/H w i r e as r e f e r e n c e e l e c t r o d e can a l s o be p o s i t i o n e d w i t h a
micrometer. The use o f micrometers a l l o w s f o r an o p t i m i z a t i o n
of the geometry which i s c r u c i a l a t lower temperatures t o keep
the c e l l as low-ohmic as p o s s i b l e . A g l a s s s e a l e d thermocouple
measures the a c t u a l temperature o f the e l e c t r o l y t e . Because o f
the h i g h e r t h e r m a l mass o f t h i s c e l l , s p e c i a l i n s u l a t i o n i s
n e c e s s a r y i n o r d e r t o r e a c h temperatures below 170K.
E1ectrochemica1 Instrumentation. For a l l e l e c t r o c h e m i c a l

experiments, r e g u l a r i n s t r u m e n t a t i o n common i n e l e c t r o c h e m i c a l
r e s e a r c h c a n be u s e d . One has t o c o n s i d e r , however, t h a t t h e
e l e c t r i c a l c h a r a c t e r i s t i c s o f the c e l l change by many o r d e r s o f
magnitude by changing the temperature from room temperature t o
c r y o g e n i c c o n d i t i o n s . The e l e c t r o l y t e t h a t has been w i d e l y used
i n our l a b o r a t o r y i s aqueous p e r c h l o r i c a c i d o f the c o m p o s i t i o n
HC104*5.5H20 which e x h i b i t s a r e l a t i v e l y h i g h c o n d u c t i v i t y even
a low t e m p e r a t u r e s . More d e t a i l s r e g a r d i n g t h i s e l e c t r o l y t e
w i l l be g i v e n below.

19. S U M M I N G FREECE Technique and Electrochemical Behavior 279
F i g u r e 2. E l e c t r o c h e m i c a l c e l l f o r measurements w i t h single
c r y s t a l s a t c r y o g e n i c measurements.

For c a p a c i t y measurements, s e v e r a l t e c h n i q u e s are

a p p l i c a b l e . Impedance s p e c t r o s c o p y , l o c k - i n technique o r p u l s e
measurements can be used, and the advantages and d i s a d v a n t a g e s
of the v a r i o u s t e c h n i q u e s a r e the same as f o r room temperature
measurements. An important f a c t o r i s the temperature dependent
t i m e c o n s t a n t o f t h e s y s t e m w h i c h s h i f t s e.g. t h e c a p a c i t i v e
b r a n c h i n an i m p e d a n c e - f r e q u e n c y diagram w i t h d e c r e a s i n g
temperature t o lower f r e q u e n c i e s . Comparable changes w i t h
temperature a r e a l s o o b s e r v e d i n the p o t e n t i a l t r a n s i e n t s due
to galvanostatic pulses.
For the i n v e s t i g a t i o n o f charge t r a n f e r p r o c e s s e s , one has
t h e w h o l e a r s e n a l o f t e c h n i q u e s c o m m o n l y u s e d a t one's
d i s p o s a l . As l o n g as t r a n s p o r t l i m i t a t i o n s do not p l a y a r o l e ,
c y c l i c v o l t a m m e t r y o r p o t e n t i o d y n a m i c sweeps c a n be u s e d .
O t h e r w i s e , impedance t e c h n i q u e s o r p u l s e measurements c a n be
e m p l o y e d . F o r a mass t r a n s p o r t l i m i t a t i o n o f t h e r e a c t i n g
s p e c i e s from the e l e c t r o l y t e , t h e d i f f u s i o n i s u s u a l l y not
u n i f o r m and does not f o l l o
a n a l y s i s of c u r r e n t
r e s u l t s r e f e r r i n g t o c h a r g e d i s t r i b u t i o n and c h a r g e t r a n s f e r
r e a c t i o n s a t the e l e c t r o d e - e l e c t r o l y t e i n t e r f a c e w i l l be
discussed later.
Charge d i s t r i b u t i o n
The charge d i s t r i b u t i o n a t metal e l e c t r o d e - e l e c t r o l y t e i n t e r -

f a c e s f o r l i q u i d and f r o z e n e l e c t r o l y t e s has been i n v e s t i g a t e d
through c a p a c i t y measurements u s i n g the l o c k - i n technique and
impedance spectroscopy. B e f o r e we d i s c u s s some o f the important
results, l e t us b r i e f l y c o n s i d e r some p r o p e r t i e s o f t h e
e l e c t r o l y t e i n i t s l i q u i d and f r o z e n s t a t e .
HC104*5.5H20 i s an aqueous p e r c h l o r i c a c i d o f s t o i c h i o -
m e t r i c c o m p o s i t i o n t h a t r e p r e s e n t s the h i g h e s t h y d r a t e o f the
p e r c h l o r i c a c i d . I t c r y s t a l l i z e s i n a c l a t h r a t e type of
s t r u c t u r e a t 228K. The c r y s t a 1 l o g r a p h i c p a r a m e t e r s have
r e c e n t l y b e e n d e t e r m i n e d u s i n g X - r a y d i f f r a c t i o n (14,15). In
c l a t h r a t e s one u s u a l l y has a h o s t l a t t i c e w i t h d i f f e r e n t types
of v o i d s . In case o f HC10 *5.5H 0 the h o s t l a t t i c e i s formed by
4 2
H2O w i t h C I O 4 and H +
a s g u e s t s . C o n d u c t i v i t y measurements
i n d i c a t e a h i g h c o n d u c t i v i t y i n t h e l i q u i d s t a t e , b u t upon
f r e e z i n g a t 228K no abrupt, j u s t a steady, decrease i s observed
w i t h d e c r e a s i n g temperature; the m o b i l e s p e c i e s a r e presumably
the protons. In o r d e r t o g a i n more i n s i g h t i n t o the c o n d u c t i o n
p r o c e s s , NMR s t u d i e s were p e r f o r m e d . The measurements were
c a r r i e d out i n d e u t e r a t e d p e r c h l o r i c a c i d s o l u t i o n s s i n c e t h e r e
a r e some a d v a n t a g e s o f d e u t e r o n v e r s u s p r o t o n NMR. B e l o w t h e
f r e e z i n g point, a l i n e broadening i n c r e a s i n g with decreasing
temperature can be observed. The l i n e broadening can be r e l a t e d
to the frequency of the d i f f u s i o n - r e o r i e n t a t i o n of the
d e u t e r o n s . F i g . 3 shows an A r r h e n i u s p l o t o f t h e c o n d u c t i v i t y ,
p l o t t e d as the i n v e r s e r e s i s t a n c e , and o f the i n v e r s e ha I f width
o f t h e l i n e b r o a d e n i n g (Huang, T.-H.; Ang, T.T.; F r e s e , U.;
S t i m m i n g , U. s u b m i t t e d f o r p u b l i c a t i o n ) . I t i s i n t e r e s t i n g t o
n o t e t h a t b e l o w 228K, t h e f r e e z i n g p o i n t o f t h e e l e c t r o l y t e ,

SUMMING FREECE Technique and Electrochemical Behavior
T [K]
300 260 220 200 180 160 K0
• • ' » i i
-2
H C 1 0 -5.5 H 0
A 2
.02 eV
\\^29eV
-6
cs melting point
\
228 K -8
^ -A
on
G
-6
Yv -10
-8
-10
-i— I l —
3.0 4.0 5.0 6.0 7.0
•I0 T '
3 1
[K ]_ l
F i g u r e 3. A r r h e n i u s p l o t o f e l e c t r i c a l c o n d u c t i v i t y o f
2
HC10 *5.5H 0 and o f the h a l f w i d t h o f the H-NMR s i g n a l .
4 2

t h e s l o p e s f o r t h e l i n e b r o a d e n i n g and t h e c o n d u c t i v i t y a r e
v e r y s i m i l a r , c o r r e s p o n d i n g t o an a c t i v a t i o n energy of approx.
0.3eV. A t 170K, a n o t h e r b r e a k i n t h e s l o p e i s o b s e r v e d . T h i s
t e m p e r a t u r e has b e e n i d e n t i f i e d as a r e v e r s i b l e h i g h e r o r d e r
p h a s e t r a n s f o r m a t i o n (14,15). W h i l e t h e a c t i v a t i o n e n e r g y o f
t h e c o n d u c t i v i t y i n c r e a s e s t o a p p r o x . 0.38eV, t h e d e c r e a s e i n
frequency i n the NMR s i g n a l i s much s t e e p e r w i t h approx. 0.7eV.
I t has t o be m e n t i o n e d , however, t h a t t h e s h a p e o f t h e NMR
s i g n a l a t v e r y low temperatures suggests t h a t the deuterons are
3
s t i l l m o b i l e w i t h a frequency o f about 10 Hz.
C a p a c i t y d a t a has b e e n o b t a i n e d f o r g o l d , s i l v e r and
c o p p e r . As m e n t i o n e d a b o v e , t h e main e f f e c t o f t e m p e r a t u r e on
t h e impedance i s a s h i f t o f t h e s p e c t r u m t o l o w e r f r e q u e n c i e s
w i t h d e c r e a s i n g temperatures. T h i s i s i l l u s t r a t e d i n Fig.4 f o r
a p o l y c r y s t a l l i n e g o l d e l e c t r o d e i n HC104*5.5H 0 ( T e l l e f s e n ,
2
K.; S t i m m i n g , U. u n p u b l i s h e d r e s u l t s ) . Comparing the two

impedance s p e c t r a , t h e one measured a t 278K i n t h e l i q u i d
e l e c t r o l y t e and t h e
e l e c t r o l y t e , the e f f e c
shape of the s p e c t r a i s e s s e n t i a l l y not changed which i n d i c a t e s
t h a t the e q u i v a l e n t c i r c u i t u n d e r l y i n g t h i s interfacial
b e h a v i o r i s p r e s e r v e d i n the f r o z e n e l e c t r o l y t e . T h i s b e h a v i o r
i s a l s o r e f l e c t e d i n the p o t e n t i a l dependence o f the c a p a c i t y
o f p o l y c r y s t a l l i n e g o l d (16). The c h a r a c t e r i s t i c p e a k s i n
c a p a c i t y - p o t e n t i a l c u r v e s o b s e r v e d i n the l i q u i d e l e c t r o l y t e
a r e p r e s e r v e d i n t h e f r o z e n e l e c t r o l y t e . The c u r v e s i n F i g . 5
show a s t r u c t u r e t h a t i s s i m i l a r t o what i s o b s e r v e d a t room
temperature i n the l i q u i d e l e c t r o l y t e . W i t h decreasing
t e m p e r a t u r e , t h e s e f e a t u r e s become l e s s p r o n o u n c e d , and at
t e m p e r a t u r e s b e l o w 150K, t h e c u r v e s become r a t h e r flat.
S i m i l i a r r e s u l t s were a l s o o b t a i n e d by I w a s i t a e t a l . (17) f o r
p o l y c r y s t a l l i n e g o l d and by Hamelin e t a l . (18) f o r g o l d [2103.
I n a s i m i l a r way, c a p a c i t y measurements f o r p o l y -
c r y s t a l l i n e s i l v e r and copper i n d i c a t e t h a t " e l e c t r o c h e m i s t r y "
s t a y s i n t a c t below the f r e e z i n g p o i n t o f the e l e c t r o l y t e . When
t h e minima o f c a p a c i t y - p o t e n t i a l c u r v e s a r e p l o t t e d as a
f u n c t i o n o f temperature, as shown i n Fig.6, a s t r a i g h t l i n e i s
o b t a i n e d i n t h e t e m p e r a t u r e r a n g e 200-300K (19). The f r e e z i n g
o f t h e e l e c t r o l y t e d o e s n o t seem t o h a v e any m a j o r e f f e c t on
t h e e l e c t r o d e c a p a c i t y o f s i l v e r and c o p p e r . As c a n be s e e n
from Fig.6, the c a p a c i t y e x h i b i t s a p o s i t i v e temperature
c o e f f i c i e n t , dC/dT; t h i s i s a l s o o b s e r v e d f o r g o l d . T h i s i s i n
c o n t r a s t t o t h e e a r l y r e s u l t s o f Grahame on m e r c u r y (20) and
a l s o on g o l d by Schmid and Hacker man (21). Hamelin e t a l . (22),
h o w e v e r , o b s e r v e d f o r Au £ 2 1 0 } a p o s i t i v e temperature
c o e f f i c i e n t a t p o t e n t i a l s p o s i t i v e o f t h e p z c and a n e g a t i v e
temperature c o e f f i c i e n t a t p o t e n t i a l s n e g a t i v e of the pzc i n
the temperature range 274 t o 323K f o r d i l u t e H C I O 4 . I t would be
i n t e r e s t i n g t o s e e i f e.g. t h e Grahame r e s u l t s , where t h e
c a p a c i t y increases with decreasing temperature, are a l s o
r e f l e c t e d i n capacity behavior of mercury i n the f r o z e n
e l e c t r o l y t e . O v e r a l l , the c a p a c i t y b e h a v i o r as found f o r g o l d ,
s i l v e r and c o p p e r s u g g e s t s t h e p o s s i b i l i t y t o use t h e FREECE
technique t o study e l e c t r o c h e m i c a l b e h a v i o r i n a wide range o f

19. STIMMING FREECE Technique and Electrochemical Behavior 283

Au/HCl0 -5.5H 0
4 2
60-
*..212K 1 H z
40-
C ••.182 K
2
[pF/cm ]
20-
151 K •*
—I 1—
0.5 1.0 1.5
Figure 5. Capacity-potential curves of gold at various

temperatures i n the frozen e l e c t r o l y t e (taken from ref.16,
with permission of the Electrochemical Society,
Pennington, N J ) .
temperature [K]
Figure 6. Temperature dependence of the electrode capacity
of copper and s i l v e r (taken from ref. 16 , with permission
of the Electrochemical Society, Pennington, NJ).

temperatures by p a s s i n g the f r e e z i n g p o i n t o f the e l e c t r o l y t e .

I t i s tempting t o c o n s i d e r , on the b a s i s o f these c a p a c i t y
measurements, t h e c o n s e q u e n c e s f o r an u n d e r s t a n d i n g o f t h e
e l e c t r o c h e m i c a l d o u b l e l a y e r . A l t h o u g h i t i s much t o o e a r l y ,
w i t h r e s p e c t t o the a v a i l a b l e data, t o j u s t i f y a q u a l i f i e d
a t t e m p t , a few a s p e c t s seem t o be c l e a r enough t o a l l o w f o r
some q u a l i t a t i v e remarks. The r e s u l t s i n d i c a t e t h a t the d o u b l e
layer is s t i l l i n t a c t i n the f r o z e n e l e c t r o l y t e . The
s o l i d i f i c a t i o n of the e l e c t r o l y t e with i t s development of a
l o n g range o r d e r o b v i o u s l y a f f e c t s the i n t e r f a c i a l r e g i o n o n l y
i n a minor way. One reason c e r t a i n l y i s t h a t the e l e c t r o l y t e i s
h i g h l y concentrated; HC104*5.5H 0 corresponds t o an approx. 7M
2
HCIO4 i n
water. T h i s l i m i t s the p o t e n t i a l drop to the v e r y
i n t e r f a c e , e x c l u d i n g d i f f u s e l a y e r e f f e c t s , i . e . t h e r e i s no
extension of the p o t e n t i a l drop i n t o the b u l k of the
e l e c t r o l y t e . The c h a r g i n g o f the i n t e r f a c e as a f u n c t i o n o f the
e l e c t r o d e p o t e n t i a l can s t i l l be a c h i e v e d s i n c e as found from
t h e NMR measurements
e l e c t r o l y t e . Reversin
i s the c a p a c i t y b e h a v i o r i n the l i q u i d e l e c t r o l y t e so s i m i l a r
t o t h a t i n the f r o z e n e l e c t r o l y t e . In the f r o z e n s t a t e , the
e l e c t r o l y t e w i l l , i d e a l l y , terminate a t the e l e c t r o d e i n some
k i n d of s t r u c t u r e d way, a t l e a s t i n the two dimensions p a r a l l e l
t o t h e m e t a l s u r f a c e . N o r m a l t o t h e s u r f a c e some d i f f e r e n c e s
may e x i s t , e s p e c i a l l y a t the l o c a t i o n s of charge and c o u n t e r -
c h a r g e where a h i g h e l e c t r i c f i e l d e x i s t s . The l o c a t i o n s o f
charge depends on the p r o t o n m o b i l i t y not o n l y normal but a l s o
p a r a l l e l t o the s u r f a c e . Any a n i s o t r o p y e f f e c t s of the proton
m o b i l i t y a r e n o t known f o r HC104*5.5H20 and t h e crystal
s t r u c t u r e d o e s n o t s u g g e s t any (14,15). T h i s a r r a n g e m e n t c a n
s t a y e s s e n t i a l l y p r e s e r v e d upon m e l t i n g , e s p e c i a l l y c l o s e t o
t h e s u r f a c e where t h e f i e l d may s t a b i l i z e advantageous
o r i e n t a t i o n s o f t h e w a t e r w i t h t h e p e r c h l o r a t e i o n s and t h e
protons. In a d d i t i o n , i t i s w e l l known t h a t aqueous s o l u t i o n s
and pure water form l a r g e agglomerates i n the l i q u i d s t a t e t h a t
a l l o w e.g. X - r a y d i f f r a c t i o n t o be o b s e r v e d . In summary,
r e g a r d i n g the m o l e c u l a r processes a t the e l e c t r o d e - e l e c t r o l y t e
i n t e r f a c e , t h e y do n o t seem t o be s t r o n g l y a f f e c t e d by t h e
phase change from l i q u i d t o s o l i d o f the b u l k e l e c t r o l y t e .
Charge t r a n s f e r r e a c t i o n s
C h a r g e t r a n s f e r r e a c t i o n s r e p r e s e n t an i m p o r t a n t c a t e g o r y o f
e l e c t r o c h e m i c a l b e h a v i o r . As a l r e a d y p o i n t e d o u t a b o v e , an
a p p r o p r i a t e i n v e s t i g a t i o n of k i n e t i c parameters of e l e c t r o -
c h e m i c a l r e a c t i o n s i n aqueous e l e c t r o l y t e s s u f f e r s f r o m t h e
s m a l l temperature range e x p e r i m e n t a l l y a c c e s s i b l e . In the
f o l l o w i n g , some p r e l i m i n a r y r e s u l t s u s i n g the FREECE technique
2 + 3 +
are presented f o r the F e / F e redox r e a c t i o n and f o r hydrogen
e v o l u t i o n a t v a r i o u s metal e l e c t r o d e s .
2 + 3 +
The r e d o x r e a c t i o n F e / F e was t h e f i r s t r e a c t i o n f o r
w h i c h i t c o u l d be d e m o n s t r a t e d t h a t t h e i n v e s t i g a t i o n o f
e l e c t r o c h e m i c a l b e h a v i o r i n f r o z e n aqueous e l e c t r o l y t e s i s
p o s s i b l e ( 9 ) . The e l e c t r o l y t e was IM H C I O 4 w h i c h has the

d i s a d v a n t a g e t h a t b e l o w 273K one has a t e m p e r a t u r e d e p e n d e n t

c o m p o s i t i o n o f t h e l i q u i d e l e c t r o l y t e i n a d d i t i o n t o i c e and
e v e n t u a l l y a s o l i d mixture o f i c e and t h e e u t e c t i c o f i c e and
HC10 *5.5H 0. T h i s r a t h e r c o m p l i c a t e d s i t u a t i o n l e d t o t h e
4 2
c h o i c e o f HC104*5.5H 0 a s e l e c t r o l y t e w h i c h h a s a d e f i n e d
2
f r e e z i n g p o i n t a t 228K and i s a l w a y s a s i n g l e p h a s e e x c e p t a t
the f r e e z i n g p o i n t i t s e l f .
2 + 3 +
The exchange c u r r e n t d e n s i t y o f t h e F e / F e reaction i n
HC 1 0 4 * 5 . 5 H 0 has been i n v e s t i g a t e d u s i n g g a l v a n o s t a t i c p u l s e s
2
i n t h e p o t e n t i a l regime o f the l i n e a r c u r r e n t - p o t e n t i a l
r e l a t i o n s h i p . C u r r e n t p u l s e s h a v e t o be c h o s e n s u c h t h a t a
steady s t a t e p o t e n t i a l i s reached. T h i s procedure a l l o w s f o r an
e a s y s e p a r a t i o n and a l s o d e t e r m i n a t i o n o f t h e ohmic d r o p and
t h e c h a r g e t r a n s f e r o v e r p o t e n t i a l . R e s u l t s were o b t a i n e d f o r
v a r i o u s c o n c e n t r a t i o n s and a r e p l o t t e d i n an A r r h e n i u s p l o t i n
F i g . 7 ( D i n a n , T.; S t i m m i n g , U. u n p u b l i s h e d r e s u l t s ) . A s
expected, s t r a i g h t l i n e s a r e found i n the l i q u i d e l e c t r o l y t e
w i t h a s l o p e t h a t correspond
t h e common v a l u e f o
dependence a l s o r e p r e s e n t s , as expected, a r e a c t i o n o r d e r o f
one. Upon f r e e z i n g , an i n c r e a s e o f t h e e x c h a n g e c u r r e n t i s
o b s e r v e d and t h e t e m p e r a t u r e h a s t o be s e v e r a l t e n d e g r e e s
below t h e f r e e z i n g p o i n t i n o r d e r f o r t h e c u r r e n t t o come back
t o the same v a l u e as a t t h e f r e e z i n g p o i n t . The c u r r e n t f o r the
two h i g h e s t c o n c e n t r a t i o n s , 0.03M a n d 0.01M, becomes a l m o s t
i d e n t i c a l upon f r e e z i n g . A t lower temperatures, t h e d i f f e r e n c e s
between t h e v a l u e s f o r 0.01M and 0.003M a l s o seem t o d i m i n i s h
t o e v e n t u a l l y become o f c o m p a r a b l e v a l u e . The d i f f e r e n c e
between t h e c u r v e s f o r 0.001M and 0.003M, however, stays
c o n s t a n t and i s a p p r o x . a f a c t o r o f t h r e e , a s e x p e c t e d f o r a
r e c t i o n o r d e r o f one. The reason f o r t h e n o n - p r o p o r t i o n a l i t y o f
t h e c u r r e n t a t h i g h e r c o n c e n t r a t i o n s i s p r o b a b l y due t o a
l i m i t e d s o l u b i l i t y o f t h e redox system i n the e l e c t r o l y t e .
P r e c i p i t a t i o n , o r b e t t e r , c r y s t a l l i z a t i o n , as opposed t o a
s o l i d s o l u t i o n o f the redox system i n t h e e l e c t r o l y t e , may l e a d
+
t o a r e d u c t i o n o f t h e e f f e c t i v e l y a v a i l a b l e number o f F e * and
3 +
Fe s i t e s a t t h e i n t e r f a c e . I f t h e c o n c e n t r a t i o n i s low
enough, t h e d i s t r i b u t i o n i s o b v i o u s l y a s random a s one w o u l d
expect i t t o be s i m i l a r l y t o the l i q u i d . From t h e s l o p e o f the
c u r v e s f o r lower c o n c e n t r a t i o n s an a c t i v a t i o n energy o f 0.35eV
can be c a l c u l a t e d s l i g h t l y h i g h e r than t h e v a l u e i n t h e l i q u i d
e l e c t r o l y t e . This, together with the current increase a t the
freezing point, r e s u l t s i n a considerably higher pre-
e x p o n e n t i a l f a c t o r . I t w i l l be shown l a t e r t h a t t h e c u r r e n t
i n c r e a s e upon f r e e z i n g o f the e l e c t r o l y t e seems t o be a r a t h e r
t y p i c a l phenomenon and i s a l s o o b s e r v e d f o r t h e h y d r o g e n
e v o l u t i o n r e a c t i o n a t v a r i o u s metal e l e c t r o d e s . Recently,
2 + 3 +
Matsunaga e t a l . (23) have i n v e s t i g a t e d t h e F e / F e reaction
i n IM HCIO4 a n
HC 1 0 4 * 5 . 5 H 0 i n t h e l i q u i d and f r o z e n s t a t e
d i n
2
o f t h e e l e c t r o l y t e . W h i l e t h e i r r e s u l t s i n IM H C I O 4 a r e v e r y
s i m i l a r t o o u r e a r l i e r r e s u l t s (9), t h e A r r h e n i u s p l o t f o r
HC104*5.5H 0 a s e l e c t r o l y t e d i f f e r s c o n s i d e r a b l y f r o m t h e
2
r e s u l t s shown i n Fig.7. In p a r t i c u l a r , Matsunaga e t a l . o b s e r v e

a d r o p i n t h e e x c h a n g e c u r r e n t d e n s i t y by more t h a n t h r e e

o r d e r s o f m a g n i t u d e b e t w e e n 180 and 175K. I t i s c u r r e n t l y n o t

c l e a r what t h e reasons f o r t h e s e d i f f e r e n c e s a r e .
Hydrogen e v o l u t i o n , t h e o t h e r r e a c t i o n s t u d i e d , i s a
c l a s s i c a l r e a c t i o n f o r e l e c t r o c h e m i c a l k i n e t i c s t u d i e s . I t was
this reaction that l e d Tafel (24) t o f o r m u l a t e h i s s e m i -
l o g a r i t h m i c r e l a t i o n b e t w e e n p o t e n t i a l and c u r r e n t w h i c h i s
named f o r him and t h a t l a t e r r e s u l t e d i n t h e d e r i v a t i o n o f t h e
e q u a t i o n t h a t today i s c a l l e d " B u t l e r - V o l m e r - e q u a t i o n " (25,26).
The i n f l u e n c e o f t h e e l e c t r o d e p o t e n t i a l i s c o n s i d e r e d t o
modify t h e a c t i v a t i o n b a r r i e r f o r t h e charge t r a n s f e r s t e p o f
the r e a c t i o n a t t h e i n t e r f a c e . T h i s r e s u l t s i n an e x p o n e n t i a l
dependence o f t h e r e a c t i o n r a t e on t h e e l e c t r o d e p o t e n t i a l , t h e
e x t e n t o f which i s g i v e n by t h e t r a n s f e r c o e f f i c i e n t , a .
The f i r s t s y s t e m s t u d i e d u s i n g FREECE was t h e h y d r o g e n
e v o l u t i o n on p l a t i n u m (27). The r e a c t i o n proceeds s i m i l a r l y i n
l i q u i d and f r o z e n H C 1 0 4 * 5 . 5 H 2 O . I t exhibits a potential
d e p e n d e n c e o f t h e c u r r e n t w i t h ot=2 w h i c h i s p r a c t i c a l l y t h e
same i n t h e l i q u i d an
dependence i n d i c a t e s
s t e p b u t t h e r e c o m b i n a t i o n o f h y d r o g e n atoms a n d / o r t h e
d i f f u s i o n o f m o l e c u l a r hydrogen from t h e s u r f a c e i s r a t e
d e t e r m i n i n g (28).
In c o n t r a s t t o p l a t i n u m , t h e hydrogen e v o l u t i o n on copper,
on s i l v e r and on g o l d show a d i f f e r e n t b e h a v i o r . S i m i l a r l y t o
p l a t i n u m , slow potentidynamic sweeps have been used t o measure
the c u r r e n t - p o t e n t i a l c u r v e s (29). W h i l e t h e b e h a v i o r o f g o l d
shows p o t e n t i a l and temperature dependent changes o f t h e s l o p e ,
s i l v e r and c o p p e r e x h i b i t s t r a i g h t l i n e s i n a T a f e l p l o t ,
h o w e v e r , w i t h no o r o n l y l i t t l e c h a n g e o f t h e s l o p e w i t h
temperature. T h i s i s i l l u s t r a t e d i n Fig.8 f o r s i l v e r i n t h e
t e m p e r a t u r e r a n g e o f 140-300K. As c a n be s e e n f r o m F i g . 8 , t h e
l i n e s a r e s t r a i g h t o v e r a b o u t t h r e e o r d e r o f m a g n i t u d e and
a l m o s t i d e a l l y p a r a l l e l i n t h e range T=160-300K w i t h a T a f e l
s l o p e o f b=85mV. The r e s u l t s f o r c o p p e r a r e v e r y s i m i l a r .
C a l c u l a t i n g t h e t r a n s f e r c o e f f i c i e n t a c c o r d i n g t o b=RT/anF
c o n s e q u e n t l y r e s u l t s i n a temperature dependent t r a n s f e r
c o e f f i c i e n t a s shown i n F i g . 9 f o r s i l v e r a n d c o p p e r ( r e f . 1 9 ) .
I n t h e t e m p e r a t u r e r a n g e f r o m 160 t o 300K a l i n e a r d e p e n d e n c e
of a v s . T i s found w i t h a n e g l i b l e i n t e r c e p t a t T=0K.
T h i s r e s u l t i s q u i t e i n c o n t r a s t t o t h e common e x p e c t a t i o n
t h a t t h e e l e c t r o d e p o t e n t i a l changes t h e a c t i v a t i o n b a r r i e r a t
the i n t e r f a c e which would r e s u l t i n a temperature independent
t r a n s f e r c o e f f i c i e n t a, F o l l o w i n g Agar's d i s c u s s i o n (30), such
a b e h a v i o r i n d i c a t e s a p o t e n t i a l dependence o f t h e e n t r o p y o f
a c t i v a t i o n r a t h e r than the e n t h a l p y o f a c t i v a t i o n . Such
"anomalous" b e h a v i o r i n which t h e t r a n s f e r c o e f f i c i e n t depends
on t h e t e m p e r a t u r e seems t o be r a t h e r common a s r e c e n t l y
r e v i e w e d by Conway (31).
A n a l y z i n g t h e d a t a i n terms o f t h e A r r h e n i u s e q u a t i o n
l e a d s t o a complementary r e s u l t (ref.19). An A r r h e n i u s p l o t o f
the d a t a o b t a i n e d on copper i s shown i n Fig.10. S t r a i g h t l i n e s
a r e o b t a i n e d f o r d i f f e r e n t p o t e n t i a l s i n t h e l i q u i d and i n t h e
f r o z e n e l e c t r o l y t e , a g a i n w i t h an i n c r e a s e o f t h e c u r r e n t a t
t h e f r e e z i n g p o i n t . The l i n e s a r e n e a r l y p a r a l l e l f o r t h e

Figure 7. Arrhenius p l o
2 + 3 +
the F e / F e reactio
F i g u r e 8. T a f e l p l o t o f the hydrogen e v o l u t i o n on s i l v e r at
various temperatures.

HClO -5.5
A H 0
2
h y d r o g e n evolution A
0
A Cu <A
A
o Ag * o
Q
A A
o o
A
B
O
OA
m e l t i n g point
228 K
A
0 H 1 1 1 1 1 r—
0 50 100 150 200 250 300
T[K]
F i g u r e 9. Temperature dependence o f the t r a n s f e r c o e f f i c i e n t
of the hydrogen e v o l u t i o n on s i l v e r and copper.
0- U/vs. RHE(V)
-0.7 A
-0.6 o A
-0.5 i
-20
melting point
-r-
6
10 * 1/T(K" ) 1
F i g u r e 10. A r r h e n i u s p l o t o f the hydrogen e v o l u t i o n on

copper a t v a r i o u s p o t e n t i a l s .

various p o t e n t i a l s . This r e s u l t s i n almost p o t e n t i a l

i n d e p e n d e n t a c t i v a t i o n e n e r g i e s b e t w e e n 0.4 a n d 0.5eV
( F i g . l l a ) . The p r e - e x p o n e n t i a l f a c t o r , on t h e o t h e r hand, as
o b t a i n e d from the e x t r a p o l a t i o n t o 1/T=0, i s s t r o n g l y p o t e n t i a l
dependent ( F i g . l l b ) . I t i s h i g h e r i n the f r o z e n e l e c t r o l y t e and
c h a n g e s by a p p r o x . f i v e o r d e r s o f m a g n i t u d e o v e r a r a n g e o f
j u s t 300mV i n o v e r p o t e n t i a 1 !
The l a t t e r d i s c u s s i o n confirms the r e s u l t s of the
p o t e n t i a l dependence o f the c u r r e n t i n t h a t the a c t i v a t i o n
b a r r i e r f o r t h e h y d r o g e n e v o l u t i o n r e a c t i o n i s , a t l e a s t on
c o p p e r and s i l v e r , n o t a f f e c t e d by t h e e l e c t r o d e p o t e n t i a l .
T h i s b e h a v i o r i s , on t h e o t h e r hand, c o n n e c t e d w i t h the
o b s e r v a t i o n o f s t r a i g h t l i n e s i n a T a f e l p l o t . I t w o u l d be
p r e m a t u r e t o come up w i t h a c o m p r e h e n s i v e model t h a t w o u l d
e x p l a i n t h i s b e h a v i o r ; more experimental work i s necessary t o
s u b s t a n t i a t e and q u a n t i f y the e f f e c t s f o r a l a r g e r v a r i e t y o f
s y s t e m s and r e a c t i o n s A few a s p e c t s however should be
p o i n t e d out.
(i) I t i s d i f f i c u l t t
l i k e c o u l d account f o r such r a d i c a l e f f e c t s , i . e . t h a t the
p o t e n t i a l dependence of the a c t i v a t i o n energy i s c o m p l e t e l y
s h i f t e d t o a p o t e n t i a l dependence o f the pre-exponential
factor.
( i i ) A p o t e n t i a l dependent coverage w i t h hydrogen may account
f o r some o f t h e o b s e r v e d e f f e c t s . However, s u r f a c e s c i e n c e
s t u d i e s i n d i c a t e t h a t h y d r o g e n i s n o t a d s o r b e d on s i l v e r o r
copper (10), but e l e c t r o c h e m i c a l systems may be d i f f e r e n t s i n c e
the change of the e l e c t r o d e p o t e n t i a l , i . e . the Fermi l e v e l ,
may a l t e r t h i s s i t u a t i o n .
( i i i ) T u n n e l i n g e f f e c t s may p l a y a r o l e w h i c h w o u l d e x p r e s s
t h e m s e l v e s i n the p r e - e x p o n e n t i a l f a c t o r ; i t i s not c l e a r ,
however, i f the t u n n e l i n g p r o b a b i l i t y w o u l d e x h i b i t such a
s t r o n g p o t e n t i a l and temperature dependence.
F o r an u n d e r s t a n d i n g o f t h e s e processes more i n f o r m a t i o n
f r o m i n - s i t u s u r f a c e s c i e n c e e x p e r i m e n t s i s d e s i r a b l e . The
s t u d y o f w a t e r a d s o r p t i o n on s i l v e r i s a good e x a m p l e f o r
p r o v i d i n g m o l e c u l a r i n f o r m a t i o n t h a t may be r e l e v a n t f o r the
u n d e r s t a n d i n g o f e l e c t r o c h e m i s t r y . As r e v i e w e d by T h i e l and
Madey (13), water, even i n amounts of f r a c t i o n s of a monolayer,
d o e s n o t s p e c i f i c a l l y i n t e r a c t w i t h t h e s i l v e r s u r f a c e . No
d i f f e r e n c e s a r e found i n the thermodesorption s p e c t r a are found
f r o m s u b m o n o l a y e r t o m u l t i l a y e r c o v e r a g e s : t h e y a l l show a
s i n g l e d e s o r p t i o n peak t y p i c a l of b u l k i c e . The bond s t r u c t u r e
w i t h i n the phases i s o b v i o u s l y much s t r o n g e r than between the
phases, i.e. i n the i n t e r f a c i a l r e g i o n . The o r i e n t a t i o n of the
w a t e r m o l e c u l e s i s t h u s d e t e r m i n e d by t h e w a t e r phase r a t h e r
than by the i n f l u e n c e o f the s u b s t r a t e .
A p p l y i n g t h i s to our e l e c t r o c h e m i c a l system c o u l d
q u a l i t a t i v e l y e x p l a i n some o f t h e o b s e r v e d e f f e c t s . A s s u m i n g
t h a t t h e r e i s o n l y a weak i n t e r a c t i o n between m e t a l and t h e
p e r c h l o r i c a c i d h y d r a t e , protons b e i n g p a r t of the c l a t h r a t e
s t r u c t u r e may n o t be i n a f a v o r a b l e p o s i t i o n f o r a c h a r g e
t r a n s f e r r e a c t i o n a t the i n t e r f a c e . T h i s c o u l d r e s u l t i n s m a l l
p r e - e x p o n e n t i a l f a c t o r s . The e l e c t r o d e p o t e n t i a l , however, may

0.7
>
frozen
o
9
UJ
0.3-
0.0
0.4 0.6 0.8
-U(Vvs.RHE)
0.4 0.5 0.6 0.7

-U(Vvs.RHE)
Figure 11. Potential dependence of the a c t i v a t i o n energy,

E , (a) and pre-exponential factor, A, (b) as obtained from
a
Fig.10.

h a v e a l a r g e i n f l u e n c e on i t s i n c e t h e p r o t o n s a r e a l s o t h e
c h a r g e c a r r i e r t h a t a l l o w t h e p o t e n t i a l d i f f e r e n c e t o be
e s t a b l i s h e d a t the i n t e r f a c e . Thus by c h a r g i n g the i n t e r f a c e ,
t h e p r o t o n s w i t h t h e w a t e r s t r u c t u r e s u r r o u n d i n g them, w i l l
a l s o be c h a n g e d w h i c h , i n t u r n , i n f l u e n c e s t h e h y d r o g e n
e v o l u t i o n r e a c t i o n . Such an e f f e c t w o u l d be e x p r e s s e d i n a
p o t e n t i a l dependent p r e - e x p o n e n t i a l f a c t o r .
Conclusions
It i s p o s s i b l e to i n v e s t i g a t e electrochemical behavior i n
aqueous e l e c t r o l y t e s i n a wide range o f temperatures by u s i n g
the FREECE t e c h n i q u e . T h i s way, u s i n g HC104*5.5H20 a s
e l e c t r o l y t e , temperatures down t o a p p r o x i m a t e l y -140°C can be
r e a c h e d . The r e s u l t s show t h a t d o u b l e c h a r g i n g and f a r a d a i c
r e a c t i o n s occur i n the f r o z e n e l e c t r o l y t e i n a comparable way
as i s known f o r t h e l i q u i d e l e c t r o l y t e . The electrode
capacities for gold, s i l v e
t e m p e r a t u r e . The r e s u l t
m e t a l s i n d i c a t e an a n o m a l o u s b e h a v i o r i n t h a t t h e t r a n s f e r
c o e f f i c i e n t shows a t e m p e r a t u r e d e p e n d e n c e . I n t h e c a s e o f
c o p p e r and s i l v e r t h e t r a n s f e r c o e f f i c i e n t a p p e a r s t o be
p r o p o r t i o n a l w i t h t e m p e r a t u r e . I t seems t h a t c u r r e n t m o d e l s
have l i t t l e a b i l i t y to e x p l a i n t h i s behavior. I t i s expected
t h a t m i c r o s c o p i c m o d e l s o f t h e e l e c t r o c h e m i c a l i n t e r f a c e are
b e t t e r s u i t e d . In t h i s r e s p e c t , the concept of s t u d y i n g the co-
a d s o r p t i o n o f w a t e r and i o n s on d e f i n e d s u r f a c e s u n d e r u.h.v.
c o n d i t i o n s d e v e l o p e d by Sass e t a l . (10,11) and r e c e n t l y a l s o
a p p l i e d by Wagner e t a l . (12) can be v e r y h e l p f u l f o r a b e t t e r
understanding o f these q u e s t i o n s .
Acknowledgments
The d i s c u s s i o n s w i t h Prof. J.K. Sass a r e v e r y much a p p r e c i a t e d .

Thanks a r e a l s o due t o D r s . A. P i n k o w s k i and K. T e l l e f s e n f o r
t h e i r h e l p i n p r e p a r i n g t h i s m a n u s c r i p t . T h i s work has been
s u p p o r t e d i n p a r t by t h e N a t i o n a l S c i e n c e F o u n d a t i o n and t h e
O f f i c e o f N a v a l Research.
Literature Cited
(1) VanDyne, R.P.; R e i l l e y , C.N.

Anal.Chem. 1972 44 142.
Anal.Chem. 1972 44 153.
Anal.Chem. 1972 44 158.
(4) Conway, B.E.; Salomon, M. J.Chem.Phys. 1964 41 3169.
(5) Conway, B.E.; McKinnon, D.J.; T i l a k , B.V.
Trans.Faraday Soc. 1970 66 1203.
(6) Yeager, E.; Scherson, D.; S i m i c - G l a v a s k i , B.
163rd Meeting o f the E l e c t r o c h e m i c a l S o c i e t y ,
San F r a n c i s c o , 1983, E x t . A b s t r a c t #706.

(7) McDonald, A.C.; Fan, F.F.; Bard, A . J .

J.Phys.Chem. 1986 90 196.
(8) F l a r s h e i m , W.M.; Tsou, Y.; T r a c h t e n b e r g , I . ;
Johnston, K.P.; Bard, A . J . J.Phys.Chem. 1986 90 3857.
(9) Stimming, U.; S c h m i c k l e r , W.
J.E1ectroanal.Chem. 1983 150 125.
(10) Sass, J.K. Vacuum 1983 (1983) 741.
(11) Stuve,E.M.; Bange, K.; S a s s , J.K. I n T r e n d s in Interfacial
E l e c t r o c h e m i s t r y ; Silva, A.F., Ed.; D.Reidel P u b l i s h i n g
Company: Dordrecht, 1986; p.255.
(12) Wagner, F.T.; Moylan, T.E. S u r f . S c i . 1987 182 125.
(13) Thiel, P.A.; Madey, T.E. S u r f . S c i . R e p . 1987 7 211;
and r e f e r e n c e s of T.E.Madey's work t h e r e i n .
(14) Wiebke, M.; Mootz, D. Z . K r i s t a l l o g r . 1985 170 194.
(15) Mootz, D.; O e l l e r s , E.-F.; Wiebke, M.
J.Am.Chem.Soc. 1987 109 1200.
(16) Dinan, T.; Stimming U J.Electrochem.Soc 1986 133 2662
(17) I w a s i t a , T.; Roettgermann
J.Electroanal.Chem
(18) Hamelin, A.; Roettgermann, S.; S c h m i c k l e r , W.
J.Electroanal.Chem. 1987 230 281.
(19) F r e s e , U.; Stimming, U. In Principles of E l e c t r o c h e m i c a l
P r o c e s s e s ; S c h u l t z e , J.W., Ed.; V C H - V e r l a g s g e s e l l s c h a f t :
Weinheim, 1986; DECHEMA Monographs V o l . 102, p.247.
(20) Grahame, D.C. J.Am.Chem.Soc. 1957 79 2093.
(21) Schmid, G.M.; Hackerman, N.
J.Electrochem.Soc. 1963 110 440.
(22) Hamelin, A.; Stoicoviciu, L.; Silva, F.
J.E l e c t r o a n a l . Chem. 1987 229 107.
(23) Matsunaga, A.; I t o h , K.; F u j i s h i m a , A.; Honda, K.
J.Electroanal.Chem. 1986 205 343.
(24) T a f e l , J . Z.Phys.Chem. 1905 50 641.
(25) B u t l e r , J.A.V. Trans.Faraday Soc. 1924 19 729.
(26) Erdey-Gruz, T.; Volmer, M. Z.Phys.Chem. 1930 150 203.
(27) F r e s e , U.; I w a s i t a , T.; S c h m i c k l e r , W.; Stimming, U.
J.Phys.Chem. 1985 89 1059.
(28) Ludwig, F.; Sen, R.K.; Yeager, E.
E l e k t r o k h i m i y a 1977 13 847.
(29) F r e s e , U.; Stimming, U. J.Electroanal.Chem. 1986 198 409.
(30) Agar, J.N. D i s c .Faraday Soc. 1947 11 81.
(31) Conway, B.E. In Modern E l e c t r o c h e m i s t r y ; B o c k r i s , J.O'M.,
Conway, B.E. and Yeager, E., Eds.; Plenum P r e s s : New York,
1987; Vol.16.

Chapter 20
Second Harmonic Generation Studies

of Chemisorption at Electrode Surfaces
Deborah J . Campbell and Robert M . Corn
Optical second harmonic generation from electrode

surfaces is employed in situ to study the
electrochemical processes of lithium deposition and
monatomic hydrogen chemisorption at silver
electrodes in acetonitrile, and the reversible
deposition of hydrogen at platinum electrodes in
aqueous perchloric acid solutions. The changes
observed in the second harmonic intensity are
ascribed to modifications in the electronic
structure of the metal surface upon adsorption.
These studies demonstrate how the nonlinear optical
response from the surface can provide both a
qualitative and quantitative probe of chemisorption.
O p t i c a l s e c o n d harmonic g e n e r a t i o n (SHG) i s s e n s i t i v e t o t h e
i n t e r f a c e o f two c e n t r o s y m m e t r i c media. A t m e t a l / e l e c t r o l y t e
i n t e r f a c e s , t h e s u r f a c e n o n l i n e a r s u s c e p t i b i l i t y a r i s i n g from
t h e s h a r p g r a d i e n t s i n t h e s t a t i c e l e c t r i c f i e l d s have been
shown t o dominate t h e b u l k m a g n e t i c d i p o l e s o u r c e s f o r SHG when
u s i n g p - p o l a r i z e d l i g h t i n a r e f l e c t i o n geometry (1-2) . T h i s
s e n s i t i v i t y o f t h e SHG t o t h e s u r f a c e has been e x p l o i t e d a t
e l e c t r o d e s f o r measurements o f charge d e n s i t y (3-4), a n i o n i c
a d s o r p t i o n (ji) , o x i d e f o r m a t i o n (£) and c h e m i s o r p t i o n (7-8) . In
t h e m a j o r i t y o f t h e c h e m i s o r p t i o n s t u d i e s t o d a t e , changes i n
t h e n o n l i n e a r o p t i c a l r e s p o n s e o f t h e m e t a l s u r f a c e upon
r e a c t i o n have been u s e d t o i n d i r e c t l y f o l l o w t h e a d s o r p t i o n
process. F o r example, t h e p r o c e s s o f u n d e r p o t e n t i a l d e p o s i t i o n
(upd) o f a monolayer o f Pb o r T l has been s t u d i e d t h r o u g h i t s
e f f e c t on t h e SHG from s i l v e r s u r f a c e s (3-4 7) . r
In t h i s p a p e r we e x t e n d o u r SHG s t u d i e s t o s i l v e r
e l e c t r o d e s i n a c e t o n i t r i l e s o l u t i o n s and t o p l a t i n u m e l e c t r o d e s
i n aqueous s o l u t i o n s . Three d i f f e r e n t examples a r e chosen t o
d e m o n s t r a t e how SHG can be u s e d b o t h q u a l i t a t i v e l y and
q u a n t i t a t i v e l y t o s t u d y t h e a d s o r p t i o n o f c h e m i c a l s p e c i e s onto
0097-6156/88/0378-0294$06.00/0

20. CAMPBELL AND CORN Second Harmonic Generation Studies 295
an e l e c t r o d e s u r f a c e . The systems examined a r e t h e d e p o s i t i o n

o f l i t h i u m onto a s i l v e r s u r f a c e i n a c e t o n i t r i l e , t h e
c h e m i s o r p t i o n o f monatomic hydrogen d u r i n g t h e e v o l u t i o n o f
m o l e c u l a r hydrogen i n nonaqueous a c i d i c media, and t h e
r e v e r s i b l e d e p o s i t i o n of hydrogen on p l a t i n u m e l e c t r o d e s p r i o r
t o t h e hydrogen e v o l u t i o n r e a c t i o n i n aqueous p e r c h l o r i c a c i d
solutions.
The SHG s t u d i e s at s i l v e r e l e c t r o d e s employed a p - p o l a r i z e d
f u n d a m e n t a l beam a t 1064 nm from a Q - s w i t c h e d Nd:YAG l a s e r (10
Hz r e p e t i t i o n r a t e , 8 ns p u l s e width) w i t h an i n c i d e n t a n g l e o f
30° r e l a t i v e t o t h e s u r f a c e normal, and t h e p l a t i n u m e l e c t r o d e
e x p e r i m e n t s u s e d p - p o l a r i z e d l i g h t a t 57 8 nm from a p u l s e d dye
l a s e r (10 Hz r e p e t i t i o n r a t e , 6 ns p u l s e width) w i t h an i n c i d e n t
a n g l e o f 60°. The c u r r e n t and second harmonic s i g n a l o b s e r v e d
d u r i n g t h e c y c l i n g of t h e e l e c t r o d e p o t e n t i a l were r e c o r d e d
s i m u l t a n e o u s l y and s t o r e d on computer. In t h e two nonaqueous
s t u d i e s , p o t e n t i a l s a r e r e p o r t e d v e r s u s a Ag|0.100M AgNC>3
r e f e r e n c e e l e c t r o d e , an
reported versus a saturate
e x p e r i m e n t a l d e t a i l s are p u b l i s h e d e l s e w h e r e (&).
Lithium Deposition on Silver Electrodes in Acetonitrile
The c y c l i c voltammogram f o r a s i l v e r e l e c t r o d e i n 0.IM LiC104

a c e t o n i t r i l e s o l u t i o n i s shown i n F i g u r e 1 (curve a ) . At a
p o t e n t i a l of -1.5 V, c a t h o d i c c u r r e n t due t o t h e r e d u c t i o n o f
+
Li i o n s commences. The upd of l i t h i u m has been r e p o r t e d
p r e v i o u s l y by K o l b e t a l . f o r p o s i t i v e p o t e n t i a l sweeps a f t e r
s u b s t a n t i a l l i t h i u m r e d u c t i o n (j£) ; however, due t o t h e
r e a c t i v i t y of t h e m e t a l l i c l i t h i u m w i t h i m p u r i t i e s i n s o l u t i o n ,
t h e a d s o r b e d l a y e r formed on t h e n e g a t i v e p o t e n t i a l sweep i s not
as s t a b l e as o t h e r upd monolayers (j£) . An a d d i t i o n a l c a t h o d i c
wave due t o t h e r e d u c t i o n o f l i t h i u m i s o b s e r v e d a t
a p p r o x i m a t e l y -2.5V, and on t h e r e t u r n sweep t h e l a c k o f an
a n o d i c wave i s i n d i c a t i v e of t h e r e a c t i v i t y of t h e c h e m i s o r b e d
atoms.
The second harmonic s i g n a l at 532 nm o b t a i n e d f r o m t h e
e l e c t r o d e d u r i n g t h i s c y c l i c voltammogram i s a l s o shown i n
F i g u r e 1 (curve b ) . The second harmonic s i g n a l s t e a d i l y
i n c r e a s e s as t h e p o t e n t i a l i s swept n e g a t i v e l y t h r o u g h t h e
l i t h i u m r e d u c t i o n r e g i o n , and d e c r e a s e s back t o i t s o r i g i n a l
l e v e l on t h e p o s i t i v e s c a n . The independence o f t h e s e c o n d
harmonic s i g n a l on t h e s c a n d i r e c t i o n s u g g e s t s t h a t t h e s u r f a c e
undergoes a change t h a t i s s o l e l y a f u n c t i o n of p o t e n t i a l . We
a t t r i b u t e t h e i n c r e a s e i n second harmonic s i g n a l f r o m t h e
s u r f a c e t o t h e p r e s e n c e of a p o t e n t i a l - d e p e n d e n t surface
c o v e r a g e of c h e m i s o r b e d l i t h i u m . The amount o f a d s o r b e d l i t h i u m
a t a g i v e n p o t e n t i a l i s d e t e r m i n e d by t h e r a t e s o f f o r m a t i o n and
d e s t r u c t i o n of the r e a c t i v e metal o v e r l a y e r . The n o n l i n e a r
s u s c e p t i b i l i t y o f the e l e c t r o d e s u r f a c e i n c r e a s e s upon l i t h i u m
d e p o s i t i o n due t o t h e i n c r e a s e i n f r e e e l e c t r o n d e n s i t y on t h e
s u r f a c e t h r o u g h t h e d e l o c a l i z a t i o n o f t h e l i t h i u m 2s e l e c t r o n .

S i m i l a r i n c r e a s e s o f t h e s u r f a c e second harmonic i n t e n s i t y have

been o b s e r v e d d u r i n g t h e f o r m a t i o n o f a l k a l i m e t a l monolayers on
Ge and Rh s u r f a c e s in vacuo (10-11) .
Hydrogen A d s o r p t i o n and E v o l u t i o n a t S i l v e r E l e c t r o d e s i n
Acetonitrile
The c y c l i c voltammogram and t h e second harmonic s i g n a l a t 532 nm

f o r a s i l v e r e l e c t r o d e i n a 0.IM LiC104 + 3.5mM HCIO4
a c e t o n i t r i l e s o l u t i o n i s shown i n F i g u r e 2. A t a p o t e n t i a l o f -
0.83V t h e r e i s a c a t h o d i c c u r r e n t peak due t o t h e i r r e v e r s i b l e
e v o l u t i o n o f m o l e c u l a r hydrogen. A r e v e r s i b l e decrease i s
o b s e r v e d i n t h e s e c o n d harmonic s i g n a l t h a t s t a r t s p r i o r t o t h e
c a t h o d i c c u r r e n t wave. We a t t r i b u t e t h i s d e c r e a s e i n t h e
o p t i c a l s i g n a l t o the modification of the nonlinear
s u s c e p t i b i l i t y o f t h e s i l v e r s u r f a c e by t h e s t e a d y s t a t e
f o r m a t i o n o f a monatomic hydrogen i n t e r m e d i a t e on t h e e l e c t r o d e
d u r i n g t h e hydrogen e v o l u t i o
The c y c l i c voltammogra
532 nm f o r a s i l v e r e l e c t r o d e i n a 0.IM TBABF4
(tetrabutylammonium t e t r a f l u o r o b o r a t e ) + 35mM a c e t i c a c i d
a c e t o n i t r i l e s o l u t i o n i s shown i n F i g u r e 3. A r e v e r s i b l e l o s s
of s e c o n d harmonic s i g n a l and an i r r e v e r s i b l e c u r r e n t wave from
hydrogen e v o l u t i o n a r e p r e s e n t j u s t as i n t h e p e r c h l o r i c a c i d
s o l u t i o n . However, t h e p o t e n t i a l s f o r t h e s e p r o c e s s e s have been
s h i f t e d by a p p r o x i m a t e l y -IV. These s h i f t s a r e d i r e c t l y r e l a t e d
t o t h e pH o f t h e s o l u t i o n ; m i l l i m o l a r s o l u t i o n s o f o t h e r a c i d s
show s h i f t s o f v a r y i n g magnitude i n a c c o r d a n c e w i t h t h e i r
a c i d i t y (_&).
We c a n q u a n t i t a t e t h e r e l a t i v e s u r f a c e c o v e r a g e o f a d s o r b e d
hydrogen, 0, from t h e second harmonic s i g n a l , I (2C0) :
2
I(2co) = I(2co)o(l + c8) (1)
where I (2co) 0 i s t h e second harmonic s i g n a l from t h e s u r f a c e i n

t h e absence o f c h e m i s o r p t i o n , and c i s a c o n s t a n t t h a t c a n be
d e t e r m i n e d by t h e second harmonic s i g n a l a t maximum s u r f a c e
c o v e r a g e (0 = 1 ) . E q u a t i o n 1 assumes t h a t t h e r e i s no change i n
phase o f t h e n o n l i n e a r s u s c e p t i b i l i t y from t h e s u r f a c e . The
r e l a t i v e s u r f a c e c o v e r a g e c a l c u l a t e d from the s e c o n d harmonic
s i g n a l u s i n g E q u a t i o n 1 f o r t h e case o f a c e t i c a c i d i s shown as
t h e s o l i d c i r c l e s i n F i g u r e 4. The p o t e n t i a l a t which t h e
r e l a t i v e s u r f a c e c o v e r a g e i s one h a l f , E 1 / 2 (0), i s -1.51V. F o r
t h e p e r c h l o r i c a c i d s o l u t i o n a s i m i l a r c u r v e c a n be c o n s t r u c t e d ,
and Ei/2(0) i s f o u n d t o be -0.45V.
These two f a c t s , ( i ) t h e shape o f t h e r e l a t i v e s u r f a c e
c o v e r a g e - p o t e n t i a l c u r v e and ( i i ) t h e pH dependence o f E1/2(0)
can b o t h be a c c o u n t e d f o r by t h e f o l l o w i n g r e a c t i o n mechanism:

CAMPBELL AND CORN Second Harmonic Generation Studies
-2.45
-2.10 toc
cn
-1.75 cn
-1.40 c
o
c
CD
-1.05
c_
D
u "O
-0.70 c
o
u
cn
-0.35
-0.80 -1.05 -1.30 -1.55 -1.80 -2.05 -2.30 -2.55
E(V v s Ag/Ag+)
F i g u r e 1. The c u r r e n t (a) and t h e s e c o n d harmonic s i g n a l (b)

1
o b t a i n e d d u r i n g t h e p o t e n t i a l c y c l i n g (10 mV s " s c a n r a t e )
from a p o l y c r y s t a l l i n e s i l v e r e l e c t r o d e i n a 0. IM LiClC>4 a c e t o -
n i t r i l e solution.
-0.70
-0.20 -0.35 .50 -0.65 -0.80
E(V v s Ag/Ag+)
1
from a p o l y c r y s t a l l i n e s i l v e r e l e c t r o d e i n a 0.IM LiC104 +
3.5mM H C I O 4 acetonitrile solution.

-1.75
-1.50
-1.25 3
CO
-1.00 -m
c
o
E
C
-0.75 (U
x
T3
-0.50 C
o
u
(D
-0.25 cn
-0.8
E(V vs Ag/Ag+)

1
f r o m a p o l y c r y s t a l l i n e s i l v e r e l e c t r o d e i n a 0.IM TBABF + 35mM
4
acetic acid acetonitrile solution.
-1.00 -1.40 -1.60 -1.80 -2.00
E(V vs Ag/Ag+)
F i g u r e 4. The r e l a t i v e s u r f a c e c o v e r a g e o f a d s o r b e d hydrogen
as a f u n c t i o n o f e l e c t r o d e p o t e n t i a l f o r a c e t i c a c i d . The
c i r c l e s a r e c a l c u l a t e d from the s e c o n d harmonic s i g n a l u s i n g
E q u a t i o n 1, and t h e s o l i d l i n e i s t h e t h e o r e t i c a l c u r v e
p r e d i c t e d from t h e r e a c t i o n mechanism ( E q u a t i o n s 2 and 3 ) .

H +
+ e ads
(2)
- 1
2H ads > »2 (3)
The s o l i d l i n e i n F i g u r e 4 i s t h e p o t e n t i a l dependence o f
t h e r e l a t i v e s u r f a c e c o v e r a g e o f H^ds by t h i s r e a c t i o n scheme i n
the steady s t a t e approximation. D e t a i l s o f t h e c a l c u l a t i o n and
r e a c t i o n scheme d e t e r m i n a t i o n have been p r e s e n t e d e l s e w h e r e (&).
Hydrogen adsorption on
solutions
As a f i n a l example o f t h e s t u d y o f c h e m i s o r p t i o n by t h e changes
i n t h e SHG f r o m m e t a l s u r f a c e s , F i g u r e 5 d e p i c t s t h e c o r r e c t e d
c u r r e n t and t h e second harmonic s i g n a l a t 28 9 nm f r o m a p l a t i n u m
e l e c t r o d e i n a 0.35M HCIO4 aqueous s o l u t i o n d u r i n g a c a t h o d i c
p o t e n t i a l sweep i n t h e hydrogen a d s o r p t i o n r e g i o n . The c u r r e n t
waveform has been c o r r e c t e d f o r d o u b l e l a y e r and hydrogen
e v o l u t i o n c o n t r i b u t i o n s by s u b t r a c t i o n o f t h e c u r r e n t o b s e r v e d
i n t h e p r e s e n c e o f 1 m i l l i m o l a r p o t a s s i u m i o d i d e (which i s known
t o b l o c k hydrogen upd on t h e p l a t i n u m s u r f a c e ) (12.) . The two
peaks i n t h e c u r r e n t waveform a t - 0 . 0 4 5 V and - 0 . 2 0 0 V c o r r e s p o n d
t o t h e f o r m a t i o n o f s t r o n g l y (H ) and weakly (H ) a d s o r b e d
s w
hydrogen on t h e p l a t i n u m s u r f a c e ( E q u a t i o n 2). Concomitant with

t h e c h e m i s o r p t i o n o f hydrogen, we o b s e r v e i n F i g u r e 5 a l a r g e
i n c r e a s e i n t h e second harmonic s i g n a l (curve b ) . In c o n t r a s t ,
t h e s e c o n d harmonic s i g n a l i s v i r t u a l l y unchanged i n t h e d o u b l e
l a y e r and o x i d e r e g i o n s o f t h e p o t e n t i a l sweep (not shown). The
increase i n s i g n a l i s e x a c t l y the opposite of the decrease that
was o b s e r v e d f o r t h e s i l v e r e l e c t r o d e s i n a c e t o n i t r i l e . It i s
u n c l e a r from t h i s d a t a a t a s i n g l e w a v e l e n g t h whether t h e
i n c r e a s e i s due t o changes i n t h e p l a t i n u m s u r f a c e ' s n o n l i n e a r
s u s c e p t i b i l i t y , o r whether i t i s due t o t h e i n t r i n s i c n o n l i n e a r
s u s c e p t i b i l i t y o f t h e chemisorbed hydride s p e c i e s .
In s p i t e o f t h i s u n c e r t a i n t y , we c a n q u a n t i t a t e t h i s
i n c r e a s e i n t h e second harmonic s i g n a l due t o c h e m i s o r p t i o n
t h r o u g h t h e use o f E q u a t i o n 1. Since, i n t h i s case, t h e
hydrogen i s c h e m i s o r b e d p r i o r t o t h e f o r m a t i o n o f m o l e c u l a r
hydrogen, we c a n a l s o m o n i t o r t h e s u r f a c e c o v e r a g e o f h y d r i d e by
the c h a r g e p a s s e d d u r i n g t h e d e p o s i t i o n . A p l o t o f "c6"
{ = [I (2co)/I (2co) 0 ] - 1 } v s . q, t h e charge p a s s e d due t h e
hydrogen d e p o s i t i o n , i s shown i n F i g u r e 6. A f u l l monolayer
c o r r e s p o n d s t o a p p r o x i m a t e l y 251 (iC/cm (12.) . As p r e d i c t e d by
2
E q u a t i o n 1, t h e n o n l i n e a r s u s c e p t i b i l i t y o f t h e s u r f a c e depends
l i n e a r l y upon t h e amount o f c h e m i s o r b e d hydrogen, and

i nl , , , I o.OO
150 100 50 0 -50 -100 -150 -200 -250
E(mV v s SCE)
F i g u r e 5. The c o r r e c t e d c u r r e n t (a) and t h e s e c o n d harmonic
s i g n a l (b) o b t a i n e d d u r i n g c a t h o d i c sweep (10 mV s " scan r a t e )
1
from a p o l y c r y s t a l l i n e p l a t i n u m e l e c t r o d e i n a 0.35M HCIO4

aqueous s o l u t i o n .
-2.45.
-2.10
-1.75
-1.40
U
-1.05
-0.70
-0.35
n nn|f* , , , , , , , I
0 -34 -67 -101 -134 -16B -201 -235
Charge OuC/square cm)
1 / 2
F i g u r e 6. The f u n c t i o n c0 ( = [I (2(0)/I (2co) ] 0 - 1 )
d e t e r m i n e d from t h e s e c o n d harmonic s i g n a l p l o t t e d v e r s u s t h e
c h a r g e p a s s e d due t o hydrogen c h e m i s o r p t i o n on t h e p l a t i n u m
electrode.

s u r p r i s i n g l y , i s independent o f t h e c h e m i c a l n a t u r e o f t h e
hydrogen s p e c i e s ( H v s . H ) .
s w We have f o u n d t h i s l a t t e r f a c t
noJi t o be t h e c a s e i n s u l f u r i c a c i d s o l u t i o n s (Campbell, D. J . ;
Corn, R. M. "Second Harmonic G e n e r a t i o n S t u d i e s from P l a t i n u m
E l e c t r o d e s i n S u l f u r i c A c i d S o l u t i o n s " , s u b m i t t e d t o J . Phys.
Chem.).
Summary
In t h i s paper we have u t i l i z e d t h e changes i n t h e SHG from m e t a l

s u r f a c e s t o monitor chemisorption processes at e l e c t r o d e
surfaces. In p a r t i c u l a r , we have seen t h a t :
i) D u r i n g t h e d e p o s i t i o n o f l i t h i u m onto s i l v e r e l e c t r o d e s
i n a c e t o n i t r i l e t h e r e i s a p o t e n t i a l dependent i n c r e a s e
i n t h e s e c o n d harmonic s i g n a l from t h e s i l v e r s u r f a c e due
t o a steady s t a t e coverage of u n r e a c t e d m e t a l l i c l i t h i u m
This increase i n
a r i s e from t h e d e l o c a l i z a t i o
with the m e t a l l i c l i t h i u m o v e r l a y e r .
ii) The c h e m i s o r p t i o n o f a monatomic hydrogen s p e c i e s onto
s i l v e r e l e c t r o d e s i n a c e t o n i t r i l e i s found t o decrease
t h e SHG from t h e s u r f a c e d u r i n g t h e i r r e v e r s i b l e p r o c e s s
o f m o l e c u l a r hydrogen e v o l u t i o n . The q u a n t i t a t i o n o f t h e
s e c o n d harmonic s i g n a l f o r t h i s p r o c e s s y i e l d s t h e
r e l a t i v e s u r f a c e c o v e r a g e o f c h e m i s o r b e d hydrogen as a
f u n c t i o n o f e l e c t r o d e p o t e n t i a l , and t h e shape and pH
dependence o f t h i s r e l a t i v e s u r f a c e c o v e r a g e - p o t e n t i a l
c u r v e can be u s e d t o a s c e r t a i n t h e r e a c t i o n mechanism f o r
hydrogen e v o l u t i o n a t s i l v e r e l e c t r o d e s i n a c e t o n i t r i l e .
iii) On p l a t i n u m e l e c t r o d e s i n p e r c h l o r i c a c i d s o l u t i o n s t h e
s e c o n d harmonic s i g n a l q u a n t i t a t i v e l y i n c r e a s e s d u r i n g
hydrogen atom u n d e r p o t e n t i a l d e p o s i t i o n , and t h i s
i n c r e a s e i s independent o f t h e t y p e o f c h e m i s o r b e d
hydrogen.
A l t h o u g h use o f t h e second harmonic s i g n a l from m e t a l
s u r f a c e s as an i n d i r e c t probe o f c h e m i s o r p t i o n l a c k s s t r u c t u r a l
s p e c i f i c i t y , the u t i l i t y of the technique i s c l e a r l y
d e m o n s t r a t e d by t h e e x p e r i m e n t s r e p o r t e d h e r e . The next s t e p i n
our s t u d i e s w i l l be t o demonstrate how one can d i r e c t l y m o n i t o r
c h e m i s o r p t i o n w i t h some degree o f m o l e c u l a r s p e c i f i c i t y v i a t h e
r e s o n a n t s e c o n d harmonic s i g n a l from t h e n o n l i n e a r
s u s c e p t i b i l i t y of adsorbed s p e c i e s .
Acknowledgment s
The a u t h o r s g r a t e f u l l y acknowledge t h e a s s i s t a n c e o f Matt Lynch

and E r i c M i l l e r i n t h e c o n s t r u c t i o n o f t h e e x p e r i m e n t a l
apparatus f o r these experiments. T h i s work was s u p p o r t e d by t h e
N a t i o n a l Science Foundation.

Literature Cited
1. Bloembergen, Ν.; Chang, R. K.; Jha, S. S.; Lee, C. H. Phys.

Rev. 1968, 174 , 813.
2. Shen, Y. R. The Principles of Nonlinear Optics; Wiley: New
York, 1984.
3. Corn, R. M.; Romagnoli, M.; Levenson, M. D.; Philpott, M. R.
Chem. Phys. Lett. 1984, 106, 30.
4. Corn, R. M.; Romagnoli, M.; Levenson, M. D.; Philpott, M. R.
J. Chem. Phys. 1984, 81, 4127.
5. Richmond, G. L. Langmuir 1986, 2, 132 and references
therein.
6. Biwer, Β. M. Surf. Sci. 1986, 176, 377 .
7. Furtak, T. E. ; Miragliotta, J . ; Korenowksi, G. M. Phys.
Rev. 1987, B35, 2569.
8. Campbell, D. J.; Corn, R. M. J. Phys. Chem., 1987, 91, 5668.
9. Kolb, D. M.; Przasnyski M.; Gerischer H J Electroanal
Chem. 1974, 54, 25
10. Chen, J. M.; Bower
Comm. 1973, 9, 132.
11. Tom, H. W. K.; Mate, C. M.; Zhu, X. D.; Crowell, J. E.;
Heinz, T. F.; Somorjai, G. A.; Shen, Y. R. Phys. Rev. Lett.
1984, 52, 348.
12. Hubbard, A. T.; Ishikawa, R. M.; Katekaru, J. J.
R E C E I V E D M a y 17, 1988

Chapter 21
Vibrational Molecular Probes

of Electrochemical Interfaces
Comparisons and Chemical Applications
M . J. Weaver, D. S. Corrigan, P. Gao, D. Gosztola, and L.-W. H. Leung
Department of Chemistry, Purdue University, West Lafayette, IN 47907

Some c h a r a c t e r i s t i c
surface-enhanced Rama
reflection-absorptio spectroscopy (IRRAS) fo
examining reactive as w e l l as stable electrochemical
adsorbates are illustrated by means of selected recent
r e s u l t s from our laboratory. The differences i n
v i b r a t i o n a l s e l e c t i o n rules for surface Raman and
infrared spectroscopy are discussed for the case of
azide adsorbed on s i l v e r , and used to d i s t i n g u i s h
between "flat" and "end-on" surface orientations.
V i b r a t i o n a l band intensity-coverage r e l a t i o n s h i p s are
briefly considered for some other systems that are
u n l i k e l y to involve coverage-induced r e o r i e n t a t i o n .
Two examples of the a p p l i c a t i o n of SERS and potential
-difference IRRAS methods to the i d e n t i f i c a t i o n of
adsorbed intermediates and reaction mechanism
e l u c i d a t i o n are also described, i n v o l v i n g the c a t a l y t i c
e l e c t r o o x i d a t i o n of carbon monoxide and small organic
molecules on transition-metal surfaces.
A major emerging area of research a c t i v i t y i n i n t e r f a c i a l

electrochemistry concerns the development of i n - s i t u surface
spectroscopic methods, e s p e c i a l l y those applicable i n conventional
electrochemical circumstances. One c e n t r a l objective i s to obtain
d e t a i l e d molecular s t r u c t u r a l information for species w i t h i n the
double layer to complement the inherently macroscopic information
that i s extracted from conventional electrochemical techniques.
V i b r a t i o n a l spectroscopic methods are p a r t i c u l a r l y valuable for t h i s
purpose i n view of t h e i r s e n s i t i v i t y to the nature of intermolecular
interactions and surface bonding as w e l l as to molecular structure.
Two such techniques have been demonstrated to be useful i n
electrochemical systems: surface-enhanced Raman spectroscopy
(SERS) (1) and several variants of infrared r e f l e c t i o n - a b s o r p t i o n
spectroscopy (IRRAS) (2).
We have recently become interested i n developing and applying
0097-6156/88/0378-0303$06.00/0

both of these techniques to the c h a r a c t e r i z a t i o n of fundamental

electrochemical phenomena. In some respects, the SERS and IRRAS
approaches can be regarded as providing complementary techniques for
the v i b r a t i o n a l c h a r a c t e r i z a t i o n of electrode surfaces. Thus SERS
has the important v i r t u e of enabling absolute spectra to be obtained
for a v a r i e t y of adsorbates, u s u a l l y without s i g n i f i c a n t bulk-phase
interferences. On the other hand, i n f r a r e d spectroscopy is
applicable to a much wider range of electrode surfaces, i n c l u d i n g
oriented s i n g l e - c r y s t a l faces.
A s u b s t a n t i a l p o r t i o n of our e f f o r t s i n t h i s area can be
characterized on the basis of three general themes. F i r s t l y , we
have been exploring methods to extend the a p p l i c a b i l i t y of SERS to
surfaces beyond the usual "SERS a c t i v e " coinage metals, s i l v e r ,
copper, and gold (3). This has been accomplished f o r a range of
materials (3a^d), including t r a n s i t i o n metals (3c.d), and also for
metal oxides (3f.g) by depositing them as t h i n (ca. 1-4 monolayer)
f i l m s on a SERS-active gold substrate Secondly, we have been
exploring the u t i l i z a t i o
induced molecular transformation
for the e l u c i d a t i o n of electrochemical r e a c t i o n mechanisms
(3c-e.4-6). T h i r d l y , comparisons between corresponding surface
Raman and i n f r a r e d spectra have been pursued i n order to examine
differences i n surface s e l e c t i o n rules as w e l l as a means of
ascertaining to what extent the adsorbate sensed by the former probe
may d i f f e r from the preponderant species presumably sensed by the
l a t t e r technique (3c.d.7). This l a s t question i s of some importance
given the l i k e l i h o o d that SERS may sense only a minority of the
adsorbate, located at or close to the surface morphologies
responsible f o r the surface enhancement (1).
The present conference paper provides a discussion of some
representative findings from our recent studies on these t o p i c s ,
with the aim of comparing and contrasting some of the d i s t i n c t i v e
properties of SERS and IRRAS as applied to fundamental i n t e r f a c i a l
electrochemistry. We l i m i t the presentation here to a b r i e f
overview; further d e t a i l s can be found i n the references c i t e d . A l l
electrode p o t e n t i a l s quoted here are with respect to the saturated
calomel electrode (SCE).
Comparisons Between Corresponding Surface Raman and Infrared

Spectra: Band Intensity-Coverage Relationships
Although by now a large number of electrochemical systems have been

examined using both SERS and IRRAS, i n c l u d i n g some common to both
techniques (2b), the conditions employed are u s u a l l y s u f f i c i e n t l y
d i f f e r e n t (e.g. disparate surface s t a t e , adsorbate concentrations)
so to preclude a quantitative comparison of the s p e c t r a l responses.
One further hindrance to such comparisons i s that i t u s u a l l y i s
d i f f i c u l t to remove e n t i r e l y the c o n t r i b u t i o n to the i n f r a r e d
spectra from solution-phase species. Two types of approaches are
commonly used i n IRRAS with t h i s objective i n mind. Firstly,
modulating the i n f r a r e d beam between s- and p - p o l a r i z a t i o n can
achieve a measure of demarcation between surface and bulk-phase
components since considerably greater i n f r a r e d absorption w i l l occur
for the former, but not the l a t t e r , species f o r p- versus s-
p o l a r i z e d l i g h t (2.8). However, a complication i s that the "surface

21. WEAVER ET AL. Vibrational Probes of Electrochemical Interfaces 305
region" i n t h i s context extends a distance of about 0.5 A, where A

i s the i n f r a r e d wavelength, away from the r e f l e c t i n g surface (8.9).
Since the thickness of the t h i n - l a y e r c a v i t y conventionally used f o r
such measurements i s of the order of A (about 5 microns), the
species i n the s o l u t i o n as w e l l as i n the double layer w i l l e x h i b i t
a p o l a r i z a t i o n - s e n s i t i v e i n f r a r e d absorbance. Consequently, i n
p r a c t i c e t h i s polarization-modulation approach w i l l not u s u a l l y
achieve a complete c a n c e l l a t i o n of the s p e c t r a l c o n t r i b u t i o n from
solution-phase species.
The second, and most widely used, approach to the separation of
surface and solution-phase contributions to IRRAS involves
p o t e n t i a l - d i f f e r e n c e methods, taking advantage of the commonly
a n t i c i p a t e d dependence of the surface i n f r a r e d spectra features to
the electrode p o t e n t i a l . We w i l l r e f e r to t h i s general approach as
" p o t e n t i a l - d i f f e r e n c e i n f r a r e d spectroscopy" (PDIRS). Although the
d e t a i l s of the experiment are d i f f e r e n t depending i f a dispersive or
Fourier transform (FT) instrument i s employed i n both cases PDIR
spectra are obtained by
acquired at a s u i t a b l e
instrument i s employed, t h i s approach i s often r e f e r r e d to as
" s u b t r a c t i v e l y normalized Fourier transform i n f r a r e d spectroscopy"
(SNIFTIRS) ( 2 ) ] . Bipolar bands are therefore u s u a l l y obtained i n
PDIR spectra, r e f l e c t i n g the difference i n the p o t e n t i a l - s e n s i t i v e
component at the p a r t i c u l a r p a i r of "base" and "sample" p o t e n t i a l s
chosen (2).
Provided that the surface species of i n t e r e s t does not undergo
adsorption/desorption between these two p o t e n t i a l s , the PDIR
spectrum thus obtained w i l l a r i s e only from the surface species.
However, i f the species undergoes s i g n i f i c a n t adsorption/desorption
(or redox transformations) under these conditions, then the PDIR
spectra may w e l l r e f l e c t the consequent changes i n the t h i n - l a y e r
s o l u t i o n composition as w e l l as i n the surface region (10). This
circumstance constitutes a solution-phase interference upon the PDIR
spectrum which w i l l obviously be detrimental i f the frequencies of
the v i b r a t i o n a l bands f o r the adsorbate i n the surface and bulk-
phase environments overlap s u b s t a n t i a l l y . On the other hand, as
noted below the synergic appearance of such band partners can y i e l d
valuable surface compositional information.
A simple example, taken from reference 7, that i l l u s t r a t e s these
points i n the context of infrared-Raman comparisons i s provided i n
Figures 1 and 2. Figure 1 consists of a series of PDIR spectra
obtained f o r azide adsorbed on s i l v e r . Each spectrum employed a
base p o t e n t i a l of -0.97 V and the series of sample p o t e n t i a l s
indicated, the l a t t e r being r a t i o e d against the former. Under the
conditions chosen, the azide coverage could be a l t e r e d from very
small values (at the most negative p o t e n t i a l s ) to approaching a
monolayer (at the most p o s i t i v e p o t e n t i a l s ) . At the most negative
1
p o t e n t i a l s , only a s i n g l e positive-going band at 2048 cm" appears,
the i n t e n s i t y increasing as the sample p o t e n t i a l i s made less
negative. This band i s i d e n t i f i e d as a r i s i n g from loss of s o l u t i o n
azide caused by corresponding increases i n the amount of adsorbed
azide at the more p o s i t i v e p o t e n t i a l s (10). The constant frequency,
-1
2048 cm , of the positive-going band i s consistent with the
asymmetric N-N-N s t r e t c h , u , f o r aqueous azide.
&s (An e s s e n t i a l l y
constant t o t a l amount of azide w i l l be trapped i n the t h i n - l a y e r

2048
i
-520
1
2300 Z/, cnf 1900
Figure 1
Potential-difference i n f r a r e d (PDIR) spectra f o r adsorbed azide
at an electrochemically roughened silver-aqueous interface i n the
asymmetric N-N-N, i / , stretch region.
a g Electrolyte: 0.01 M
NaN + 0.1 M NaC10 . Base (reference) p o t e n t i a l was -0.97 V vs.
3 A
SCE; sample p o t e n t i a l s (mV vs. SCE) are as indicated. Spectra

were obtained by acquiring 1024 interferometer scans at the base
and sample p o t e n t i a l s , the p o t e n t i a l being a l t e r e d a f t e r every 32
scans (see references 7 and 10 f o r further d e t a i l s ) .

21. WEAVER ETAL. Vibrational Probes of Electrochemical Interfaces 307
_I I I I I / / II I I 1// J I 1 1
91
2100 1950 1350 1250 " 650 550
RAMAN SHIFT, c r r f 1
Figure 2
Surface-enhanced Raman (SER) spectra f o r adsorbed azide at an
electrochemically roughened silver-aqueous interface at electrode
potentials indicated. Frequency regions shown r e f e r to
asymmetric N-N-N s t r e t c h ( ^ ) , symmetric N-N-N s t r e t c h ( i / ) ,
as s
N-N-N bending modes. E l e c t r o l y t e : 0.01 M NaN + 0.1 M NaC10 .

3 A
1 1
Monochromator scan rate was 0.5 cm" s" ' with 50 mW l a s e r
e x c i t a t i o n at 514.5 nm (see reference 7 f o r further d e t a i l s ) .

c a v i t y under the conditions of these experiments ( 1 0 ) , where the use

of excess supporting e l e c t r o l y t e e s s e n t i a l l y eliminates the
c o n t r i b u t i o n of N3" to the ion migration to and from the t h i n layer
which occurs upon p o t e n t i a l a l t e r a t i o n ( 3 2 ) . )
I n t e r e s t i n g l y , however, the corresponding negative-going i/ &s
band expected f o r adsorbed azide i s not observed u n t i l the most

p o s i t i v e p o t e n t i a l s , E > -0.05 V, whereupon a feature a t 2 0 7 5 - 2 0 8 5
1
cm" appears and grows markedly i n i n t e n s i t y as the sample
p o t e n t i a l , and hence the azide coverage, i s increased f u r t h e r . From
a knowledge of the e f f e c t i v e integrated a b s o r p t i v i t y , A , of the L
azide band i n the t h i n - l a y e r s o l u t i o n , the positive-going band

i n t e n s i t y can y i e l d a semiquantitative measure of the p o t e n t i a l -
dependent azide coverage since, u n l i k e the corresponding surface
i n f r a r e d band, the s o l u t i o n feature w i l l accurately obey Beer's Law.
In favorable cases, then, p l o t s of the integrated i n t e n s i t i e s of the
negative-going (surface) versus the positive-going (solution) bands,
I s o l and I , once corrected f o r band overlap therefore provide a
s u r
r e l i a b l e means of assessin
a b s o r p t i v i t y o f a give
coordination.
In the a z i d e - p o l y c r y s t a l l i n e s i l v e r case i l l u s t r a t e d i n
Figure 1, I s u r «
s o l I f o r f r a c t i o n a l azide coverages below
ca. 0.3-0.5, whereas f o r higher coverages, A I s u r ~ AI s o l (7• 10^ •
These r e s u l t s have been interpreted as i n d i c a t i n g the presence of
predominantly " f l a t " adsorbed azide g i v i n g way to a more " v e r t i c a l "
o r i e n t a t i o n of the N3" i o n a t higher coverages ( 1 0 ) . This
i n t e r p r e t a t i o n follows from the well-known surface dipole s e l e c t i o n
r u l e , which decrees that only v i b r a t i o n s having a dipole component
normal to the surface can i n t e r a c t with the incident p-polarized
l i g h t (JL3) . S i m i l a r r e s u l t s were obtained with e l e c t r o p o l i s h e d and
electrochemically roughened ( i . e . SERS-active) s i l v e r surfaces
(7.10). Corresponding measurements f o r azide adsorbed at low-index
s i n g l e - c r y s t a l s i l v e r faces y i e l d e d comparable findings f o r the
A g ( l l l ) and Ag(100) planes as obtained f o r the p o l y c r y s t a l l i n e
surfaces ( 1 4 ) . S i g n i f i c a n t l y , however, the Ag(110) surfaces y i e l d e d
no detectable surface i / fts band over the e n t i r e range of azide
coverages. This was a t t r i b u t e d to the preference o f a l i n e a r N3"
anion to be oriented f l a t along the p a r a l l e l atomic-scale "furrows"
which are c h a r a c t e r i s t i c of the Ag(110) surface ( 1 4 ) .
A set of SER spectra f o r adsorbed azide on s i l v e r , obtained f o r
the same surface and s o l u t i o n conditions and f o r a s i m i l a r sequence
of electrode p o t e n t i a l s as f o r the PDIR spectra i n Figure 1, i s
shown i n Figure 2. (See the f i g u r e caption and reference 7 f o r
experimental details.) Inspection of these SER spectra i n
comparison with the PDIR r e s u l t s i l l u s t r a t e some c h a r a c t e r i s t i c
differences i n the information provided by the two techniques. Most
prominently, i n a d d i t i o n to the N3" i / band around 2060 cm" , the
a s
1
former spectra e x h i b i t three other features a t lower frequencies

a t t r i b u t a b l e to adsorbed azide v i b r a t i o n s . By analogy with bulk-
1
phase spectra f o r free and coordinated azide ( 1 5 ) , the 1330 cm"
SERS band i s a t t r i b u t e d to the N-N-N symmetric s t r e t c h , i / ( 7 ) . The
g
observation o f both v and i/ features i n the SER spectra d i f f e r s

% &s
from the surface i n f r a r e d r e s u l t s i n that only the i / a s band i s

obtained i n the l a t t e r (7) . The appearance of the i / band i n SERS a s
i s of i n t e r e s t since t h i s feature i s symmetry forbidden i n the

s o l u t i o n azide Raman spectrum.

An i n t e r e s t i n g d i f f e r e n c e , however, i s seen i n the p o t e n t i a l

dependence of the SERS u and 1/ features, i n that the l a t t e r i s
s
only observed at the l e a s t negative p o t e n t i a l s (E > -0.2 V), where

the surface i n f r a r e d i / band also appears, whereas the former band
a s
survives u n t i l the most negative p o t e n t i a l s (E < -0.8 V),

corresponding to v i r t u a l l y complete azide desorption (10)
(Figure 2) . The appearance of the SERS 1/ feature i s i n d i c a t i v e of
azide coordinated "end on", i . e . bound by a s i n g l e nitrogen, since
the reduction i n symmetry required by the v i b r a t i o n a l s e l e c t i o n
rules i s thereby obtained. No such symmetry lowering would occur,
however, f o r azide bound i n a f l a t surface configuration, which can
account f o r the loss of the SERS 1/ feature at more negative
potentials. The r e t e n t i o n of the v band under these conditions
s
(Figure 2) i s consistent with such an adsorbate o r i e n t a t i o n since,

u n l i k e surface i n f r a r e d spectra, the occurrence of surface Raman
t r a n s i t i o n s does not require the presence of a v i b r a t i o n a l tensor
normal to the surface plane provided that they are allowed on the
basis of bulk-phase s e l e c t i o
Examination of the
the SER spectra (Figure 2) i s also i n s t r u c t i v e with regard to
adsorbate o r i e n t a t i o n . Thus, the p a i r of bands (at ca. 610 and 670
-1
cm ) seen at the l e a s t negative p o t e n t i a l s are c h a r a c t e r i s t i c of
end-on coordinated azide (15); the l o s s of the lower-frequency
partner f o r E < -0.15 V i s therefore also i n d i c a t i v e of the removal
of azide bound i n t h i s adsorbate geometry, again i n harmony with the
i n t e r p r e t a t i o n of the i n f r a r e d spectra (7).
O v e r a l l , then, t h i s simple example i l l u s t r a t e s how the form of
surface Raman as w e l l as i n f r a r e d spectra can y i e l d u s e f u l
complementary (and even consistent!) information on surface
o r i e n t a t i o n , at l e a s t f o r small symmetric adsorbates. Even though
the surface v i b r a t i o n a l s e l e c t i o n rules are markedly l e s s c l e a r c u t
for the former technique, the wide frequency range and
correspondingly r i c h s p e c t r a l features commonly obtained with SERS
can provide major b e n e f i t s . Another v a r i a n t of such a p p l i c a t i o n s of
SERS that we have pursued recently involves the e l u c i d a t i o n of the
adsorbate-surface binding geometries f o r various monosubstituted
benzenes on gold (16). In t h i s case a d i s t i n c t i o n between surface
binding v i a the aromatic r i n g and the substituent group could be
made by examining the r e l a t i v e frequency s h i f t s and i n t e n s i t i e s of
some c h a r a c t e r i s t i c i n t e r n a l modes i n SERS r e l a t i v e to the bulk-
phase Raman spectra (.16) .
Quite apart from the s t r u c t u r a l information that can be obtained
by inspecting the dependence of the surface v i b r a t i o n a l band
i n t e n s i t i e s , I , upon adsorbate coverage, 0, a knowledge of these
r e l a t i o n s h i p s are obviously of importance when employing such
spectra f o r surface a n a l y t i c a l purposes. A p a r t i c u l a r case of
i n t e r e s t to us concerns u t i l i z i n g p o t e n t i a l - and/or time-dependent
band i n t e n s i t i e s as a means of monitoring the progress of
electrochemical reactions i n v o l v i n g adsorbed species (4-6.17). We
have made several q u a n t i t a t i v e comparisons between the p o t e n t i a l -
dependent SERS i n t e n s i t i e s f o r e l e c t r o a c t i v e adsorbates engaged i n
r e v e r s i b l e one-electron redox e q u i l i b r i a with corresponding surface
concentration-potential data obtained from faradaic electrochemical
measurements (6a.17). Generally speaking, the corresponding I - E SER

and 0-E p l o t s e x h i b i t reasonable agreement, as would be expected i f

the SERS band i n t e n s i t y I was at l e a s t roughly proportional to $
g E R
under the appropriate conditions.

Figure 3 shows p l o t s of the r e l a t i v e I values against the g E R
r e l a t i v e adsorbate coverage, 0 - i f o r two such adsorbates at e l
3+ 3
s i l v e r , Ru(NH ) and Os(NH ) py ™ (py - p y r i d i n e ) , extracted from
3 3 5
the corresponding potential-dependent data i n references 6a and 17,

respectively. Both these species are adsorbed by e l e c t r o s t a t i c
a t t r a c t i o n to the chloride monolayer present under the experimental
+
conditions employed (18). The I values f o r Ru(NH )g and
g E R 3
3+ IIX
0s(NH ) py
3 5 adsorbates r e f e r to the Ru -NH s t r e t c h i n g mode at 3
1 1
500 cm" and the p y r i d i n e r i n g "breathing" mode a t 1020 cm" '
+
respectively. For Ru(NH )g , the ^ E f i - ^ r e i
3 relation i s
+
approximately l i n e a r , whereas f o r 0s(NH ) p]p the p l o t e x h i b i t s
3 5
s i g n i f i c a n t deviations from l i n e a r i t y (Figure 3). I n both cases,

however, the maximum adsorbate coverage i s w e l l below that
corresponding to a close-packed monolayer, the surface concentration
being around 3 to 5 x 10"
Figure 3 also contain
simple s p e c i f i c a l l y adsorbed species, bromide on s i l v e r ( s o l i d
curve). This p l o t was extracted from bromide coverage-potential
data, obtained from d i f f e r e n t i a l capacitance measurements, along
with the corresponding potential-dependent i n t e n s i t y of the SERS
1
bromide-surface stretching mode at ca. 160 cm" (19). I n t h i s case,
the maximum ( i . e . unity) value of 0 corresponds to a close-packed
r e l
9 2
bromide monolayer, ca. 1.4 x 10" mol cm' . Again, the l - 0 S E R r e l
p l o t i s decidedly nonlinear. Such behavior i s unsurprising, not

only i n view of the l i k e l y influence of adsorbate-adsorbate
i n t e r a c t i o n s , but also given the i n e v i t a b l e nonuniform nature of the
roughened surfaces necessary f o r SERS a c t i v i t y . Similar I - 0 S E R r e i
comparisons using potential-dependent data, but i n a less

quantitative v e i n , have been made f o r other h a l i d e and pseudohalide
adsorbates on s i l v e r and gold electrodes (19.20). Generally
speaking, although there i s a rough correspondence between the
corresponding I - E and 0 -E p l o t s , s u b s t a n t i a l n o n l i n e a r i t i e s i n
gER rel
the I - 0 S E R r e l a t i o n s can be i n f e r r e d from these data.

r e l Recent
d e t a i l e d examinations of l - 0 r e l a t i o n s f o r resonantly enhanced
S E R r e l
adsorbates also indicate the occurrence of marked n o n l i n e a r i t i e s

(21).
Aside from coverage-induced adsorbate s t r u c t u r a l changes such as
are noted above f o r the a z i d e - s i l v e r system, the form and
i n t e r p r e t a t i o n of i n f r a r e d band intensity-coverage r e l a t i o n s h i p s has
a reasonable fundamental footing (22). Substantial n o n l i n e a r i t i e s
i n i n f r a r e d I - 0 p l o t s are both predicted and observed to occur i n
sur
u l t r a - h i g h vacuum (uhv) f o r adsorbed carbon monoxide a t both single-

c r y s t a l and p o l y c r y s t a l l i n e surfaces as a r e s u l t of dipole-dipole
coupling e f f e c t s (22). For CO adsorbed at p o l y c r y s t a l l i n e platinum
electrodes, however, approximately I a $ over a wide range of s u r
coverages (5b.23), although s i g n i f i c a n t deviations from l i n e a r i t y

have been reported (24). Coverage measurements can be obtained i n
t h i s case from the charge required f o r e l e c t r o o x i d a t i o n of
i r r e v e r s i b l y adsorbed CO (vide i n f r a ) (5b). A l i n e a r I - 0 sur
r e l a t i o n has also been obtained f o r cyanate (OCN") adsorbed on a

p o l y c r y s t a l l i n e s i l v e r electrode, again by u t i l i z i n g the r e l a t i v e
i n t e n s i t i e s of I and I
g u r bands i n PDIR spectra a r i s i n g from
g o l
potential-dependent adsorption-desorption e q u i l i b r i a (10).

0
Relative Coverage , 9\ re
Figure 3
P l o t s of r e l a t i v e SERS band i n t e n s i t y , I , against r e l a t i v e
S E R
3+ 3+
adsorbate coverage, 0 , f o r Ru(NH ) , Os(NH ) py
rel 3 (py -
3 5
pyridine), and Br" adsorbed on s i l v e r , extracted from

corresponding I - p o t e n t i a l and 6-potential
S E R data. Experimental
data taken from references 6a, 17, and 19, respectively (see text
and the references f o r further d e t a i l s ) .

Another method of probing dipole-dipole adsorbate coupling

e f f e c t s involves examining band i n t e n s i t y and frequency s h i f t s f o r
adsorbate i s o t o p i c mixtures (22). S i m i l a r l y to r e s u l t s obtained f o r
uhv systems, Severson et a l . have observed strong coupling e f f e c t s
12 13
i n the i n f r a r e d spectra f o r CO/ CO mixtures adsorbed on
polycrystalline platinum, manifested i n substantially higher
i n t e n s i t i e s of the higher-frequency forms ("intensity borrowing")
and large frequency s h i f t s f o r the mixed isotope layers (24).
We have recently examined such dipole-dipole coupling e f f e c t s
for cyanide adsorbed at gold electrodes using both surface i n f r a r e d
and SER spectroscopies, with the objective of probing any
differences i n the nature of the surface environment f o r the
i n f r a r e d and SERS-active adsorbate (25). Such differences might be
a n t i c i p a t e d given the l i k e l i h o o d that SERS senses only a minority of
the adsorbate, probably i n the v i c i n i t y of p a r t i c u l a r metal
microstruetures (1). Somewhat s u r p r i s i n g l y , only r e l a t i v e l y small
isotope dipole-dipole coupling e f f e c t s were observed f o r cyanide at
gold despite the s i m i l a r i t
coordination f o r CN" an
shows a p l o t of the peak frequencies f o r high and low-frequency
bands i n the i s o t o p i c mixture p l o t t e d against the percentage of CN"
12
present as CN". Although both bands s h i f t to progressively lower
frequencies as a given i s o t o p i c species i s d i l u t e d i n c r e a s i n g l y i n
12 13 1
the CN"/ CN" mixture, the s h i f t s are small (< 8 cm" ). S i m i l a r
i n f r a r e d r e s u l t s have been reported e a r l i e r by Kunimatsu et a l .
(27). I n a d d i t i o n , the degree of " i n t e n s i t y borrowing" by the high-
frequency band i s only moderate i n comparison with the corresponding
e f f e c t s f o r CO. I n t e r e s t i n g l y , the magnitude of these coupling
e f f e c t s i s very s i m i l a r f o r SER and i n f r a r e d spectroscopies, both
the frequencies and r e l a t i v e band i n t e n s i t i e s i n the i s o t o p i c
mixtures being v i r t u a l l y i d e n t i c a l i n both cases.
Irrespective of the d e t a i l e d i n t e r p r e t a t i o n of these r e s u l t s
(25), they provide further evidence against the oft-popular notion
that SERS f o r cyanide and other strongly coordinating adsorbates
arises from s p e c i f i c "surface complexes" [such as Au^N)^] (2jJ) as
d i s t i n c t from the preponderant adsorbate species presumably sensed
by i n f r a r e d spectroscopy (also see reference 7).
Applications to Mechanistic Surface Electrochemistry
As noted i n the Introduction, a c e n t r a l focus of our current

i n t e r e s t s i n both surface Raman and i n f r a r e d spectroscopies i s
d i r e c t e d towards t h e i r u t i l i z a t i o n i n r e a c t i v e electrochemical
systems (3-6). An important v i r t u e of i n - s i t u v i b r a t i o n a l
spectroscopies f o r t h i s purpose i s that they can y i e l d information
on the molecular i d e n t i t y (as w e l l as d e t a i l e d p h y s i c a l state) of
electrogenerated species, and hence can provide considerable
mechanistic information f o r multistep electrode processes. We have
recently discussed several facets of such a p p l i c a t i o n s i n a
conference paper f o r "Surface Vibrations V" (6b).
Although both SER and i n f r a r e d spectroscopies are w e l l s u i t e d to
providing information of t h i s type, several factors conspire to
slant t h e i r applications i n noticeably d i f f e r e n t d i r e c t i o n s . At
l e a s t with s u i t a b l y SERS-active surfaces, the former technique can

21. WEAVER ETAL. Vibrational Probes ofElectrochemical Interfaces 313
l m M [ C N V » 3 C N ] / 0 . 5 M K S0
, 2
2 4
Figure 4
12 13
P l o t s of the C-N peak frequencies, i / , f o r various CN"/ CN"
C N
mixtures adsorbed on electrochemically roughened gold electrode,

observed with SERS ( c i r c l e s ) and p o t e n t i a l - d i f f e r e n c e i n f r a r e d
12 13
(PDIR, squares) methods. Total CN" concentration ( CN" + CN")
held constant at 1 mM, with 0.5 M K S0 supporting e l e c t r o l y t e .
2 4
Electrode p o t e n t i a l was -0.8 V vs. SCE. PDIR spectra obtained by

stepping from -0.8 V to 0.8 V so to remove s o l u t i o n interference
(25).

provide absolute v i b r a t i o n a l spectra f o r adsorbed species i n the

presence of high concentrations of s o l u t i o n species i n conventional
electrochemical c e l l s . Consequently, SERS can y i e l d s e n s i t i v e ,
a l b e i t q u a l i t a t i v e , information on the changes i n i n t e r f a c i a l
composition and structure accompanying electrode reactions f o r a
v a r i e t y of electrochemical techniques and c e l l configurations. For
example, SERS can r e a d i l y be coupled with steady-state p o t e n t i a l -
dependent techniques, e i t h e r with r o t a t i n g - d i s k voltammetry (4a.c)
or i n quiescent s o l u t i o n (3c.d.4b-h). Such t a c t i c s enable the
experimental timescale to be s u f f i c i e n t l y long to enable
conventional scanning monochromators to be employed, even though the
markedly shorter measurement times afforded by the use of o p t i c a l
multichannel analyzer (OMA) detection o f f e r considerable b e n e f i t s .
The l a t t e r detection scheme also enables sequences o f SER spectra to
be obtained during c y c l i c voltammetrie and other potential-time
excursions ( 4 i . j . 6 b ) .
The examination of surface compositional changes accompanying
electrochemical processe
amenable to study by IRRAS
t h i n - l a y e r c e l l configuration i n order to minimize solution-phase
interferences. The use o f p o t e n t i a l - d i f f e r e n c e i n f r a r e d techniques
to f u r t h e r n u l l i f y s o l u t i o n interferences i s advantageous f o r the
examination o f electrochemical reactions since these processes are
inherently p o t e n t i a l s e n s i t i v e . However, a d i f f i c u l t y with the use
of potential-modulation i n f r a r e d methods ( i . e . employing repeated
p o t e n t i a l a l t e r a t i o n between base and sample values) i s that they
are s e n s i t i v e only to the occurrence of s t r i c t l y r e v e r s i b l e
processes, while most multi-step processes of mechanistic i n t e r e s t
are i r r e v e r s i b l e i n nature. This d i f f i c u l t y can be surmounted, a t
l e a s t i n favorable cases, by employing a Fourier transform
spectrometer and applying only a s i n g l e p o t e n t i a l a l t e r a t i o n during
the s p e c t r a l a c q u i s i t i o n , s e q u e n t i a l l y a t the base and sample
p o t e n t i a l s (5a.b). This "single p o t e n t i a l - a l t e r a t i o n i n f r a r e d "
(SPAIR) procedure, l i k e other PDIR techniques, has the v i r t u e of
enabling potential-induced compositional changes i n the t h i n - l a y e r
s o l u t i o n as w e l l as the electrode surface to be detected. It
therefore can enable the i d e n t i t y of p a r t i c u l a r s o l u t i o n
intermediates and/or products, trapped i n the t h i n layer c a v i t y , to
be i d e n t i f i e d and t h e i r formation k i n e t i c s established. We now
describe b r i e f l y two examples, chosen with the aim of i l l u s t r a t i n g
some o f these points.
Figure 5 shows SER spectra i n the C-0 s t r e t c h i n g , i / , region c o
obtained a t the positive-going sequence of electrode p o t e n t i a l s

indicated f o r carbon monoxide adsorbed on a rhodium-coated gold
electrode from a CO-saturated 0.1 M HC10 s o l u t i o n (3d). A This
surface was formed by electrodepositing a f i l m (ca. 3 equivalent
monolayers) of rhodium on to the SERS-active gold substrate. This
procedure enables the SERS e f f e c t to be imparted to s u i t a b l e
adsorbates, such as CO, bound to the t r a n s i t i o n - m e t a l overlayer
(Id). At the i n i t i a l , l e a s t p o s i t i v e p o t e n t i a l s (< 0.4 V), two u CQ
1
bands are observed, a strong feature centered a t 2025-2055 cm" and
1
a weaker band a t 1900 cm' (Figure 5). These features are
c h a r a c t e r i s t i c o f CO bound to rhodium i n a terminal ("linear") and
bridged configuration, r e s p e c t i v e l y , by analogy with i n f r a r e d data
gathered at rhodium-gas interfaces (29).

20
j?' T500
A lcps
f V -0.2V
{** 2055
2..0 A JJE
J Sm0^
î/ / r\—2046
..!...! 1 1 1 1 1 1 1 1 1 1 1 1 1 1
2100 1900 2100 1900
Raman shift, cm" 1
Figure 5
Representative sequence o f SER spectra i n C-0 s t r e t c h i n g , v QQy
region f o r CO adsorbed on rhodium-coated gold electrode.

E l e c t r o l y t e was CO-saturated 0.1 M HC10 . Spectra were obtainedA
i n numbered sequence f o r p o t e n t i a l s (V vs. SCE) as indicated.

Laser e x c i t a t i o n was 70 mW at 647.1 nm; monochromator scan rate
1 1
was 0.5 cm" s" . Rhodium electrodeposition employed a faradaic
2
charge o f 2.0 mC cm" (corresponding to ca. 3 equivalent
monolayers) (3d).

As the p o t e n t i a l i s a l t e r e d to sequentially more p o s i t i v e values

i n the region where CO e l e c t r o o x i d a t i o n commences, 0.5-0.6 V, an
a d d i t i o n a l pronounced i / feature a t 2110 cm" appears (Figure 5).
c o
1
Each o f these bands eventually disappear a t p o t e n t i a l s , > 0.7 V,

corresponding to the passivation of the rhodium surface by oxide
f i l m growth, although they sequentially reappear when the p o t e n t i a l
i s readjusted i n the negative d i r e c t i o n (spectra 8-12 i n Figure 5).
Corresponding PDIR spectra obtained under comparable conditions d i d
1
not e x h i b i t the 2110 cm" band, although the other two i/ features Q0
were observed.
1
One possible assignment of the 2110 cm" feature i s to
I
v i b r a t i o n s i n v o l v i n g a dicarbonyl, Rh (C0) , surface species (30);
2
however, t h i s seems u n l i k e l y since the a n t i c i p a t e d band partner (30)

1
i s absent. Most l i k e l y , the 2110 cm" band signals the appearance
of CO bound to "oxidized" rhodium s i t e s , where rhodium has undergone
formal oxidation to Rh(I) or R h ( I I I ) , and/or adjacent to s i t e s where
surface oxide has formed (3d). A s i m i l a r high-frequency i/ feature CQ
has been observed a t supporte

(31).
These r e s u l t s , as w e l l as s i m i l a r findings obtained f o r CO
adsorbed a t ruthenium-coated gold (3d), are of relevance to the
mechanism of CO electrooxidation since they indicate that a
s i g n i f i c a n t f r a c t i o n of the CO adsorbed at p o t e n t i a l s where reaction
proceeds i s modified s u b s t a n t i a l l y by the e a r l y stages o f metal
oxidation. This suggests that adsorbed 0 or OH may be responsible
f o r CO e l e c t r o o x i d a t i o n on these surfaces, although such s i t e s
admittedly may not be e l e c t r o c a t a l y t i c i n nature.
The second example taken from recent work i n our laboratory
involves the a p p l i c a t i o n o f SPAIRS under potential-sweep conditions
f o r examining the electrooxidation mechanisms of organic molecules
on platinum (5b.c.l2b). Figure 6 shows a p a r t i a l sequence of
i n f r a r e d spectra obtained during a positive-going p o t e n t i a l sweep a t
1
2 mV s" from -0.25 V, f o r a s o l u t i o n of 50 mM benzaldehyde a t
p o l y c r y s t a l l i n e platinum. Each spectrum shown involved acquiring 25
interferometer scans (consuming ca. 15 s) and r a t i o i n g these to a
corresponding set of scans obtained a t the i n i t i a l p o t e n t i a l p r i o r
to s t a r t i n g the p o t e n t i a l sweep. (The p o t e n t i a l s indicated r e f e r to
the average values during each spectral a c q u i s i t i o n . )
Several features of these SPAIR spectra provide information
regarding the e l e c t r o o x i d a t i o n mechanism o f benzaldehyde. Most
1
prominently, a negative-going band a t 2343 cm" i s observed a t
p o t e n t i a l s following the commencement o f faradaic oxidation a t ca.
0.6 V. This i s i d e n t i f i e d as gaseous C0 formed i n the t h i n layer
2
by benzaldehyde electrooxidation. (The negative-going form of t h i s

band i n the "transmittance" spectra shown denotes that the species
i s being formed at the sample p o t e n t i a l . ) Furthermore, the quantity
of C0 formed can be deduced from a knowledge o f the band
2
a b s o r p t i v i t y , obtained i n separate experiments i n v o l v i n g the

formation of C0 from the e l e c t r o o x i d a t i o n of an i r r e v e r s i b l y
2
adsorbed CO monolayer on platinum (5b). By t h i s means, we deduce

9 2
that about 3 x 10" mol cm" of C0 i s formed by the end (1.26 V) of
2
the p o s i t i v e p o t e n t i a l sweep.
The o r i g i n of a t l e a s t a portion of t h i s C0 i s i d e n t i f i e d by
2
1
the band appearing around 2050-2070 cm' (Figure 6). The frequency
and potential-dependent c h a r a c t e r i s t i c s of t h i s feature are

2400 1000
y/crrf 1
Figure 6
Sequence of single p o t e n t i a l a l t e r a t i o n i n f r a r e d (SPAIR) spectra
1
i n 1000-2400 cm" region obtained during voltammetrie oxidation
of benzaldehyde at platinum-aqueous i n t e r f a c e . Solution
contained 50 mM benzaldehyde i n 0.1 M HC10 . Voltammetric sweep
4
1
rate was 2 mV s" ; i n i t i a l (base) p o t e n t i a l was -0.25 V vs. SCE.
Each spectrum shown, r e f e r r i n g to average p o t e n t i a l s indicated,
was obtained by acquiring 25 interferometer scans (consuming ca.
15 s ) , and r a t i o i n g against spectrum obtained s i m i l a r l y at the
i n i t i a l p o t e n t i a l j u s t p r i o r to the p o t e n t i a l sweep (see
references 5b and c f o r further d e t a i l s ) .

diagnostic of l i n e a r l y bound carbon monoxide, formed by d i s s o c i a t i v e

chemisorption of benzaldehyde. We have noted recently that high
coverages of CO are r e a d i l y formed on platinum from a v a r i e t y of
aldehydes, alcohols, and amides, providing that the molecule
contains a t l e a s t one hydrogen bound to the a carbon atom (5c) . At
p o t e n t i a l s p r i o r to i r r e v e r s i b l e CO oxidation (ca. 0.55 to 0.75 V) a
b i p o l a r band i s observed, a r i s i n g from the potential-dependent s h i f t
i n the i/ peak frequency. Beyond t h i s point, a unipolar p o s i t i v e -
CQ
going band i s obtained, r e f l e c t i n g only the i / c ofeature a t the

i n i t i a l p o t e n t i a l (Figure 6). From the r e l a t i o n between i n f r a r e d
absorbance and CO coverage noted above (5b), the CO surface
9 2
concentration i s estimated to be about 1 x 10" mol cm" .
These r e s u l t s therefore indicate that a s i g n i f i c a n t p o r t i o n (ca.
two-thirds) of the C0 formed during the positive-going sweep arises
2
from e l e c t r o o x i d a t i o n of benzaldehyde (or possibly other i n t e r f a c i a l

species) rather than from adsorbed CO. I n addition, the SPAIR
spectra indicate that the formation of C0 commences only upon CO
2
e l e c t r o o x i d a t i o n , and e s s e n t i a l l
previously adsorbed CO
small (0 < 0.1). Although these r e s u l t s do not r u l e out the
possible role of adsorbed CO as an intermediate i n the
e l e c t r o o x i d a t i o n of s o l u t i o n benzaldehyde to C0 , they suggest that
2
the majority of the adsorbate acts as a poison f o r t h i s process,

removal of which i s required f o r i n i t i a t i o n of the e l e c t r o c a t a l y t i c
pathway.
We have recently performed a v a r i e t y of these and r e l a t e d
SPAIRS-voltammetrie measurements on platinum and palladium (5c.12b).
and have concluded that the adsorbed CO formed i n most cases acts
predominantly as a poison f o r organic electrooxidation.
Interestingly, the p o t e n t i a l a t which the CO undergoes
e l e c t r o o x i d a t i o n , and hence where the e l e c t r o c a t a l y s i s commences,
can be strongly dependent on the structure of the s o l u t i o n species
involved. Thus f o r acetaldehyde, f o r example, t h i s process occurs
at about 0.3 V lower overpotentials than f o r benzaldehyde under
comparable conditions (5c).
The t h i r d mechanistically i n s t r u c t i v e feature o f the spectra i n
Figure 6 concerns the appearance of several a d d i t i o n a l negative-
going bands a t r e l a t i v e l y p o s i t i v e p o t e n t i a l s . While the intense
1
band a t 1110 cm" i s due to potential-induced migration (and
p o s s i b l y adsorption) of perchlorate anion (32), the appearance of
1
other bands a t 1280, 1321, and ca. 1700-1720 cm' (Figure 6) r e s u l t s
from the e l e c t r o o x i d a t i o n of benzaldehyde. On the basis o f t h e i r
frequencies and r e l a t i v e i n t e n s i t i e s , these features can be assigned
with confidence to C-0, C-C, and C-0 s t r e t c h i n g modes f o r s o l u t i o n
benzoic a c i d (5d.33). (The r e l a t i v e l y weak and d i s t o r t e d form of
the C-0 band i s probably due to p a r t i a l overlap with the
corresponding positive-going band associated with the loss of
s o l u t i o n benzaldehyde.) Although benzoic a c i d preadsorbed on
platinum undergoes exhaustive oxidation of a l l seven carbons to C0 , 2
s o l u t i o n benzoic a c i d i s apparently e l e c t r o i n a c t i v e (5d), thus

accounting f o r i t s appearance as a benzaldehyde oxidation product
even at f a r p o s i t i v e p o t e n t i a l s .
S i m i l a r experiments performed with other aldehydes and primary
alcohols indicate that t h e i r e l e c t r o o x i d a t i o n on platinum produce
p r i m a r i l y the corresponding carboxylic a c i d i n a d d i t i o n to C0 , 2

whereas secondary alcohols y i e l d ketones. Moreover, the product

d i s t r i b u t i o n can be established q u a n t i t a t i v e l y as a function of
p o t e n t i a l and/or time from the measured SPAIR band i n t e n s i t i e s
combined with a knowledge of the e f f e c t i v e molar a b s o r p t i v i t i e s
(12b).
While such measurements u t i l i z e a relatively conventional
spectroelectrochemical procedure, they have the s u b s t a n t i a l v i r t u e
for e l e c t r o c a t a l y t i c purposes of providing at l e a s t p a r t i a l
information on the involvement of both surface and solution-phase
intermediates and/or products.
Concluding Remarks
At the present time, both surface-enhanced Raman and i n f r a r e d

spectroscopies have reached an i n t e r e s t i n g l e v e l of maturity and
demonstrated a p p l i c a b i l i t y to problems of genuine electrochemical
significance. The frenzy that surrounded the e a r l y development of
SERS, e s p e c i a l l y regardin
l a r g e l y subsided. Nevertheless
as a t r u l y s e n s i t i v e , as w e l l as molecular s e l e c t i v e , surface
a n a l y t i c a l probe. Although hampered by the l i m i t e d realm of
substrates d i s p l a y i n g s u i t a b l e surface enhancement e f f e c t s , t h i s
difficulty i s i n c r e a s i n g l y becoming circumvented so that the
electrochemical (and chemical) impact of SERS should grow s t e a d i l y
i n the future.
Surface i n f r a r e d spectroscopy, on the other hand, appears to
provide opportunities and challenges having a noticeably d i f f e r e n t
flavor. A major emerging area i s i n i t s a p p l i c a t i o n to examining
oriented s i n g l e - c r y s t a l and other surfaces having s o - c a l l e d "well-
defined" structures, f o r which SERS i s l i k e l y to remain
inapplicable. Within the greater l i m i t a t i o n s of s e n s i t i v i t y and
frequency response faced by IRRAS i n comparison with SERS, one might
a n t i c i p a t e that i n f r a r e d techniques w i l l play a s i g n i f i c a n t r o l e i n
exploring the r e a c t i v e , as w e l l as purely s t r u c t u r a l , properties of
such surfaces. The examination of chemically modified electrodes
c o n s i s t i n g of organized microstruetures i s another obvious area of
a p p l i c a t i o n f o r IRRAS where the demands on s e n s i t i v i t y w i l l often be
less stringent.
As a consequence, the development paths of surface Raman and
i n f r a r e d techniques w i l l , given t h e i r d i f f e r e n t strengths and
weaknesses, probably continue to proceed along divergent avenues of
chemical a p p l i c a t i o n . Nevertheless, i t seems i n e v i t a b l e that both
w i l l contribute i n an i n c r e a s i n g l y important fashion to the d e t a i l e d
molecular-level e l u c i d a t i o n of r e a c t i v e as w e l l as stable
electrochemical systems.
Acknowledgments
This work i s supported by the National Science Foundation and the

O f f i c e of Naval Research.
Literature Cited
1. Recent reviews include (a) Chang, R. K.; Laube, B. L., CRC C r i t .

Rev. S o l i d State Mat. S c i . , 1984, 12, 1; (b) Weitz, D. A.;

Moskovits, M.; Creighton, J . A., in "Chemistry and Structure at

Interfaces - New Laser and O p t i c a l Techniques", H a l l , R. B.;
Ellis, A. B., eds., VCH Publishers, D e e r f i e l d Beach, FL, 1986,
p. 197; (c) Moskovits, M., Rev. Mod. Phys., 1985, 59, 783.
2. Recent reviews include (a) Bewick, A.; Pons, S., in "Advances in
Infrared and Raman Spectroscopy", Clark, R. J . H.; Hester, R.
E., eds., V o l . 12, Wiley Heyden, New York, 1985, Chapter 1; (b)
Foley, J . K.; Korzeniewski, C.; Dashbach, J . L.; Pons, S., in
" E l e c t r o a n a l y t i c a l Chemistry - A Series of Advances", Bard, A.
J . , ed., V o l . 14, Marcel Dekker, New York, 1986, p. 309.
3. (a) Leung, L.-W. H.; Weaver, M. J . , J. E l e c t r o a n a l . Chem., 1987,
217, 367; (b) Leung, L.-W. H.; Gosztola, D., Weaver, M. J.,
Langmuir, 1987, 3, 45; (c) Leung, L.-W. H., Weaver, J . Am. Chem.
Soc., 1987, 109, 5113; (d) Leung, L.-W. H.; Weaver, M. J.,
Langmuir, i n press; (e) D e s i l v e s t r o , J . ; Corrigan, D. A.;
Weaver, M. J . , J. Phys. Chem., 1986, 90, 6408; ( f ) D e s i l v e s t r o ,
J . ; Corrigan, D. A.; Weaver, M. J . , J. Electrochem. Soc., 1988,
135, 885; (g) Gosztola
4. (a) Farquharson, S.
J . , J . E l e c t r o a n a l . Chem., 1984, 178, 143; (b) Patterson, M. L.;
Weaver, M. J . , J . Phys. Chem., 1985, 89, 1331; (c) Tadayyoni, M.
A.; Gao, P.; Weaver, M. J . , J . Electroanal. Chem., 1986, 198,
125; ( f ) Tadayyoni, M. A.; Weaver, M. J . , Langmuir, 1986, 2,
179; (g) D e s i l v e s t r o , J . ; Weaver, M. J . , J. E l e c t r o a n a l . Chem.,
1986, 209, 377; (h) D e s i l v e s t r o , J . ; Weaver, M. J . , J.
Electroanal. Chem., 1987, 234, 237; (i) Gao, P.; Gosztola, D.;
Weaver, M. J . , Anal. Chim. Acta, i n press; ( j ) Gao, P.;
Gosztola, D.; Weaver, M. J . , J . Phys. Chem., submitted.
5. (a) Corrigan, D. S.; Leung, L.-W. H.; Weaver, M. J . , Anal.
Chem., 1987, 59, 2252; (b) Corrigan, D. S.; Weaver, M. J ., J.
Electroanal. Chem., 1988, 241, 143; (c) Leung, L.-W. H.; Weaver,
M. J . , J . Electroanal. Chem., 1988, 240, 341; (d) Corrigan, D.
S.; Weaver, M. J., Langmuir, in press.
6. (a) Weaver, M. J . ; Gao, P.; Gosztola, D.; Patterson, M. L.;
Tadayyoni, M. A., ACS Symp. Ser., 1986, 307, 135; (b) Weaver, M.
J . ; Corrigan, D. S.; Gao, P.; Gosztola, D.; Leung, L.-W. H., J .
Electron. Spect. Related Phen., 1987, 45, 291.
7. Corrigan, D. S.; Gao, P.; Leung, L.-W. H.; Weaver, M. J.,
Langmuir, 1986, 2, 744.
8. For example, Golden, W. G., in "Fourier Transform Infrared
Spectroscopy", Vol. 4, Academic Press, New York, 1985, Chapter
8.
9. Seki, H.; Kunimatsu, K.; Golden, W. G., Applied Spect., 1985,
39, 437.
10. Corrigan, D. S.; Weaver, M. J . , J. Phys. Chem., 1986, 90, 5300.
11. A complication in determining absolute A values f o r s o l u t i o n
i
species in r e f l e c t i o n - a b s o r p t i o n cell geometries is that these

will d i f f e r somewhat from the values determined using a
conventional transmittance cell arrangement as a r e s u l t of the
influence of the metal surface on the l o c a l electromagnetic
field. (8,9) For t y p i c a l conditions using electrochemical IRRAS
with p-polarized l i g h t , the e f f e c t i v e A values f o r aqueous
i
s o l u t i o n species appears to be ca. 2-4 times those obtained i n

transmittance measurements. (12)
12. (a) Corrigan, D. S.; Krauskopf, E. K.; Rice, L. M.; Wiekowski,

21. WEAVER ET AL. Vibrational Probes ofElectrochemical Interfaces 321
A.; Weaver, M. J . , J. Phys. Chem., 1988, 92, 1596; (b) Leung,

L.-W. H.; Weaver, M. J., J. Phys. Chem., submitted.
13. (a) Moskovits, M., J . Chem. Phys., 1982, 77, 4408; (b)
Moskovits, M.; Suh, J. S., J. Phys. Chem., 1984, 88, 5526; (c)
Greenler, R. G., J. Chem. Phys., 1966, 44, 310.
14. Corrigan, D. S.; Brandt, E. S.; Weaver, M. J . , J. Electroanal.
Chem., 1987, 235, 327.
15. (a) Nelson, J . ; Nelson, S. M., J . Chem. Soc. A, 1969, 1597; (b)
Forster, D.; Horrocks, W. DeW., J r . , Inorg. Chem., 1966, 5,
1510.
16. Gao, P.; Weaver, M. J., J. Phys. Chem., 1985, 89, 5040.
17. Farquharson, S.; Guyer, K. L.; Lay, P. A.; Magnuson, R. H.;
Weaver, M. J., J. Am. Chem. Soc., 1984, 106, 5123.
18. Tadayyoni, M. A.; Farquharson, S.; Weaver, M. J . , J. Chem.
Phys., 1984, 80, 1363.
19. Weaver, M. J . ; Hupp, J . T.; Barz, F.; Gordon I I , J . G.;
P h i l p o t t , M. R., J Electroanal Chem., 1984 160 321
20. Gao, P.; Weaver, M.
21. (a) Zeman, E. J . ; Carron
P., J. Chem. Phys., 1987, 87, 4189. (b) Cotton, T. M.; Kim, J .
H.; Uphans, R. A.; Möbius, D., to be submitted to J . Phys. Chem.
22. For a review, see H o l l i n s , P.; P r i t c h a r d , J . , Prog. Surf. Sci.,
1985, 19, 275.
23. Kunimatsu, K.; K i t a , H., J. Electroanal. Chem., 1987, 218, 155.
24. Severson, M. W.; R u s s e l l , A.; Campbell, D.; R u s s e l l , J . W.,
Langmuir, 1987, 3, 202.
25. Gao, P.; Weaver, M. J., in preparation.
26. Monocyanogen (CN), however, has been observed to u s u a l l y be
adsorbed parallel to the surface in uhv on the basis of electron
energy loss spectroscopy: (a) Kordesch, M. E.; Stenzel, W.;
Conrad, H., Surf. S c i . , 1986, 175, L689; (b) Kordesch, M. E.;
Stenzel, W.; Conrad, H.; Weaver, M. J., J. Am. Chem. Soc., 1987,
109, 1878.
27. Kunimatsu, K.; Seki, H.; Golden, W. G.; Gordon II, J. G.;
P h i l p o t t , M. R., Langmuir, i n press.
28. Baltruschat, H.; Heitbaum, J . , J. Electroanal. Chem., 1983, 157,
319.
29. For a review, see: Sheppard, N.; Nguyen, T. T., in "Advances in
Infrared and Raman Spectroscopy", Clark, R. J . H.; Hester, R.
E., eds., Heyden, London, 1978, V o l . 5, p. 67.
30. For example, Yates, J. T.; K o l a s i n s k i , K., J. Chem. Phys., 1983,
79, 1026.
31. K i s s , J . T.; Gonzalez, R. D., J . Phys. Chem., 1984, 88, 898.
32. Corrigan, D. S.; Weaver, M. J . , J . Electroanal. Chem., 1988,
239, 55.
33. Gonzalez-Sanchez, F., Spectrochim Acta, 1958, 12, 17.
RECEIVED May 17,1988

Chapter 22
In Situ Optical Vibrational

Spectroscopy of Simple Ions
at the Electrode—Electrolyte Interface
IBM Research Division, Almaden Research Center, San Jose,

CA 95120-6099
The combination of surface enhanced Raman scattering (SERS)

and infrared reflection absorption spectroscopy (IRRAS)
provides an effective in-situ approach for studying the
electrode-electrolyte interface. The extreme sensitivity to surface
species of SERS is well known. By using polarization
modulation of the infrared beam for IRRAS, the complete band
shape is obtained without modulating the electrode potential.
Thus, besides being sensitive to absorbing species on the
electrode surface as well as in the solution in the region very
close to the surface, it is possible to obtain potential dependent
behavior in fine detail. We have applied these techniques to
examine the interaction of simple ions such as CN- and N- with 3
polycrystalline electrodes of silver, gold and copper. The

observed vibrational spectra can be interpreted with the help of
selection rules based on symmetry and analysis of ab-initio SCF
wavefunctions of clusters. The results of these studies will be
reviewed.
T h e d i s c o v e r y o f t h e surface e n h a n c e d R a m a n scattering p h e n o m e n o n ( S E R S ) (1,2)

i n 1977 a n d t h e d e m o n s t r a t i o n o f s t r a i g h t f o r w a r d , m o d u l a t e d s p e c u l a r reflectance
s p e c t r o s c o p y i n t h e i n f r a r e d r e g i o n (3) h a v e c o m b i n e d t o give t h e electro c h e m i s t s a
m e a n s t o investigate in-situ t h e electrode-electrolyte interface w h i c h h a s a r e l a t i v e l y
h i g h degree o f m o l e c u l a r specificity. T h e m e c h a n i s m s u n d e r l y i n g S E R S h a s t u r n e d
o u t t o b e m o r e c o m p l e x t h a n h a d b e e n a n t i c i p a t e d (4). T h e electrode surface
generally requires s o m e p r e t r e a t m e n t w h i c h gives i t a n a t o m i c scale r o u g h n e s s . T h i s
is u s u a l l y a c h i e v e d b y repeated o x i d a t i o n - r e d u c t i o n cycles, a n d t h e p o t e n t i a l r a n g e i n
w h i c h S E R S spectra c a n b e o b s e r v e d i s l i m i t e d . T h e e n h a n c e m e n t is also l i m i t e d t o
c e r t a i n m e t a l s s u c h as A g , A u a n d C u . W i t h i n these l i m i t a t i o n s , h o w e v e r , S E R S
p r o v i d e s v e r y h i g h s e n s i t i v i t y a n d e x c e p t i o n a l l y w i d e frequency range. T h e a b i l i t y t o
- 1
go d o w n t o t h e 100 c m r e g i o n , w h e r e t h e m e t a l l i g a n d s t r e t c h i n g m o d e s are f o u n d ,
is e s p e c i a l l y c o m p l e m e n t a r y t o t h e present l i m i t a t i o n o f i n f r a r e d s p e c t r o s c o p y t o g o
d o w n t o l o w frequency.
0097-6156788/0378-0322$06.00/0

22. S E K I Vibrational Spectroscopy of Simple Ions 323
I n this p a p e r s o m e o f the w o r k i n v o l v i n g in-situ v i b r a t i o n a l s p e c t r o s c o p y ,

m a i n l y those f r o m o u r laboratory, w i l l be reviewed w h i c h illustrate the k i n d o f
u n d e r s t a n d i n g w e h a v e b e e n able t o a c h i e v e . It h a s often b e e n o u r experience t h a t
considerable insight, regarding the adsorption o f molecules a n d ions, is gained w h e n
the results o b t a i n e d b y v i b r a t i o n a l s p e c t r o s c o p y are c o n s i d e r e d i n c o n j u n c t i o n w i t h
t h e results o f ab initio S C F cluster-adsorbate c a l c u l a t i o n s .
Experimental
T h e e l e c t r o c h e m i c a l c e l l u s e d i n o u r l a b o r a t o r y h a s b e e n fully d e s c r i b e d elsewhere
(5). T h e c e l l b o d y is m a d e o f c h e m i c a l l y inert K e l - F a n d the electrode is m o u n t e d o n
a p i s t o n so t h a t i t s surface c a n b e p u s h e d t o t h e o p t i c a l w i n d o w , t o a s p a c i n g o f t h e
order o f 1-3 m i c r o n s , i n o r d e r t o m i n i m i z e t h e s i g n a l f r o m t h e b u l k electrolyte. F o r
R a m a n scattering s p e c t r o s c o p y t h e w i n d o w is o f flat fused q u a r t z , a n d the e x c i t i n g
laser b e a m i s i n c i d e n t at a b o u t 6 0 ° . T h e scattered l i g h t is c o l l e c t e d o f f - n o r m a l , b u t
the g e o m e t r y is n o t c r i t i c a l f o r S E R S d u e t o t h e h i g h s e n s i t i v i t y . D e t a i l s o n t h e S E R S
m e a s u r e m e n t s i n o u r l a b o r a t o r y h a v e b e e n r e p o r t e d p r e v i o u s l y (6,7)
V a r i o u s techniques hav
w i t h t h e m a series o f a c r o n y m s
i n f r a r e d s p e c t r o s c o p y ) (8), S N I F T I R S ( s u b t r a c t i v e l y n o r m a l i z e d i n t e r f a c i a l f o u r i e r
t r a n s f o r m i n f r a r e d s p e c t r o s c o p y ) (9), P D I R ( p o t e n t i a l difference i n f r a r e d
s p e c t r o s c o p y ) (10) a n d S P A I R S (single p o t e n t i a l - a l t e r a t i o n I R s p e c t r o s c o p y ) (II).
T h e y a l l i n v o l v e t a k i n g t h e spectral difference b e t w e e n t w o p o t e n t i a l s i n o r d e r t o
i m p r o v e t h e s i g n a l t o n o i s e r a t i o , a n d a d i s c u s s i o n o f t h e details h a s b e e n g i v e n b y
C o r r i g a n et a l . ( H ) . I n o u r l a b o r a t o r y w e use t h e I B M I n s t r u m e n t s , I n c . I R / 9 8 F T I R
(fourier t r a n s f o r m infrared) s p e c t r o m e t e r a n d , besides P D I R , w e often e m p l o y P M
F T I R R A S (polarization modulated F T I R reflection absorption spectroscopy). This
latter t e c h n i q u e e v o l v e d f r o m t h e w o r k o f G o l d e n et a l . (12,13) a n d uses a
p h o t o e l e a s t i c m o d u l a t o r t o s w i t c h t h e p o l a r i z e d i n f r a r e d b e a m ( i n c i d e n t at c a . 6 0 ° )
b e t w e e n p a n d s p o l a r i z a t i o n (14). I t takes a d v a n t a g e o f t h e surface s e l e c t i o n r u l e
(13) t o o b t a i n essentially t h e a b s o r p t i o n r e f l e c t i o n s p e c t r a o f species v e r y close t o t h e
electrode surface w h i c h h a v e d y n a m i c d i p o l e c o m p o n e n t s n o r m a l t o t h e surface. T h e
detector s i g n a l consists o f a n A C c o m p o n e n t c o r r e s p o n d i n g t o ( I — I ) a n d a D C p s
c o m p o n e n t c o r r e s p o n d i n g t o ( I - f I ) , w h e r e I a n d I a r e detected intensities o f t h e
p s p s
p a n d s p o l a r i z e d l i g h t . B y c i r c u i t r y o u t l i n e d elsewhere (13) w e o b t a i n
( I - I )/(I + I ). T h e m a i n a d v a n t a g e o f this t e c h n i q u e is t h a t ( I - I ) , w h i c h
p S P s p s
c o n t a i n s t h e a b s o r p t i o n spectra o f t h e species o n / n e a r t h e electrode surface, is

a m p l i f i e d d i r e c t l y b y t h e l o c k - i n a m p l i f i e r before d i g i t i z a t i o n , r e s u l t i n g i n a h i g h s i g n a l
t o noise r a t i o . F u r t h e r m o r e this is d o n e at a fixed p o t e n t i a l a n d t h e b a n d shape is
observed directly.
T h e o p t i c a l c o n f i g u r a t i o n w h i c h w e h a v e b e e n u s i n g r e c e n t l y f o r I R R A S is
s h o w n i n F i g u r e 1. T h i s a r r a n g e m e n t h a s fewer b e a m reflections after t h e s a m p l e
c o m p a r e d t o w h a t w a s s h o w n i n a n earlier r e p o r t (5). T h e highest s e n s i t i v i t y is
o b t a i n e d b y u s i n g a n I n S b detector b u t this l i m i t s o u r l o w e s t w a v e n u m b e r t o a b o u t
- 1
1850 c m . W i t h a slight sacrifice i n sensitivity, use o f a H g C d T e ( M C T ) detector
- 1
w o u l d l o w e r t h e l i m i t t o 1030 c m , t h e c u t o f f o f t h e C a F p r i s m w i n d o w w h i c h w e
2
use. H o w e v e r f o r t h e studies presented here this w a s n o t a l i m i t a t i o n .
Adsorbate Structure
T h e c y a n i d e i o n w a s o n e o f t h e first a d s o r b e d i o n s w h i c h w a s f o u n d t o b e surface
e n h a n c e d ( 8 ^ ) o n silver electrodes. I n t h i s first stage o f S E R S i n v e s t i g a t i o n o f t h e
cyanide i o n , it was assumed to be linearly bonded to A g , t h r o u g h the carbon a t o m ,
p e r p e n d i c u l a r t o t h e m e t a l surface (9). H o w e v e r f a c e d w i t h t h e pressure o f e x p l a i n i n g
the S E R S m e c h a n i s m , a l t e r n a t i v e structures were p r o p o s e d . W i t h t h e c o n c e p t i o n o f
the 'ad-atom' m o d e l for S E R S , O t t o conjectured that the m a i n S E R S b a n d w a s due

SIDE VIEW
Figure 1. A s c h e m a t i c d i a g r a m g i v i n g t h e t o p v i e w a n d side v i e w o f the o p t i c s

a n d electrochemical cell for obtaining P M F T I R R A S .

22. S E K I Vibrational Spectroscopy of Simple Ions 325
2 _
t o a n [ A g ( C N ) ] surface c o m p l e x (10). B a s e d o n a w e l l c o n c i e v e d S E R S e x p e r i m e n t
3
i n v o l v i n g i s o t o p e s , F l e i s c h m a n n et a l . (U) p r o p o s e d t h a t t h e m a i n b a n d w a s d u e t o
[ A g ( C N ) ] ~ . U n f o r t u n a t e l y t h e r e s o l u t i o n o f the spectra w a s insufficient t o b a c k t h i s
2
p r o p o s a l f i r m l y . B a l t r u s c h a t a n d V i e l s t i c h i n d e p e n d e n t l y also p r o p o s e d t h a t t h e m a i n
a d s o r b e d species w a s [ A g ( C N ) ] ~ b a s e d o n e l e c t r o c h e m i c a l a r g u e m e n t s (19). T h i s
2
m o d e l w a s further r e i n f o r c e d b y S E R S w o r k o f c y n i d e o n A u electrode (2Q).

A s w e b u i l t u p o u r P M - I R R A S c a p a b i l i t y , o n e o f the interests w a s t o c o m p a r e
the i n f r a r e d a n d S E R S spectra o f the same species. F i g u r e 2 presents spectra t a k e n
b y I R R A S a n d S E R S f o r c y a n i d e o n A g (21). I n t h e series o f I R R A S spectra, there
1 1
are three d i s t i n c t b a n d s (22,23). T h o s e at 2080 c m " a n d 2136 c m " , w h i c h d o n o t
c h a n g e t h e i r b a n d p o s i t i o n s are r e a d i l y assigned t o c y a n i d e a n d t h e [ A g ( C N ) ] ~ 2
c o m p l e x , respectively, i n t h e s o l u t i o n i n agreement w i t h r e p o r t e d v a l u e s (; ;)• T h e

- 1
t h i r d b a n d , a r o u n d 2100 c m , shifts t o l o w e r w a v e n u m b e r s as t h e electrode p o t e n t i a l
b e c o m e s m o r e n e g a t i v e a n d m a t c h e s t h e m a i n b a n d i n t h e S E R S spectra. I f t h e
surface species w e r e a d i c y a n o c o m p l e x , i t c o u l d b e b e n t w i t h a C s y m m e t r y , a n d 2 v
have v i b r a t i o n a l modes corresponding t o the symmetric, r a m a n active m o d e a n d the

a s y m m e t r i c , i n f r a r e d a c t i v e m o d e o f the s o l u t i o n c o m p l e x w i t h symmetry. T h e
n e a r perfect m a t c h o f the I R R A
a d s o r b e d species r e s p o n s i b l e f o
c o m p l e x i o n b u t d u e t o a singl c y a n i d cyanid
o n A u (23,25), i.e., t h e p o s i t i o n a n d p o t e n t i a l d e p e n d e n t shift o f the I R R A S a n d
S E R S b a n d s o f the a d s o r b e d c y a n i d e are i d e n t i c a l .
A n o t h e r i n d i c a t i o n , t h a t t h e surface species is a single c y a n i d e i o n , is seen i n
the reversible series o f I R R A S spectra i n F i g u r e 3 (25). A s t h e p o t e n t i a l is stepped
- 1
p o s i t i v e f r o m - 1 . 0 V u p t o - 0 . 7 V a n d t h e n reversed, t h e 2146 c m b a n d w h i c h is
_
assigned t o t h e [ A u ( C N ) ] c o m p l e x i o n i n s o l u t i o n (23,25) u n d e r g o e s a reversible
2
- 1
increase a n d t h e n a decrease. T h e a p p e a r a n c e o f the 2146 c m b a n d is a c c o m p a n i e d
- 1
b y t h e d i s a p p e a r a n c e o f the 2080 c m s o l u t i o n c y a n i d e b a n d , a n d v i c e versa. W h e n
the p o t e n t i a l d r o p s t o - 0 . 9 V a l l t h e [ A u ( C N ) ] ~ c o m p l e x i n s o l u t i o n is r e d u c e d as
2
- 1
i n d i c a t e d b y t h e d i s a p p e a r a n c e o f the 2146 c m b a n d . It is h i g h l y i m p r o b a b l e t h a t
the c o m p l e x c o u l d r e m a i n u n r e d u c e d o n t h e g o l d surface at p o t e n t i a l s m o r e n e g a t i v e
- 1
t h a n - 0 . 9 V . T h e f r e q u e n c y shifting b a n d a r o u n d 2100 c m m u s t therefore b e
assigned t o a single c y a n i d e , l i n e a r l y b o n d e d t o t h e surface.
S i n c e t h e b a n d o f the surface c y a n i d e is s l i g h t l y sharper f o r I R R A S t h a n f o r
S E R S , i s o t o p e e x p e r i m e n t s were c a r r i e d o u t w i t h I R R A S , p a r t l y t o r e e x a m i n e t h e
S E R S i s o t o p e e x p e r i m e n t s r e p o r t e d b y F l e i s c h m a n n et a l . (18). I n F i g u r e 4 a series
1 2 I 3
o f spectra are s h o w n , e a c h f o r a different r a t i o o f C N ~ a n d C N ~ . T h e t o t a l
c o n c e n t r a t i o n o f the c y a n i d e w a s m a i n t a i n e d at 0 . 0 I M a n d t h e spectra were t a k e n at
1 2
- 1 . 0 V w h e r e t h e single i s o t o p e ( C N ~ ) s o l u t i o n gave t h e m a x i m u m i n t e n s i t y .
A l t h o u g h a slight shift i n t h e b a n d frequency is seen w i t h t h e c h a n g e i n c o m p o s i t i o n
( w h i c h w i l l b e d i s c u s s e d later), there is n o n o t i c e a b l e l i n e b r o a d e n i n g w h i c h w o u l d
h a v e b e e n e x p e c t e d d u e t o t h e f o r m a t i o n o f some m i x e d i s o t o p e c o m p l e x e s , i f the
surface species w e r e a d i c y a n o c o m p l e x . T h e fact t h a t there are o n l y t w o d i s t i n c t
f r e q u e n c y b a n d s i n t h e presence o f the t w o i s o t o p e s regardless o f t h e i r r a t i o s u p p o r t s
the single c y a n i d e surface m o d e l . T h i s c o n c l u s i o n i s also consistent w i t h t h e
cluster-adsorbate c o m p u t a t i o n s w h i c h are d i s c u s s e d later. A t this p o i n t suffice i t t o
say t h a t c a l c u l a t i o n s p e r f o r m e d f o r t h e single l i n e a r l y a d s o r b e d c y a n i d e c o u l d a c c o u n t
for a l l t h e essential s p e c t r a l o b s e r v a t i o n s .
Potential Dependent Band Shift
O n e o f the i m p o r t a n t v a r i a b l e s i n t h e e l e c t r o c h e m i c a l s y s t e m is t h e electrode
p o t e n t i a l . B y c o n t r o l l i n g t h e electrode p o t e n t i a l , v e r y h i g h electric fields, u p t o t h e
7
o r d e r o f 10 V / c m , c a n b e a p p l i e d t o a n a d s o r b e d m o l e c u l e o r i o n , w h i c h is n o t as
easily a c c o m p l i s h e d f o r m e t a l - v a c u u m o r metal-gas interfaces. T h e first o b s e r v a t i o n
o f field d e p e n d e n t shift o f the v i b r a t i o n a l b a n d w a s r e p o r t e d i n 1981 b y S E R S

Figure 2. P M - I R R A S (left) a n d S E R S (right) spectra f o r A g electrode i n 0 . 0 1 M

cyanide solution for various potentials, -0.4V to -1.4V ( A g / A g C I ) .

22. SEKI Vibrational Spectroscopy of Simple Ions 327
Figure 3. The reversible change of the IRRAS spectra seen at the Au/O.OIM
CN" interface when the potential is changed from -1.0V to -0.7V and reversed . 25

J I I L
2150 2100 2050 2000
Wavenumber/cm" 1
1 2
Figure 4. Change i n the bands o f the adsorbed C N " with isotopic composition o f C N "
1 3
and C N " while the electrode potential was at - 1 . 0 V and the total cyanide concentration
in the solution is 0.01 M / l . (Reprinted from ref. 25. Copyright 1988 American Chemical
Society.)

i n v e s t i g a t o r s (26,27), i.e., the shift w i t h p o t e n t i a l o f the S E R S b a n d f r o m a n A g

electrode i n c y a n i d e s o l u t i o n . I n the f o l l o w i n g 1982, p o t e n t i a l d e p e n d e n t shift i n the
C O stretching b a n d w a s o b s e r v e d w i t h I R R A S (28,29). E x p e r i m e n t s h a v e also b e e n
carried out for C O o n N i i n U H V (ultra h i g h v a c u u m ) ( 3 0 ) , but f?r lower applied
fields.
S i n c e the d e t e c t i o n o f i n f r a r e d spectra is n o t d e p e n d e n t o n s p e c i a l active sites
as i n S E R S a n d the b a n d s are s l i g h t l y n a r r o w e r , the use o f P M - I R R A S is e s p e c i a l l y
suitable f o r s t u d y i n g the p o t e n t i a l dependent b e h a v i o r , a n d careful studies h a v e b e e n
m a d e o f C O o n P t (31,32) a n d C N " o n A g (22,23), A u (23,25) a n d C u (33). T h e
i n f r a r e d b a n d s o f b c t h l i n e a r l y a n d bridge b o n d e d C O h a v e b e e n o b s e r v e d o n P t
i m m e r s e d i n a c i d s o l u t i o n s (31). T h e p o t e n t i a l d e p e n d e n t b e h a v i o u r o f the l i n e a r l y
b o n d e d C O is s u m m a r i z e d f o r three different acids i n F i g u r e 5, i n w h i c h the i n t e g r a t e d
b a n d i n t e n s i t y a n d the b a n d p o s i t i o n s are p l o t t e d as a f u n c t i o n o f the p o t e n t i a l . T h e
_ 1
frequency shift irrespective o f the a n i o n is c a . 30 c m / V . It s h o u l d be n o t e d t h a t the
i n t e n s i t y o f the C O b a n d is c o n s t a n t o v e r m o s t o f the p o t e n t i a l r a n g e i n d i c a t i n g t h a t
the coverage is c o n s t a n t . T h e r e f o r e the shift i n frequency seen here is n o t due t o
c h a n g e i n the l a t e r a l a d s o r b a t e - a d s o r b a t e i n t e r a c t i o n w h i c h w a s o b s e r v e d as coverage
dependent frequency shift i n U H
O u r investigations o f
h a v e s h o w n t h a t the p o t e n t i a
-
frequency shift seen f r o m C N o n A u is s h o w n i n F i g u r e 6 (25). It is seen t h a t
b e t w e e n -1.2 a n d - 0 . 5 V ( A g / A g C l ) the b a n d i n t e n s i t y is r e l a t i v e l y c o n s t a n t a n d i n this
- 1
r e g i o n there is a l i n e a r rate o f shift o f a b o u t 33 c m / V w h i c h c a n be a t t r i b u t e d
m a i n l y t o the p o t e n t i a l change. O u t s i d e the a b o v e p o t e n t i a l range, the c o v e r a g e is
decreasing a n d the shift deviates f r o m the l i n e a r i t y . T h i s d e v i a t i o n f r o m l i n e a r i t y c a n
be c o n s i d e r e d t o be due t o decrease i n frequency w i t h surface c o n c e n t r a t i o n w h i c h is
seen i n F i g u r e 4 a n d m o r e e x p l i c i t l y p l o t t e d i n F i g u r e 7. F i g u r e s 6 a n d 7 s h o w t h a t
the the t o t a l shift due t o the field o r p o t e n t i a l is larger t h a n t h a t due to the coverage.
T h e d i r e c t i o n o f the p o t e n t i a l shift o f the surface C - N b a n d is the same as f o r
the C - O b a n d o n P t a n d the shift rates are c a . 30 c m - y v f o r A g a n d A u (22,23,25)
_ 1
a n d ca. 45 c m / V f o r C u (33). T h e m e a s u r e m e n t f o r c o p p e r is less a c c u r a t e due t o
f o r m a t i o n o f i o n c o m p l e x e s w i t h large a b s o r p t i o n c r o s s e c t i o n s a n d the r e l a t i v e l y w e a k
s i g n a l f r o m the surface species itself.
T h e most widely accepted m o d e l o f C O linearly adsorbed o n metal, based o n
studies o f m e t a l c a r b o n y l s (37), is w i t h C t o w a r d s the m e t a l . T h e b o n d is c o v a l e n t
w i t h the l o n e p a i r 5o- o r b i t a l d o n a t i n g charge to the m e t a l w h i l e there is a n b a c k
d o n a t i o n i n t o the e m p t y C O 2n* l e v e l (38). T h e o c c u p a t i o n o f the a n t i b o n d i n g 2n*
o r b i t a l w e a k e n s the C - O b o n d a n d causes the l o w e r i n g o f the C - O v i b r a t i o n o f the
a d s o r b e d C O . T h u s it is r e a s o n a b l e t o p r o p o s e t h a t this b a l a n c e o f charge exchange
i n the o r b i t a l s is affected b y the a p p l i e d field, a l t e r i n g the C - 0 force c o n s t a n t
(39,40). F a c e d w i t h the s i m i l a r i t y o f the p o t e n t i a l d e p e n d e n t b a n d shift a n d the fact
-
t h a t C O a n d C N are i s o e l e c t r o n i c , it c o u l d be a r g u e d t h a t the o b s e r v e d p o t e n t i a l
-
d e p e n d e n t shift is due t o s i m i l a r m e c h a n i s m s f o r b o t h C O a n d C N . I n d e e d this
-
e x p l a n a t i o n w a s g i v e n f o r the i n i t i a l o b s e r v a t i o n o f the C N frequency shifts (41).
L a m b e r t h o w e v e r p r o p o s e d a n i n t e r e s t i n g a l t e r n a t i v e e x p l a n a t i o n , i.e., the
p o t e n t i a l d e p e n d e n t frequency shift c a n be e x p l a i n e d b y a first-order S t a r k effect
w i t h o u t i n v o l v i n g a change i n the c o v a l e n t b o n d i n g due t o the field (42). T h i s w a s
d e m o n s t r a t e d b y c a l c u l a t i n g the S t a r k t u n i n g rates u s i n g first order p e r t u r b a t i o n
t h e o r y a n d e x p e r i m e n t a l l y m e a s u r e d v i b r a t i o n a l frequencies a n d m o l e c u l a r c o n s t a n t s
o f a n u m b e r o f m o l e c u l e s ( i n c l u d i n g C O ) i n the gas phase.
S C F Cluster Calculations
T h e d e v e l o p m e n t o f ab-initio self-consistent field ( S C F ) w a v e f u n c t i o n s f o r clusters

b y B a g u s et a l . p r o v i d e s a p o w e r f u l basis f o r i n t e r p r e t i n g the e x p e r i m e n t a l
o b s e r v a t i o n s r e l a t e d t o the l o c a l i z e d b o n d i n g o f a d s o r b e d m o l e c u l e s (43-47). I n these

E/V(NHE)
Figure 5. The integrated band intensity (1) and the band position (2) of linearly adsorbed
CO are plotted as a function of potential in (a) 1 M HC10 , (b) 1 M H S0 , and (c) 1 M
4 2 4
HC1. (Reprinted from ref. 31. Copyright 1985 American Chemical Society.)

Figure 6. The potential dependenc (1) (2) integrate

-
intensity of adsorbed CN~ on Au, and (3) the integrated band intensity of the [AutCN)^
complex. (Reprinted from ref. 25. Copyright 1988 American Chemical Society.)
Au/( CN"+ CN")

12 13
I I I I I I I I I I I
0 50 100
% 1 3
CN"
12 13
Figure 7. The dependence of the C-N bands of the adsorbed CN" and CN~ on the
isotopic composition based on the data of Figure 4. (Reprinted from ref. 25. Copyright
1988 American Chemical Society.)

c a l c u l a t i o n s t h e m e t a l surface is represented b y a m e t a l cluster w h i c h ranges i n size

f r o m a single m e t a l a t o m u p t o o v e r 30 m e t a l a t o m s , t h e larger cluster g i v i n g ,
generally, m o r e r e a l i s t i c results at t h e cost o f i n c r e a s e d c o m p u t a t i o n a l t i m e .
S u b s t i t u t i o n o f t h e r e a l surface w i t h a m e t a l cluster is a n a p p r o x i m a t i o n a r d w e a k e n s
the v a l i d i t y o f t h e c o m p u t a t i o n a l results relative t o t h e cases o f a n i s o l a t e d m o l e c u l e .
H o w e v e r t h e a d v a n t a g e o f t h e ab initio m e t h o d , t h a t i t does n o t i n v o l v e adjustable
p a r a m e t e r s t o fit t h e e x p e r i m e n t a l results, is still q u i t e persuasive.
V e r y briefly w h a t this m e a n s is t h e f o l l o w i n g : T h e electrons i n the s y s t e m
(cluster) are d e s c r i b e d b y m o l e c u l a r o r b i t a l s w h i c h generally c o n s i s t o f a s u m o f a
finite set o f basis f u n c t i o n s (e.g., a t o m i c o r b i t a l s ) , e a c h basis f u n c t i o n h a v i n g a
coefficient. T h e w a v e f u n c t i o n o f the s y s t e m is a Slater d e t e r m i n a n t o f these m o l e c u l a r
o r b i t a l s . T h e S C F w a v e f u n c t i o n , f o r a g i v e n fixed p o s i t i o n o f t h e a t o m s , is
d e t e r m i n e d b y c a r r y i n g o u t v a r i a t i o n a l S C F c o m p u t a t i o n s o f t h e t o t a l energy o f t h e
system, i.e., t h e coefficients o f t h e basis f u n c t i o n s are v a r i e d i n order t o select a set
o f coefficients w h i c h gives t h e m i n i m u m energy. T h e r e are n o e m p i r i c a l p a r a m e t e r s
w h i c h c a n b e adjusted t o m a t c h t h e results t o e x p e r i m e n t . T h e i n v e s t i g a t o r c h o o s e s
the m o d e l f o r t h e c a l c u l a t i o n , i.e., t h e basis set, its size, the level o f s o p h i s t i c a t i o n o f
the c o m p u t a t i o n (e.g., c o n f i g u r a t i o
potentials to approximate th
validity o f the c o m p u t a t i o n i y Physica insigh
c o m p u t a t i o n a l experience are needed t o m a k e t h e a p p r o p r i a t e s e l e c t i o n o f t h e
c o m p u t a t i o n a l m o d e l d e p e n d i n g o n t h e i n f o r m a t i o n b e i n g sought. T h i s u s u a l l y
involves trade o f f w i t h the c o m p u t a t i o n a l power a n d time available. ( A m o r e
c o m p l e t e d i s c u s s i o n o f t h e ab-initio m e t h o d s c a n b e f o u n d e.g., i n reference (48)).
T h e degree o f c o n f i d e n c e w e c a n h a v e i n t h e c o m p u t a t i o n a l result is u l t i m a t e l y
d e t e r m i n e d b y t h e a b i l i t y o f t h e m o d e l t o p r o d u c e results w h i c h agree w i t h
e x p e r i m e n t s . A s a n e x a m p l e , t h e e q u i l i b r i u m i n t e r a t o m i c distance o f a m o l e c u l e is
o b t a i n e d b y c o m p u t i n g t h e S C F energy f o r v a r i o u s a t o m i c separations a n d f i n d i n g
the l o c a t i o n f o r t h e r n i n i m u m energy. T h e m o d e l s u s e d i n t h e w o r k here h a v e b e e n
successful i n a r r i v i n g at t h e p r o p e r a d s o r p t i o n b o n d distances (44) a n d i n i n t e r p r e t i n g
p h o t o e m i s s i o n spectra (43).
M o s t o f t h e c a l c u l a t i o n s h a v e b e e n d o n e f o r C u since i t h a s t h e least n u m b e r
o f electrons o f t h e m e t a l s o f interest. T h e clusters represent t h e C u ( 1 0 0 ) surface a n d
the p o s i t i o n s o f t h e m e t a l a t o m s are f i x e d b y b u l k fee g e o m e t r y . T h e a d s o r p t i o n site
m e t a l a t o m is u s u a l l y t r e a t e d w i t h a l l i t s electrons w h i l e t h e rest are treated w i t h o n e
4s e l e c t r o n a n d a p s e u d o p o t e n t i a l f o r t h e core electrons. H i g h e r z metals c a n b e
s t u d i e d b y u s i n g p s e u d o p o t e n t i a l s f o r a l l t h e metals i n t h e cluster. T h e a d s o r b e d
m o l e c u l e is treated w i t h a l l its electrons a n d t h e e q u i l i b r i u m p o s i t i o n s are d e t e r m i n e d
b y m i n i m i z i n g t h e S C F energy. T h e p o s i t i o n s o f t h e a d s o r b a t e a t o m s are v a r i e d
a r o u n d t h e e q u i l i b r i u m p o s i t i o n a n d S C F energies at several p o i n t s are fitted t o a
p o t e n t i a l surface t o o b t a i n t h e i n t e r a t o m i c force c o n s t a n t s a n d t h e v i b r a t i o n a l
frequency.
T h e ab initio S C F cluster w a v e f u n c t i o n h a s b e e n u s e d t o investigate t h e
-
b o n d i n g o f C O a n d C N o n C u (5,4,1), (5 surface layer, 4 s e c o n d l a y e r a n d 1 b o t t o m
1 0
l a y e r a t o m s ) , a n d t o c a l c u l a t e t h e i r field d e p e n d e n t v i b r a t i o n a l frequency shifts i n

7
fields u p t o 5.2 x 1 0 V / c m ( 4 6 ) . A s c h e m a t i c v i e w o f t h e C u ( 5 , 4 , l ) C O c l u s t e r is
1 0
s h o w n i n F i g u r e 8. I n order t o assess t h e significance o f L a m b e r t ' s p r o p o s a l , t h a t t h e

l i n e a r S t a r k effect i s t h e d o m i n a n t f a c t o r i n t h e field d e p e n d e n t frequency shift, t h e
effect o f t h e field w a s c a l c u l a t e d b y three m e t h o d s . O n e is b y a fully v a r i a t i o n a l
a p p r o a c h (i.e., t h e a d s o r b a t e is a l l o w e d t o r e l a x u n d e r t h e influence o f the a p p l i e d
field) i n w h i c h the H a m i l t o n i a n f o r t h e cluster i n a u n i f o r m electric field, F , i s g i v e n
by

where i- and R^ are the position of the electrons and the nuclei of the adsorbate. The
energy obtained from this Hamiltonian is E (F) and the resulting wavefunction
SCF
includes the total effect of the field, changes in the chemical bonding and the Stark
effect. The second method uses first-order perturbation theory energy,
E (F)= E (0) — /i(0)F where E {0) and /i(0) are the zero field SCF energy and
p SCF SCF
dipole moment, respectively. The third method follows the formalism of Lambert
(42) in which Taylor series expansions of the ligand potential and the dipole moment
are used. The coefficients in the expansions are calculated from the zero field SCF
wavefunctions, instead of using the measured molecular parameters as was done by
Lambert. The latter two methods calculate changes based on zero field parameters
and do not involve changes in the chemical bonding. (For a complete description and
discussion of the SCF cluster analysis in general, references given here (43-47) and
references therein should be consulted).
The frequency shifts calculated by the latter two methods agree quite well as
might be expected since both are essentially variations of first order perturbation
theory. More importantly, the difference between the shifts calculated by the fully
SCF method and the pertubation methods are relatively small and this endorses the
proposal by Lambert (42) tha
7
of 10 V/cm arise mainly from
claimed by Bauschlicher (49) bu was based only o results o SC calculations o
the isolated CO in an applied field parallel to the molecule). The results of these
analyse hs also showed that the metal-ligand bonding for CO and CN~ is quite
different. In the case of CO the bond is covalent with dominantly metal to CO 2k*
-
back donation and for C N the bonding is mainly ionic. It is also interesting that the
bond energy did not change very much, when the orientation of CN~ was changed,
consistent with the picture that covalency of the bonding is small. The fact that the
infrared intensity of the surface C-N stretch is weak on Cu most likely is an indication
-
that all the C N is not oriented perfectly normal to the surface. Since the intensity
is stronger on Ag and Au electrodes, this may indicate that as the metal d shell is
filled the covalency of the metal ligand bond increases and the degree of normal
orientation improves.
It is quite interesting that due to this difference in the bonding, the way by
which the field affects the frequency is different for the two adsorbates. In the case
-
of CO the change is a direct change in ligand frequency but in the case of C N the
change in the calculated ligand frequency is considerably smaller than for CO. This
does not agree with the experimental observation that the frequency shifts were
-
comparable for CO and C N . This discrepancy is resolved by recognizing that the
ligand vibration and the metal ligand vibration are coupled. Due to the ionicity of
_
the metal-CN bond, the Cu-C distance and the metal ligand frequency are changed
appreciably by the applied field. Through the interaction between the two oscillators
the frequency of the normal mode corresponding to the C-N stretch is also increased.
This has been investigated in more detail using a Cu (5,4,5)CO cluster (47) which
14
can be visualized by surrounding the bottom Cu atom in Figure 8 with 4 more Cu

atoms. In this study it is shown more clearly how the change in the Cu-C distance
also causes a change in the ligand force constant due to a "wall" effect of the metal
surface electrons and this brings the C-N vibrational frequency shift within a factor
of 2 of the C-O frequency shift. The shift in the metal cyanide frequency was, in fact,
reported in the initial SERS observation of the potential dependent shifts (26,27).
The final experimental verification of these analyses will be to see if the metal-ligand
stretching frequency for CO is little affected by the field as our model predicts.
Azide on Silver
Recently the vibrational spectra of azide (N3) on Ag has been investigated using PM
FTIRRAS (50). In solution the azide ion has two vibrational modes, the Raman
-1
active symmetric mode at ca. 1340 cm and the ir active asymmetric mode at

- 1
ca. 2050 c m . T h e surface species w a s i d e n t i f i e d w i t h some difficulty d u e t o t h e
n a r r o w p o t e n t i a l r a n g e i n w h i c h i t c o u l d b e seen a n d the presence o f a n intense b a n d
o f the s o l u t i o n N y . T h e spectra o f t h e surface species c a n be seen i n F i g u r e 9 shifting
- 1 - 1
f r o m 2048 c m t o 2083 c m . T h e b a n d d u e t o the su-face species is seen i n t h e
potential range o f about 0 to 0 . 2 5 V ( A g / A g C l ) . Differential capacitance
m e a s u r e m e n t s h o w e v e r h a v e i n d i c a t e d t h a t a z i d e is a d s o r b e d o n t h e A g electrode o v e r
the range e x t e n d i n g d o w n t o - 0 . 9 V (50,51). T h e frequency o f the b a n d shifts w i t h
- 1
p o t e n t i a l at a b o u t 100 c m / V , a s s u m i n g a l i n e a r dependence. T h e s e spectra were
extracted b y s u b t r a c t i n g t h e s p e c t r u m at - 0 . 9 5 V w h e r e differential c a p a c i t a n c e
m e a s u r e m e n t s (51,52) a n d S E R S m e a s u r e m e n t s i n d i c a t e there is n o azide a d s o r p t i o n
(53,54).The i n t e r p r e t a t i o n o f t h e a z i d e I R R A S spectra w a s also f a c i l i t a t e d b y t h e
c o m p u t a t i o n s o f the ab-initio S C F w a v e f u n c t i o n s (50). I n this case the simplest
cluster, c o n s i s t i n g o f a single A g a t o m , w a s used. T h e objective w a s m o r e t o identify
trends a n d changes i n t h e values relevent t o t h e surface spectra r a t h e r t h a n t o o b t a i n
precise v a l u e s o f m o l e c u l a r p a r a m e t e r s a n d v i b r a t i o n a l frequencies. T h e clusters,
[ A g N ] ° a n d [ A g N ] ~ , i n t w o geometries were investigated. I n o n e w i t h
3 3
s y m m e t r y , t h e A g a t o m a n d t h e azide are c o l i n e a r , m o d e l l i n g t h e azide a d s o r b e d

n o r m a l t o t h e A g surface, a n
b e n e a t h t h e center o f t h e l i n e a
surface. T h e c a l c u l a t i o n s s h o
frequency shift is also d u e m a i n l y t o t h e first order S t a r k effect. W h e n N y is c o l i n e a r
7
w i t h t h e A g a t o m t h e effect o f a p p l i e d fields o f ± 5.2 x 1 0 V / c m is t o greatly alter t h e
-
A g - a z i d e distance. A s i n the case o f C N (47), this t h e n causes t h e a s y m m e t r i c m o d e
frequency t o shift. H o w e v e r t h e a n a l y s i s , i n t e r e s t i n g l y , shows t h a t t h e field d e p e n d e n t
shifts i n t h e s y m m e t r i c m o d e f r e q u e n c y f o r b o t h t h e c o l i n e a r a n d flat o r i e n t a t i o n s are
m u c h s m a l l e r t h a n that i n t h e a s y m m e t r i c m o d e .
W h e n t h e e x p e r i m e n t a l results are c o n s i d e r e d together w i t h the c a l c u l a t i o n s
the f o l l o w i n g m o d e l c a n b e e n v i s i o n e d . I n t h e r e g i o n o f negative p o t e n t i a l N is 3
a d s o r b e d p a r a l l e l t o t h e surface a n d c a n n o t b e o b s e r v e d b y I R R A S . T h e s y m m e t r i c
v i b r a t i o n a n d t h e b e n d i n g m o d e s are o b s e r v e d i n this r e g i o n b y S E R S (53) a n d t h e
v i b r a t i o n a l frequency is n o t seen t o shift v e r y m u c h w i t h p o t e n t i a l , consistent w i t h t h e
S C F c a l c u l a t i o n s . A s t h e p o t e n t i a l is m a d e m o r e p o s i t i v e the c o n c e n t r a t i o n increases
a n d a d s o r p t i o n tends t o p e r p e n d i c u l a r o r i e n t a t i o n w h i c h is detected b y I R R A S .
Summary
E x a m p l e s o f i n v e s t i g a t i o n , w h i c h i n v o l v e in-situ v i b r a t i o n a l s p e c t r o s c o p y o f t h e
electrolyte interface, h a v e b e e n r e v i e w e d , d e m o n s t r a t i n g the k i n d o f i n s i g h t s u c h
spectral d a t a c a n p r o v i d e . B y a c o m b i n a t i o n o f S E R S , I R R A S a n d i s o t o p e effects it
c a n b e e n c l e a r l y seen t h a t t h e structure o f c y a n i d e a d s o r b e d o n C u , A g a n d A u
electrodes is l i n e a r l y b o n d e d t o t h e surface. T h i s s i m p l e c o n c l u s i o n is i m p o r t a n t since
alternative, m o r e c o m p l e x structures h a v e b e e n discussed i n t h e literature u n t i l q u i t e
recently. Ab-initio S C F cluster c a l c u l a t i o n s s t r o n g l y suggest t h a t t h e b o n d i n g o f
c y a n i d e t o the m e t a l is essentially i o n i c . T h e a b i l i t y t o c o n t r o l t h e p o t e n t i a l i n a n
e l e c t r o c h e m i c a l c e l l a n d hence t h e field a p p l i e d t o t h e a d s o r b a t e p r o v i d e s a p o w e r f u l
h a n d l e i n the i n v e s t i g a t i o n o f t h e a d s o r b a t e substrate i n t e r a c t i o n . T h e p o t e n t i a l
dependent shift o f t h e v i b r a t i o n a l b a n d c a n serve t o identify w h e t h e r t h e source is a
surface species. T h e case o f C O a n d C N " i l l u s t r a t e t h a t i n s i g h t i n t o t h e m e c h a n i s m s
u n d e r l y i n g this shift c a n b e g a i n e d i n m o l e c u l a r d e t a i l t h r o u g h c a l c u l a t i o n s o f ab-initio
S C F w a v e f u n c t i o n s o f clusters. W h a t h a s b e e n presented here is o n l y a b e g i n n i n g .
T h e v e r y r a p i d a d v a n c e i n t h e c o m p u t o r t e c h n o l o g y w i l l i n s u r e t h a t w e w i l l see
increasingly more sophisticated computations o f more complex molecules a n d
clusters. T h i s w i l l greatly e n h a n c e t h e v a l u e o f d a t a o b t a i n e d b y v i b r a t i o n a l
s p e c t r o s c o p y . I n c o m b i n a t i o n w i t h o t h e r in-situ t e c h n i q u e s s u c h as differential
c a p a c i t a n c e m e a s u r e m e n t s , r a d i o t r a c e r m e a s u r e m e n t s , X - r a y scattering a n d q u a r t z

Figure 8. A schematic view of the C u (5,4,l)CO cluster. (Reprinted with permission

1 0
from ref. 45b. Copyright 1985 American Institute of Physics.)
2100 2000
—i 1 1 1 1 1—
1 i i i i i i I
2100 2000
Wavenumbers ( c m ) - 1
Figure 9. P M - I R R A S spectra for A g electrode i n 0.03 M azide i n 0.1 M N a C 1 0 . These

4
are obtained by taking the difference of the spectra taken at the specified potential and at
-0.95 V (Ag/AgCI). (Reprinted with permission from ref. 50. Copyright 1988 American
Institute of Physics.)

c r y s t a l m i c r o b a l a n c e w e c a n expect e x c i t i n g progress i n o u r u n d e r s t a n d i n g o f the

electrode electrolyte interface.
Acknowledgment
T h e w o r k has b e e n s u p p o r t e d i n p a r t b y the Office o f N a v a l R e s e a r c h . A large p a r t

o f the w o r k discussed here w a s d o n e i n c o l l a b o r a t i o n w i t h m y colleagues, P . S. B a g u s ,
W . G . Golden, J . G . G o r d o n , K . Kunimatsu, C . J . Nelin, M . R . Philpott,
M . G . S a m a n t . I h a v e benefitted greatly f r o m this pleasant i n t e r a c t i o n for w h i c h I
a m v e r y grateful. I t h a n k O . M e l r o y for c o n s t r u c t i v e c o m m e n t s r e g a r d i n g the
manuscript.
References
1. Jeanmaire, D. J.; Van Duyne, R. P. J. Electroanal. Chem. 1977, 84, 1.

2. Creighton, J. A. J. Am. Chem. Soc. 1977, 99, 5215.
3. Bewick, A.; Kunimatsu
4. Surface Enhanced Rama
Press, N. Y., 1982.
5. Seki, H.; Kunimatsu, K.; Golden, W. G. Appl. Spectrosc. 1984, 39, 437.
6. Kunz, R. E.; Gordon, J. G., II; Philpott, M. R.; Girlando, A. J. Electroanal.
Chem. 1980, 112, 391.
7. Pettinger, B.; Philpott, M. R.; Gordon, J. G., II, J. Chem. Phys. 1981, 74, 934.
8. Beden, B.; Lamy, C.; Bewick, A.; Kunimatsu, K. J. Electroanal. Chem. 1981,
122, 343.
9. Bewick, A.; Pons, S. Adv. Infrared Raman Spectrosc. 1985, 12, 1.
10. Corrigan, D. S.; Weaver, M. J. J. Phys. Chem. 1986, 90, 5300.
11. Corrigan, D. S.; Leung, L. H.; Weaver, M. J. Anal Chem. 1987, 59, 2252.
12. Golden, W. G.; Dunn, D. S.; Overend, J. J. Catal. 1981, 71, 395.
13. Golden, W. G.; Saperstein, D. D. J. Electron Spectrosc. 1983, 30, 43.
14. We have been using the Hinds International, PEM-80 Series II ZnSe
photoelectic modulator which modulates the polarization at 74kHz.
15. Greenler, R. G. J. Chem. Phys. 1966, 44, 310.
16. Otto, A. Surface Sci. 1978, 75, L392.
17. Furtak, T. E. Solid State Commun. 1978, 28, 903.
18. Fleischmann, M.; Hill, I. R.; Pemble, M. E. J. Electroanal. Chem. 1982, 136,
362.
19. Baltruschat, H.; Vielstich, W. J. Electroanal. Chem. 1983, 154, 141.
20. Baltruschat, H.; Heitbaum, J. J. Electroanal. Chem. 1983 .us 157, 319.
21. H. Seki, K. Kunimatsu and W. G. Golden, presented at the meeting of the
International Society of Electrochemistry, Berkeley, 1984.
22. Kunimatsu, K.; Seki, H.; Golden, W. G. Chem. Phys. Letters 1984, 108, 195.
23. Kunimatsu, K.; Seki, H.; Golden, W. G.; Gordon, J. G., II and
Philpott, M . R. Surface Sci. 1985, 158, 596.
24. Jones, L. H.; Penneman, R. A. J. Chem. Phys. 1954, 22, 965.
25. Kunimatsu, K.; Seki, H.; Golden, W. G.; Gordon, J. G., II; Philpott, M. R.
Langmuir in press, 1988.
26. Kötz, R.; Yeager, E. J. Electroanal. Chem. 1981, 123, 335.
27. Wetzel, W.; Gerischer, H.; Pettinger, B. Chem. Phys. Lett. 1981, 80, 159.
28. Kunimatsu, K. J. Electroanal. Chem. 1982, 140, 205.
29. Russell, J. W.; Overend, J.; Scanlon, K.; Severson, M.; Bewick, A. J. Phys.
Chem. 1982, 86, 3066.
30. Lambert, D. K. Solid State Comm. 1984, 51, 297.
31. Kunimatsu, K.; Golden, W. G.; Seki, H.; Philpott, M. R. Langmuir 1985, 1,
245.

32. Kunimatsu, K.; Seki, H.; Golden, W. G.; Gordon, J. G., II; Philpott, M. R.
Langmuir. 1986, 2, 464.
33. Lee, K. A. B.; Kunimatsu, K.; Gordon, J. G., II; Golden, W. G.; Seki, H.
J. Electrochem. Soc. 1987, 134, 1676.
34. Shigeishi, R. A.; King, D. A. Surface Sci. 1976, 58, 379.
35. King, D. A., in Vibrational Spectroscopy of adsorbates, edited by
Willis, R. F., Springer Series in Chem. Phys. 15, Springer-Verlag, Berlin, 1980.
36. Hayden, B. E.; Bradshaw, A. M. Surf. Sci. 1983, 125, 787.
37. Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 3rd edition,
John Wiley, New York, 1972.
38. Blyholder, G. J. Phys. Chem. 1964, 68, 2773.
39. Ray, N. K.; Anderson, A. B. J. Phys. Chem. 1982, 86, 4851.
40. Holloway, S.; Norskov, J. K. J. Electroanal. Chem. 1984, 161, 193.
41. Anderson, A. B.; Kötz, R.; Yeager, E. Chem. Phys. Lett. 1981, 82, 130.
42. (a) Lambert, D. K. J. Electron. Spectrosc. 1983, 30, 59; (b) Lambert, D. K.
Phys Rev. Letters 1983, 50, 2106; (c) Lambert, D. K. Solid State Commun.
1984, 51, 297.
43. Bagus, P. S.; Hermann
44. (a) Bagus, P. S.; Nelin,
(b) Bagus, P. S.; Nelin, C. J.; Bauschlicher, C. W. J. Vac. Sci. Technol. 1984,
A2, 905.
45. (a) Bagus, P. S.; Müller, W. Chem. Phys. Letter 1985, 115, 540;
(b) Müller, W.; Bagus, P. S. J. Vac. Sci. Technol. 1985 A, 3, 1623; (c) Müller,
W.; Bagus, P. S. J. Electron. Spectrosc. 1986, 38, 103.
46. Bagus, P. S.; Nelin, C. J.; Müller, W.; Philpott, M. R.; Seki, H. Phys. Rev.
Letters 1987, 58, 559.
47. Bagus, P. S.; Nelin, C. J.; Hermann, K.; Philpott, M. R. Phys. Rev. B 1987,
36, 8169.
48. H. F. Schaefer, III, Electronic Structure of Atoms and Molecules ,
Addison-Wesley, Reading, Mass., 1972, and Quantum Chemistry , Clarendon
Press, Oxford, 1984.
49. Bauschlicher, C. W. Chem. Phys. Letter 1985, 118, 307.
50. Samant, M. G.; Viswanathan, R.; Seki, H.; Bagus, P. S. Nelin, C. J.;
Philpott, M . R. J. Chem. Phys. 58, submitted, 1988.
51. Larkin, D.; Guyer, K. L.; Hupp, J. T.; Weaver, M. J. J. Electroanal. Chem.
1982, 113, 401.
52. Hupp, J. T.; Larkin, D.; Weaver, M. J. Surf. Sci. 1983, 125, 429.
53. Kunz, R. E.; Gordon, J. G., II; Philpott, M. R.; Girlando, A. J. Electroanal.
Chem. 1980, 112, 391.
54. Corrigan, D. S.; Gao, P.; Leung, L. H.; Weaver, M. J. Langmuir 1986, 2, 744.
55. Corrigan, D. S.; Weaver, M. J. J. Phys. Chem. 1986, 90, 5300.
R E C E I V E D May 17, 1988

Chapter 23
Infrared Spectroelectrochemistry
of Surface Species
In Situ Surface Fourier Transform Infrared Study
of Adsorption of Isoquinoline at a Mercury Electrode
1 2 1 1
Daniel Blackwood , Carol Korzeniewski , William McKenna , Jianguo Li ,
1
and Stanley Pons
1
Department of Chemistry, University of Utah, Salt Lake City,
UT 84112
2
Department of Chemistry University of Michigan Ann Arbor
Subtractively normalized i n t e r f a c i a l Fourier

transform i n f r a r e d spectroscopy (SNIFTIRS), has been
used extensively to examine interactions of species
at the electrode/electrolyte interface. In the
present work, the method has been extended to probe
interactions at the mercury s o l u t i o n i n t e r f a c e . The
diminished p o t e n t i a l dependent frequency s h i f t s of
species adsorbed at mercury electrodes are compared
with s h i f t s observed for s i m i l a r species adsorbed at
d-band metals.
Several spectroscopic techniques have been developed for the
i n v e s t i g a t i o n of electrode - s o l u t i o n i n t e r f a c i a l phenomena (1-7).
The i n f r a r e d techniques include ( i ) s u b t r a c t i v e l y normalized
i n t e r f a c i a l Fourier transform i n f r a r e d spectroscopy, (SNIFTIRS) (7)
i n which i n f r a r e d spectra are c o l l e c t e d at two d i f f e r e n t p o t e n t i a l s
and a difference spectrum obtained by subtraction and normalization,
( i i ) electrochemically modulated i n f r a r e d spectroscopy, EMIRS (4), a
dispersive spectrophotometric technique i n which the electrode
p o t e n t i a l i s modulated at a set frequency and the r e s u l t i n g
attenuation of the r e f l e c t i n g i n f r a r e d r a d i a t i o n i s analyzed by phase
s e n s i t i v e detection, and ( i i i ) i n f r a r e d r e f l e c t i o n absorption
spectroscopy, IRRAS (6), i n which the p o l a r i z a t i o n of the incident
i n f r a r e d r a d i a t i o n i s modulated at a high rate (ca. 74 kHz) between
the s- and the p- states to d i s t i n g u i s h between adsorbed and s o l u t i o n
dissolved i n f r a r e d absorbers. The attenuated i n f r a r e d s i g n a l i s
again monitored with the a i d of phase s e n s i t i v e detection techniques.
The c h a r a c t e r i s t i c s of the two types of spectra are l i s t e d i n Table
I. The s e l e c t i o n rules that determine i n t e r a c t i o n of i n f r a r e d
r a d i a t i o n with adsorbates are w e l l known, and a r i s e from the
differences i n the r e l a t i v e i n t e n s i t i e s of the s- and p-polarized
components of the electromagnetic f i e l d vectors of the incident
i n f r a r e d r a d i a t i o n at the metal-solution interface. The s-polarized
component undergoes a phase s h i f t upon r e f l e c t i o n from a metal
surface which r e s u l t s i n zero f i e l d strength at the surface, while
the p-component f i e l d strength increases at the surface as the angle
0097-6156/88/0378-0338$06.00/0
* 1988 American Chemical Society

23. B L A C K W O O D ET AL. Infrared Spectroelectrochemistry of Surface Species 339
Table I. A Comparison of the C h a r a c t e r i s t i c s of Infrared

V i b r a t i o n a l Bands A r i s i n g from Bulk Solution
Species and Adsorbed Species
BULK SOLUTION SPECIES ADSORBED SPECIES

i) Bands present with either s- i) Bands present only with
or p-polarized l i g h t . p-polarized l i g h t .
i i ) Band positions independent of ii) Band positions may
potential. s h i f t with p o t e n t i a l .
i i i ) Relative i n t e n s i t y of bands i i i ) Relative i n t e n s i t y may
independent of p o t e n t i a l . change with p o t e n t i a l .
i v ) Normally IR inactive bands iv) Some may be observed.
not observed.
of incidence increases. As a r e s u l t , only p-polarized l i g h t can

i n t e r a c t with species which are either adsorbed onto or are very
close to the electrode surface
adsorbate that i n t e r a c t
the derivative of the dipole moment (with respect to the normal
coordinate) perpendicular to the metal surface. In addition, modes
of an adsorbate activated by v i b r o n i c coupling to the surface may
i n t e r a c t with the r a d i a t i o n (vide i n f r a ) .
P o t e n t i a l dependence of the frequencies of i n f r a r e d bands a r i s e
because of the change i n extents of bonding of the adsorbate to the
metal surface as the p o t e n t i a l i s changed. The e f f e c t has been
explained by several models (vide i n f r a ) . To i l l u s t r a t e the
p o t e n t i a l dependence of adsorbed species, the SNIFTIRS spectra of the
b 3 r i n g bending mode of p-difluorobenzene a t a platinum electrode i s
u
i l l u s t r a t e d i n Figure 1 (8) The upward pointing band i s c l e a r l y

independent of p o t e n t i a l and i s assigned to the s o l u t i o n species
whereas the p o s i t i o n of the downward pointing band s h i f t s
monotonically (at constant i o n i c strength) with p o t e n t i a l and i s
therefore due to an adsorbed species.
The p a r t i c u l a r system investigated i n t h i s work was the
adsorption of isoquinoline at a mercury electrode, which has been
previously studied by several techniques, including e l e c t r o c a p i l l a r y
measurements (9), ellipsometry (10), double layer capacity
measurements (11), and a range of p o t e n t i a l step techniques (12-15).
The i n t e r e s t i n t h i s system i s due i n part to the f a c t that one
observes w e l l defined t r a n s i t i o n s i n the measurements as the adsorbed
molecules undergo t r a n s i t i o n s i n surface o r i e n t a t i o n and packing
density under c e r t a i n experimental conditions. Isoquinoline has been
shown to be adsorbed on mercury i n four d i f f e r e n t orientations
(Figure 2). The previous investigations indicate the following
behavior for the isoquinoline o r i e n t a t i o n as a function of p o t e n t i a l
and concentration: at low negative potentials and low bulk
concentrations, the molecules are believed to l i e f l a t on the mercury
surface (molecular plane p a r a l l e l to the surface). On increasing
e i t h e r the p o t e n t i a l ( i n the negative d i r e c t i o n ) or the bulk
concentration, the isoquinoline molecules are forced up into either
the 4,5 p o s i t i o n (10) or the 5,6 p o s i t i o n (9). This r e o r i e n t a t i o n
occurs gradually with the changing coordinates, and proceeds through
a series of phases containing mixtures of these three orientations of
isoquinoline molecules.

Figure 1. SNIFTIRS difference spectra of the D3 r i n g bending

U
mode of p-difluorobenzene at a platinum electrode as a function

of modulation p o t e n t i a l .

23. BLACKWOOD ETAL. Infrared Spectroekctrochemistry of Surface Species 341
Figure 2. L i k e l y orientations f o r the adsorption of isoquinoline

on mercury.

Increases i n the p o t e n t i a l to more negative values (at

s u f f i c i e n t l y high concentrations) r e s u l t s i n an abrupt r e o r i e n t a t i o n
to the 6,7 p o s i t i o n . The reason that t h i s second t r a n s i t i o n i s much
sharper than the f i r s t l i e s i n the f a c t that mixed phases which would
contain the 6,7 o r i e n t a t i o n are e n e r g e t i c a l l y less favorable than a
complete monolayer of any of the pure standing o r i e n t a t i o n a l phases.
G i e r s t et a l (9) have produced a graph showing the dependence of the
s u p e r f i c i a l excess on both p o t e n t i a l and bulk concentration from
t h e i r e l e c t r o c a p i l l a r y data; we reproduce some of t h e i r data i n
Figure 3.
For an isoquinoline molecule adsorbed onto the surface of
mercury, the component of i t s t o t a l dipole moment that i s
perpendicular to the surface w i l l increase as i t s o r i e n t a t i o n changes
from:
Flat - 4 , 5 - 5 , 6 - 6 , 7
As the isoquinoline molecul

absorption of i n f r a r e d r a d i a t i o
would be expected to increase, while that of the out-of-plane modes
would be predicted to decrease ( i n accordance with the surface
s e l e c t i o n r u l e as described above). In the f l a t o r i e n t a t i o n there i s
no component of the dipole moment perpendicular to the surface f o r
the in-plane modes, and under the surface s e l e c t i o n r u l e these modes
w i l l not be able to absorb any of the incident r a d i a t i o n . However,
as mentioned above, i n f r a r e d active modes (and i n some cases i n f r a r e d
forbidden t r a n s i t i o n s ) can s t i l l be observed due to f i e l d - i n d u c e d
v i b r o n i c coupled i n f r a r e d absorption (16-20). We have determined
that t h i s type of i n t e r a c t i o n i s present i n t h i s p a r t i c u l a r system.
EXPERIMENTAL
Isoquinoline ( A l d r i c h 97%) was p u r i f i e d by r e f l u x i n g with BaO f o r 30

minutes and d i s t i l l i n g i n vacuo. The r e s u l t i n g white c r y s t a l l i n e
s o l i d had a melting point of 26°C. The p u r i f i e d isoquinoline was
stored i n the dark, at 0°C and under an argon atmosphere. Mercury
was t r i p l y d i s t i l l e d (American S c i e n t i f i c ) and a l l other chemicals
were of AnalaR grade. Solutions were prepared with t r i p l y d i s t i l l e d
water. Glassware was cleaned i n a 50:50 (v:v) mixture of HNO3 and
H2SO4, and rinsed and steamed ( t r i p l y d i s t i l l e d water) f o r h a l f an
hour. A t h i n layer c e l l was designed (Figure 4) which could be
mounted v e r t i c a l l y on top of the sample chamber of the spectrometer.
The mercury was held i n p o s i t i o n by a glass tube, and e l e c t r i c a l
contact was achieved with a piece of platinum wire inserted into the
mercury. P o t e n t i a l s are measured with respect to a saturated calomel
electrode (SCE).
The technique used to acquire the data i n t h i s paper was
SNIFTIRS. A schematic diagram of the required apparatus i s shown i n
Figure 5, and has been described i n d e t a i l elsewhere. The FTIR
spectrometer used was a vacuum bench Bruker IBM Model IR/98, modified
so that the o p t i c a l beam was brought upwards through the sample
compartment and made to r e f l e c t from the bottom of the h o r i z o n t a l
mercury surface. The methods used herein are adapted from a
configuration that has been used by Bewick and co-workers (21) at
Southampton.

23. BLACKWOOD ETAL. Infrared Spectroelectrochemistry ofSurface Species 343
'o
a 7.50
5.00
2.50
w
o
<
0.00
CO
0.00
-POTENTIAL / VOLTS vs. SCE

Figure 3. S u p e r f i c i a l excess as a function of p o t e n t i a l f o r a
3
mercury electrode i n 0.5 mol dm" Na2S04 and the f o l l o w i n g
isoquinoline concentrations: (a) 2.1 x 10"^ (saturated),
3 4 3
(b) 6.3 x 10" , and (c) 2.1 x 10" mol-dm" . (Data from G i e r s t et
a l . (9))
Pt Contact Electrode
Glass Tube for Holding

Mercury in Position
Vapor Lock
Secondary Electrode
Mercury Pool Electrode
Trapped Solution Thin Layer
Calcium Fluoride Window
Aluninun
Base Plate
Figure 4. Thin layer mercury reflectance c e l l .

RESULTS AND DISCUSSION
The abrupt t r a n s i t i o n to the 6,7 o r i e n t a t i o n manifests i t s e l f

i n c y c l i c voltammetry as a sharp current spike (Figure 6). The
cathodic spike was found to contain a charge of 2.9 /xC cm"^, while
i t s anodic counterpart contained 3.3 /iC cm"^. The peak separation
was 100 mV; t h i s large value i s due to the large iR losses suffered
i n the t h i n layer c e l l .
Figure 7 shows SNIFTIRS spectra f o r isoquinoline molecules
adsorbed on mercury. The reference spectrum i n each case was
obtained at 0.0V vs. a SCE reference electrode; at t h i s p o t e n t i a l the
molecules are believed to be oriented f l a t on the metal surface. The
v i b r a t i o n a l frequencies of the band structure ( p o s i t i v e values of
absorbance) are e a s i l y assigned since they are e s s e n t i a l l y the same
as those reported by Wait et a l . (22.) f o r pure i s o q u i n o l i n e . The
differences i n the spectra are that the bands f o r the adsorbed
species e x h i b i t blue s h i f t i n g of 3-4 cm"^ r e l a t i v e to those of the
neat m a t e r i a l , and the r e l a t i v
adsorbed species are markedl
The major v i b r a t i o n a l modes observed f o r isoquinoline are l i s t e d
i n Table I I . The assignments made by Wait et a l . (22) are also
included. These authors made t h e i r assignments from considerations
of the higher D^ symmetry parent species, instead of the C symmetry s
group; they demonstrated that the assignments a r i s i n g from t h i s

representation are reasonable.
Table I I . Assignments of the Major Infrared Bands f o r

Isoquinoline at the Mercury/water Interface
Symmetry
Band Assignment C s D2h In- or out-of-plane
A B I n
1628 i / 8 ' 3g
1589 1/9 A' A g In
+ A + A A + B I n + 0 u t
1575 1/26 ^38 ' " g 3u
1500 i / n A' B 2 u In
1462 i/i2 A' A g In
1435 i / 1 3 A' B 3 g In
1380 A' A g In
1376 i / 1 5 A' B l u In
1273 i / 1 7 A' B l u In
1257 i / 1 8 A' B 2 u In
1215 i/ 3 6 + 1/42 A"+ A" A + B u l g Out + Out
1180 i / 1 9 A' B 3 g In
The difference spectra show a complete absence of bands with

negative absorbances (Figure 7). This can be explained i f the
v i b r a t i o n a l frequencies of the bands do not s h i f t with changes i n the
electrode p o t e n t i a l , and i f they are adsorbed over the e n t i r e
p o t e n t i a l region investigated. This i s consistent with r e s u l t s of

BLACKWOOD ET AL. Infrared Spectroelectrochemistry of Surface Species 345
POLARIZER
MIRROR
CELL
MIRROR
MIRROR MIRROR
Figure 5. Schematic representation of the SNIFTIRS

instrumentation.
4.00
<
3-
£ -2.00
CO
w
Q
-5.00
-0.90 -0.50 -0.10
POTENTIAL / VOLTS vs. SCE

2 3
Figure 6. C y c l i c voltammogram f o r a 2.1 x 10" mol-dm"
3
isoquinoline / 0.5 mol-dm" Na2S04 s o l u t i o n at a mercury
electrode at 10 rnV-s"^-.

00 CD O C v J l O O rO N ^ o
CM 00 O CO hO 00 r ^ i T ) r - 0 0
C£> m m ^ x t r o CM CM CM <-
~j 1.0 x 10
ENERGY / WAVENUMBERS
2
Figure 7. SNIFTIRS difference spectra f o r 1.3 x 10" mol-dm"
isoquinoline s o l u t i o n at a mercury electrode. Reference
p o t e n t i a l was 0.0 V vs. SCE, sample p o t e n t i a l (a) -0.60V,
(b) -0.75V, (c) -0.80V, and (d) -0.9V vs. SCE.

23. B L A C K W O O D E T A L . Infrared Spectroelectrochemistry of Surface Species 347
electrochemical double layer experiments. The spectra can now be

interpreted as r e l a t i v e l y simple changes i n the absorption of
i n f r a r e d r a d i a t i o n . The i n t e n s i t i e s of the bands are markedly
p o t e n t i a l dependent; an e s p e c i a l l y large change i n the i n t e n s i t i e s i s
observed at p o t e n t i a l s where the o r i e n t a t i o n changes to the v e r t i c a l
6,7 configuration.
Two types of mechanisms have been proposed to e x p l a i n the
p o t e n t i a l dependent s h i f t of v i b r a t i o n a l frequencies. The f i r s t
involves molecular o r b i t a l arguments; the second i s based on
arguments f o r i n t e r a c t i o n s between the e l e c t r i c f i e l d across the
double layer and the p o l a r i z a b l e electrons of the adsorbed molecule
(an electrochemical Stark e f f e c t ) . In the molecular o r b i t a l
mechanism, electrons can be donated to empty metal o r b i t a l s through
σ-type overlap with f i l l e d ligand o r b i t a l s of the appropriate
symmetry. The metal can "back" donate electrons from f i l l e d
d - o r b i t a l s to empty π* antibonding o r b i t a l s on the adsorbate. When a
molecule i s adsorbed on a clean uncharged metal surface, i t s
v i b r a t i o n a l frequency ma
frequency of the unadsorbe
contributions of the σ- and π-bonding i n t e r a c t i o n s . I f the π-bonding
i n t e r a c t i o n i s dominant the frequency w i l l decrease; conversely, the
frequency w i l l increase i f the α-bonding i n t e r a c t i o n i s dominant.
When the charge on the electrode i s made negative, the bond i s
weakened due to donation of charge from the metal into adsorbate π*
o r b i t a l s and the band frequency s h i f t s to lower wavenumber. When the
charge on the metal i s made p o s i t i v e a s h i f t to higher frequency
occurs. At a mercury electrode, however, there are no p- or d-
electrons a v a i l a b l e to p a r t i c i p a t e i n a back-bonding i n t e r a c t i o n .
The observation of p o t e n t i a l dependent frequency s h i f t s are therefore
not expected according to t h i s model.
The e l e c t r i c f i e l d mechanism involves coupling of the e l e c t r i c
f i e l d across the double layer with h i g h l y p o l a r i z a b l e electrons of
the adsorbate. According to the Gouy-Chapman-Stern model, f o r high
concentrations of supporting e l e c t r o l y t e s , most of the p o t e n t i a l drop
w i l l occur w i t h i n the f i r s t 5-10Â of the electrode surface, and the
drop w i l l be approximately l i n e a r with distance. When a layer of
adsorbed species i s present, i t can act as a d i e l e c t r i c across which
the greatest p o r t i o n of the p o t e n t i a l drop w i l l occur. E l e c t r i c
f i e l d s on the order of 10^ V m'^ can e x i s t i n t h i s region.
I n t e r a c t i o n of t h i s e l e c t r i c f i e l d with the dipole moment of the
molecule leads to changes i n the v i b r a t i o n a l frequency of the
molecule.
The absorbances i n Figure 7 have p o s i t i v e values. This
indicates that the i n t e r a c t i o n with i n f r a r e d r a d i a t i o n i s strongest
when the isoquinoline molecules are l y i n g f l a t on the electrode
surface ( i n these difference spectra, p o s i t i v e values of absorbance
denote stronger absorption at the p o s i t i v e p o t e n t i a l , i . e . p o t e n t i a l s
where the isoquinoline i s adsorbed i n the f l a t c o n f i g u r a t i o n ) . This
i s an opposite r e s u l t than that expected from the surface s e l e c t i o n
r u l e , and suggests that there i s a strong field-induced absorption
for the in-plane modes i n t h i s configuration, s i m i l a r to that
observed i n previous work f o r pyrene adsorbed on platinum (18).
A c l o s e r examination of the SNIFTIRS difference spectra shows
that there are marked differences i n the changes i n i n t e n s i t y of the
in-plane and out-of-plane v i b r a t i o n a l modes of the adsorbed

1.0x10 2.8x10
AR -0.9V -0.9V
R
1380cn 1215cm
band
band
IN-PLANE •UT-DF-PLANE
-0.6V -0.6V
WAVENUMBERS / cn
l 20 c n " 1
Figure 8. Expanded section of Figure 5 showing examples of

differences i n the magnitude of integrated area f o r two
absorption bands with the same changes i n electrode p o t e n t i a l .
SYMMETRY
10.0 1215 A u + B1g
1575 Ag + B3u
6.67
J(E=x
m J (E—0.1)
0.0
-0.3 -0.6 -0.9
POTENTIAL / VOLTS vs. S C E
Figure 9. P l o t of the normalized i n t e n s i t i e s of the bands

observed i n the SNIFTIRS difference spectra at a mercury
electrode i n 1.3 x 1 0 m o l - d m " ^ isoquinoline s o l u t i o n vs. those
at the sample p o t e n t i a l (see t e x t ) . Reference p o t e n t i a l = 0.0V vs
SCE.

23. B L A C K W O O D ET A L . Infrared Spectroelectrochemistry ofSurface Species 349
isoquinoline with p o t e n t i a l (Figure 8). In the f i g u r e , the

p o t e n t i a l s f o r the difference spectra are -0.6 and -0.9V. The change
i n area f o r the 1380cm"^ i n - plane mode has increased by a f a c t o r of
~4 , whereas that of the 1215cm"^ out-of-plane mode has increased by
a f a c t o r of «10. The normalized i n t e n s i t i e s (against t h e i r i n t e n s i t y
at -0.1V vs. SCE) of the v i b r a t i o n a l bands shown i n Figure 7 were
p l o t t e d against p o t e n t i a l (Figure 9). Since the bands i n Figure 7
have p o s i t i v e values of absorbance, the p o s i t i v e v e r t i c a l axis i n
Figure 9 represents a decrease i n the amount of i n f r a r e d r a d i a t i o n
absorbed. The Figure c l e a r l y shows that the amount of r a d i a t i o n
absorbed by the out-of-plane v i b r a t i o n a l modes decreases up to a
factor of 10 as the p o t e n t i a l i s changed from -0.1 to -1.0V, whereas
the in-plane v i b r a t i o n a l modes only change by a f a c t o r of 3-4 over
the same p o t e n t i a l range. (We point out at t h i s point that s o l u t i o n
soluble isoquinoline would not e x h i b i t t h i s e f f e c t ) .
The explanation of the trends seen i n Figure 9 i s that the out-
of-plane v i b r a t i o n a l modes have dipole d e r i v a t i v e changes
perpendicular to the meta
on the surface. Absorptio
r u l e i s thus allowed. When the o r i e n t a t i o n changes to the 6,7
configuration, absorption by these modes, which are now p a r a l l e l to
the surface i s forbidden, as i s any f i e l d induced i n t e r a c t i o n since
most of the molecule l i e s outside of most of the f i e l d gradient. A
large decrease i n absorption (large increase i n p o s i t i v e absorbance
i n the difference spectra) i s thus expected and observed. In the
case of the in-plane modes, the high e l e c t r i c f i e l d i n the double
layer leads to strong f i e l d induced absorption f o r the f l a t l y
adsorbed isoquinoline as expected. When r e o r i e n t i n g to the 6,7
configuration, the modes become allowed by the surface s e l e c t i o n
r u l e . A smaller decrease i n absorption i s then observed.
CONCLUSIONS
Subtractively normalized i n t e r f a c i a l Fourier transform i n f r a r e d

spectroscopy has been used to follow the r e o r i e n t a t i o n s of
isoquinoline molecules adsorbed at a mercury electrode. F i e l d
induced i n f r a r e d absorption i s a major c o n t r i b u t i o n to the
i n t e n s i t i e s of the v i b r a t i o n a l band structure of aromatic organic
molecules adsorbed on mercury. Adsorbed isoquinoline was observed to
go through an abrupt r e o r i e n t a t i o n at p o t e n t i a l s more negative than
about -0.73 V vs SCE (the actual t r a n s i t i o n p o t e n t i a l being dependent
on the bulk s o l u t i o n concentration) to the v e r t i c a l 6,7 p o s i t i o n .
There was a lack of any p o t e n t i a l dependence i n the frequencies
of the v i b r a t i o n a l modes of the adsorbed i s o q u i n o l i n e . The
explanation of t h i s may be the f a c t that mercury has no a v a i l a b l e
vacant p- or d - o r b i t a l s into which back-bonding (which i s observed
for adsorbates on d metals) can occur.
ACKNOWLEDGMENTS
We thank the O f f i c e of Naval Research f o r support of t h i s work.
LITERARURE CITED
1. Bewick, Α.; Robinson, J . J . Electroanal. Chem. 1975, 60 ,163.
2. Bewick, A.; Robinson, J . Surf. S c i . 1976, 55, 349.
3. Adzic, R.; Cahan, B.; Yeager, Ε J . Chem. Phys. 1973, 58, 1780.

4. Pons, S. Ph.D. t h e s i s , U n i v e r s i t y of Southampton, England, 1979.

5. Bewick, A.; Mellor, J . M.; Pons, S. Electrochim. Acta 1980, 25,
931.
6. Golden, W. G.; Dunn, D. S.; Overend, J. J. Catal. 71 (1981) 395.
7. Pons, S. J. Electroanal. Chem. 1983, 150, 495.
8. Pons, S.; Bewick, A. Langmuir 1985, 1, 141.
9. Buess-Herman, C.; Vanlaethem-Meuree, N,; Quarin, G.; G i e r s t , L.
J . Electroanal. Chem. 123 (1981) 21.
10. Humphreys, M. W.; Parsons, R. J . ; Electroanal. Chem. 1977, 82,
369.
11. Greef, R. In r e f . 9.
12. Quarin, G.; Buess-Herman, C.; G i e r s t , L.; J. Electroanal. Chem.
1981, 123, 35.
13. Buess-Herman, C. J. Electroanal. Chem. 1985, 186, 27.
14. Buess-Herman, C. J. Electroanal. Chem. 1985, 186, 41.
15. Buess-Herman, C.; Franck, C.; G i e r s t , L. Electrochim. Acta 1986,
31, 965.
16. Crawford, M.F.; MacDonald
17. Korzeniewski, C.; S h i r t s
89, 2297.
18. Korzeniewski, C.; Pons, S. Langmuir 2 (1986) 468.
19. Korzeniewski, C.; University of Utah Ph.D Thesis (1987).
20. Foley, J . K.; Korzeniewski, C.; Daschbach, J . ; Pons, S. In
E l e c t r o a n a l y t i c a l Chemistry; Bard, A. J., Ed.; Marcel Dekker:
New York, 1986; Vol.14, p 309.
21. A. Bewick, private communication.
22. Wait, Jr, S.C.; McNerney, J . C. J. Mol. Spectrosc. 1970, 34, 56.
R E C E I V E D M a y 17, 1988

Chapter 24
Fourier Transform Infrared Spectroscopic

Investigation of Adsorbed Intermediates
in Electrochemical Reactions
1
J. O'M. Bockris and K. Chandrasekaran
Surface Electrochemistry Laboratory, Texas A&M University,

College Station, TX 77843-3255
The adsorption of electrochemical intermediates during
the hydrogen evolutio
and the oxidatio
using Fourier Transform Infrared Spectroscopy. Two Fe
-1
H v i b r a t i o n s at 2060 and 980cm were i d e n t i f i e d . A
slope of F/6RT is obtained f o r a p l o t of θ vs. η, if
-1
one assumes that the area under the peak a t 2060cm
i s proportional to the hydrogen coverage, θ . The H
mechanism of the electrochemical reduction of CO2 i n

a c e t o n i t r i l e on a platinum electrode has been shown to
involve adsorbed CO2 and adsorbed CO2 concentrations
.-
of the adsorbed species. A new mechanism is proposed

for the oxidation of methanol on platinum i n aqueous
s u l f u r i c a c i d accounting f o r the observed structure of
the electrochemical intermediates.
The i n f r a r e d spectroscopy of electrodes was f i r s t introduced by

Hansen (1), Kuwana and Osteryoung (2). However, the early methods
were i n t e r n a l reflectance methods. Bewick e t a l . developed d i r e c t
i n f r a r e d methods (3-5) and Pons e t a l . developed the Fourier
transform version thereof (6.7). The use of p o l a r i z a t i o n modulation
i n the electrochemical s i t u a t i o n was introduced by Habib and Bockris
i n 1985 (8).
These several techniques f o r the s o l i d - s o l u t i o n i n t e r f a c e give
d i f f e r e n t kinds of information. However, the one which gives most
information about the nature of e n t i t i e s on the surface, and
p o t e n t i a l l y near the surface, i s f o u r i e r transform IR spectroscopy,
which i s not r e s t r i c t e d to a p a r t i c u l a r metal, or, indeed, to the
type of substrate (except that t h i s must be r e f l e c t i n g ) .
ASPECTS OF THE FTIR TECHNIQUE IN SOLUTION
One of the most important parts of the FTIR technique i s the movable
electrode i n order to allow proper d i f f u s i o n of species to and f r o
1
Current address: E. I. du Pont de Nemours and Company, P.O. Box 505, Towanda,
PA 18848-0505
0097-6156/88/0378-0351$06.00/0

from the electrode surface and the a b i l i t y to r e e s t a b l i s h the

electrode to t h i s p o s i t i o n . Another aspect of the p o s i t i o n i n g of the
electrode near the c e l l a r i s e s because of the danger that current
l i n e s w i l l not f a l l uniformly onto the electrode.
The basic advantage of FTIR i s the overcoming of noise. In
order of magnitude terms, the s o l u t i o n before the electrode i s about
1/im i n thickness i n a 0.1 M s o l u t i o n of a solute, the adsorption of
which i t i s desired to measure, and t h i s layer w i l l thus contain
8 2
about 10" moles per cm" . At 10% coverage, the s o l u t i o n would
1
contain about l O " ^ moles, and therefore the signal-to-noise r a t i o
would be expected to be on the order of 0.01. There are circum-
stances when the signal-to-noise r a t i o may be as l i t t l e as 10"^.
This r e s u l t s due to the use of s i g n a l averaging. Such low s i g n a l -
to-noise r a t i o s are commonly obtained with non-aqueous e l e c t r o l y t e s
which eliminate the introduction of noise from the broad water
bands.
To get over t h i s d i f f i c u l t y FTIR uses the basic p r i n c i p l e of
an interferogram. A sourc
IR frequencies) i s inciden
an o p t i c a l device, the beam s p l i t t e r at which about h a l f the l i g h t
i s r e f l e c t e d and h a l f allowed to pass through shown i n Figure l a
(£).
A f t e r s t r i k i n g the f i x e d mirror, the l i g h t i s r e f l e c t e d back to
the beam s p l i t t e r , and part of t h i s l i g h t then i n t e r f e r e s with l i g h t
returning from the moving mirror. When the l i g h t r e f l e c t e d from the
f i x e d mirror meets that from the moving mirror, a number of
extinctions and augmentations of l i g h t occur, and the d e t a i l e d
nature of these depend on the p o s i t i o n of the mirror at a given
instance.
The degree to which augmentation or destruction occurs when the
two l i g h t beams meet depends on the wavelengths i n the beam and the
distance of displacement of the mirror a t a given instance. As the
mirror sweeps to and f r o , c e r t a i n (changing) frequencies are
augmented and transferred to the electrode where, a f t e r absorptive
i n t e r a c t i o n with the adsorbed material, and r e f l e c t i o n , the l i g h t i s
analyzed i n respect to i n t e n s i t y .
When the signal-to-noise r a t i o i s poor, r e p e t i t i o n of the
s i g n a l means that minor peaks which are merely due to f l u c t u a t i o n s
and errors are not repeated and therefore not enhanced, only those
peaks which are repeated with every sweep of the mirror ( i . e . , peaks
representing absorbed e n t i r e l y ) , are f i n a l l y left i n the
information.
The f i n a l step i n obtaining the spectrum by the FTIR method i s
turning back the data obtained as a r e s u l t of the r e p e t i t i v e
interference action of the moving mirror i n t o an i n t e n s i t y
wavelength l i n e . I t i s here that Fourier Transform mathematics i s
utilized. I t i s the s i g n a l i n t e n s i t y that i s stored i n a d i g i t a l
representation of the interferogram. This information i s then
Fourier transformed by the computer into the frequency spectrum.
There are two l i g h t sources involved, a white l i g h t and a l a s e r
source. The white l i g h t uses the same moving mirror and therefore
makes up a second interferometric system w i t h i n the spectrometer.
When the moving mirror and the f i x e d mirror of t h i s secondary
interferometer are equidistant, a centerburst i s produced which i s

24. BOCKRIS & CHANDRASEKARAN Adsorption of Intermediates 353
used to t r i g g e r the e l e c t r o n i c c o l l e c t i o n system so that each scan

begins when the moving mirror i s at the same p o s i t i o n , known as zero
path difference. The l a s e r source being monochromatic, has a known
frequency and therefore can be used to d i g i t i z e the c o l l e c t e d data.
The spectrum obtained i n the way described so f a r i s , however,
not s u f f i c i e n t l y s e n s i t i v e , and two methods are used, then, to
obtain r e s u l t s which may be u t i l i z e d f o r the i n v e s t i g a t i o n of
surface phenomena i n electrochemistry.
The SNIFTIRS approach. The acronym SNIFTIRS means Subtractively

Normalized I n t e r f a c i a l Fourier Transform Infrared Spectroscopy. The
basic concept of t h i s method involves the f a c t that the raw data
obtained d i r e c t l y from the Fourier Transform process contain
components which are undesirable. F i r s t l y , there i s material i n the
s o l u t i o n which may have affected the spectrum. Secondly, unwanted
information on c e r t a i n material on the electrode (adsorbed water,
for example) i s best eliminated
In an i d e a l case,
methods, e.g., a voltammogram
I f i t i s then possible to obtain a spectrum (using p a r a l l e l
p o l a r i z e d l i g h t ) t h i s spectrum i s subtracted from the spectrum
obtained i n the p o t e n t i a l region i n which the adsorption i s known to
occur. The r e s u l t i n g intensity-wavelength l i n e (free from
i n t e n s i t i e s of material i n s o l u t i o n , or from bonds on the electrode
which do not change with p o t e n t i a l ) i s the SNIFTIRS spectrum.
The SNIFTIRS equations used f o r working out the r e s u l t s , also
shown below. The SNIFTIRS spectrum i s noisy, and suffers from the
fact that i t i s sometimes not possible to designate a region i n
which there i s no adsorption.
AR_ _ p - I r e f (1)
R
o I Iref -
(I ( I }
A « f P>V ' P R (2)
(Ip>R
P o l a r i z a t i o n modulation. Figure l b (9) shows relevant properties of
the i n t e r a c t i o n of the two p r i n c i p a l modes of p o l a r i z a t i o n of l i g h t
with the surface. This i s d i f f e r e n t (as was f i r s t shown by Greenler
(10).) depending on whether one i s u t i l i z i n g the p a r a l l e l or the
v e r t i c a l plane of p o l a r i z a t i o n . In respect to the v e r t i c a l plane of
p o l a r i z a t i o n (the left-hand diagram i n Figure l b ) , the e l e c t r o s t a t i c
components of l i g h t which a r i s e when the l i g h t i n t e r a c t s with the
surface are 180° out of phase, so the r e f l e c t e d l i g h t contains no
information from the surface, only from the s o l u t i o n .
On the other hand, with the p a r a l l e l plane of p o l a r i z a t i o n the
r e s u l t o f the l i g h t i n t e r a c t i n g with the surface i s to produce
components which add to each other; thus, the r e f l e c t e d beam
contains information from the surface as w e l l as that from the
solution.
The statements made above are only true when the angle of
incidence of t h i s l i g h t i s nearer to 90°. An instant angle of about
85° i s used.

HI Source
FM = Focusing Mirror ^
PM = Parabolic Mirror
BS = Beam Splitter
Detector
ELECTRODE
MOVING MIRROR
FIXED MIRROR
To Cell
Figure l a . The o p t i c a l arrangements of an FT-IR Spectro-
photometer with reflectance attachments i n the sample chamber
for electrochemical experiments. (Reproduced with permission
from Ref. 9. Copyright 1984 E l s e v i e r . )

BOCKRIS & CHANDRASEKARAN Adsorption of Intermediates 355
b REFLECTED LIGHT
PHASE C H A N G E
1. A N G L E O F INCIDENC
2. S T A T E O F POLARIZATION
0° 30° 60* 90°
Angle of Incidence <f>

180° OUT OF PHASE 9 0 ° OUT OF PHASE
Figure l b . Schematic diagram of polarized l i g h t used with the

p o l a r i z a t i o n modulation technique. (Reproduced with permission
from Ref. 9. Copyright 1984 Elsevier.)

I t can be r e a d i l y seen from the above discussion that a

s i m p l i s t i c version of the p o l a r i z a t i o n modulation method f o r using
Fourier Transform Infrared method would be to say that i f one
subtracted the message obtained from the v e r t i c a l l i g h t from that
obtained from the p a r a l l e l l i g h t , the r e s u l t w i l l be information
from the surface only. The relevant equation i s shown below.
Absorbance « AR
(3)
R
The statements made h i t h e r t o are a l l based upon Greenler's

paper. I f the p a r a l l e l l i g h t i n t e r a c t s with surface and the
s o l u t i o n , but the v e r t i c a l l i g h t only with the s o l u t i o n . In the
case of adsorption from the gas phase, the adsorbed phase i s sharp
and consists e s s e n t i a l l y only of molecules a c t u a l l y i n contact with
the surface. In electrochemical s i t u a t i o n s , however, s u b s t a n t i a l
amounts of "absorbed" solut
c a r e f u l examination of th
from the p a r a l l e l and v e r t i c a component ligh y
information from the s o l u t i o n phase as w e l l as from the e l e c t r i c a l
phase.
For t h i s reason, Chandrasekaran and Bockris (11) c a r r i e d out an
examination of the extent to which t h i s f a c t introduced an error
into the electrochemical Fourier Transform measurements of surface
occupancy, an error which perhaps would mean that the information
contained contributions from material i n the s o l u t i o n .
A c a l c u l a t i o n which can be made to show e s s e n t i a l l y AR/R f o r
the p a r a l l e l and v e r t i c a l components as a function of distance from
the electrode. The c a l c u l a t i o n s involve separating the p a r a l l e l and
perpendicular components f o r each phase utilizing Fresnel
coefficients.
Figure 2a shows the r e s u l t of these c a l c u l a t i o n s . The values
obtained are dependent upon the assumptions made, i n p a r t i c u l a r the
concentration of the s o l u t i o n f o r which the c a l c u l a t i o n s are c a r r i e d
out, and the coverage on the electrode. The s i t u a t i o n i s worse
(maximum interference from the solution) when the coverage i s small
and the concentration of the s o l u t i o n high, and then 60% of the
information can come from the s o l u t i o n . In more usual
circumstances, however, when the s o l u t i o n concentration i s medium or
low, and the electrode concentration i s medium or high, more than
90% of the information does come from the electrode surface i t s e l f
(Figure 2b). The d e t a i l s are given elsewhere (11).
The conclusions apply to the information before subtracting the
spectra at the no adsorption condition. The upshot of a l l these
considerations i s that one has to be c a r e f u l when using FTIR
spectroscopy to see that the information i s indeed surface
information. One of the most encouraging ways of doing t h i s i s to
look at the frequency of a peak as a function of electrode
potential. I f the information i s t r u l y coming from adsorbed
substances, there w i l l usuall y be a s l i g h t v a r i a t i o n of the peak
with p o t e n t i a l . However, t h i s i s only confirmatory, and not a
necessary c h a r a c t e r i s t i c of the information.

Figure 2a. Absorbance f o r the surface and s o l u t i o n as a

function of distance at a surface coverage of 0.5. (Reproduced
with permission from Ref. 11. Copyright 1987 North Holland.)

A B S O R B A N C E VS d
3600
Figure 2b. Relative absorbance as a function of thickness of

the f i l m . Relative absorbance (AR/R)/d; values normalized to
unity a t the surface. (Reproduced with permission from Ref. 11.
Copyright 1987 North Holland.)

THE SURFACE CONCENTRATION OF HYDROGEN ON IRON DURING HYDROGEN

EVOLUTION
One o f the questions i n the mechanism of hydrogen evolution, and

a n c i l l a r y topics connected with the surface hydrogen involved i n
corrosion, i s the dependence o f the surface hydrogen upon
overpotential. This topic has importance not only because of the
evidence i t gives on the mechanism of hydrogen evolution, but also
because i t relates to the embrittlement aspects of hydrogen evolved
during corrosion (12).
Recently, Carbajal e t a l . (13) i n the Texas A&M Surface
Electrochemistry Laboratory have been able to show two bonds f o r
FeH, the f i r s t (at about 2060 wave numbers) i s due to symmetric
stretching v i b r a t i o n and the second (at about 980 wave numbers) to
the asymmetric s t r e t c h i n g v i b r a t i o n . The basic r e s u l t s are shown i n
Figure 3, where the coverage i s p l o t t e d against overpotential.
From these r e s u l t s i t turns out that:
*log ( 4 )
av 5.6RT
The t h e o r e t i c a l r e s u l t f o r a slow discharge mechanism followed

by a f a s t recombination reaction i s F/4RT f o r t h i s r a t i o . The
discrepancy i s not too serious, because the predicted value depends
upon an observed T a f e l slope of 2RT/F and the value obtained on i r o n
i s about twice t h i s , which would correspond to the lower value f o r ,
dlog$/dV observed on Fe.
This r e s u l t represents the f i r s t use of FTIR measurements to
obtain information about the hydrogen evolution r e a c t i o n on iron.
I t also represents one of the f i r s t uses o f FTIR to study the
mechanism of the electrode k i n e t i c r e a c t i o n (14).
SURFACE RADICALS IN THE PHOTOELECTROCHEMICAL REDUCTION OF C 0 2
Information on the mechanism of the reduction of CO2 can be made

with great ease when using FTIR spectroscopy.
Thus, the mechanism which has been proposed (15.16) i s given by
the f o l l o w i n g equations.
C C ( 5 )
°2aq * °2ads
C + e C ( 6 )
°2ads " " °2ads
-
C0 2 a d s + H 0 + e" -* HCOO" + OH
2 (7)
There has h i t h e r t o been no d i r e c t evidence of the presence of

adsorbed CO2". Some spectroscopic r e s u l t s are shown i n Figure 4a.
The frequency of 1670 (reactions c a r r i e d out i n a c e t o n i t r i l e )
doubtless represents the CO2" r a d i c a l . The IR spectrum of t h i s
r a d i c a l has been recorded at -190°C, and i t has a sharp maximum at
-1
1671 c m (17).
I t i s noteworthy that the adsorbed concentration o f CO2"
r a d i c a l a t various electrode p o t e n t i a l s shows an increase i n the
C02~ i n the more negative d i r e c t i o n . The mechanistic s i g n i f i c a n c e
of t h i s observation i s indicated below. F i n a l l y , i n Figure 4b i t

0.15 -
0.12 -
a>
2 0.09 -
>
O 0.06-
0.03 ~
-0.1 -0.2 -0.3 -0.4 -0.5 -0.6
Overpotential/V(NHE)
Figure 3. Coverage-overpotential r e l a t i o n f o r hydrogen

adsorbed on i r o n corrected f o r reference p o t e n t i a l . (Reproduced
with permission from Ref. 13. Copyright 1987 The
Electrochemical Society, Inc.)

i 1 1 1 1 1 1 1 1 1 1 1 1 r
1750 1730 1710 1690 1670 1650 1630 1610
Wavenumbers
Figure 4a. Absorption spectrum of CO2 r a d i c a l adsorbed on

platinum i n a c e t o n i t r i l e containing 0.4M LiClC>4. (Reproduced
with permission from Ref. 11. Copyright 1987 North Holland.)

4
8.75 X 10"
2400 2350 2300 2250 2200

Figure 4b. Absorption spectra of adsorbed CO2 (2340 cm"l) and
CH3CN (2250 cm"I) on platinum i n a c e t o n i t r i l e containing 0.4 M
L i C l O ^ (Reproduced with permission from Ref. 11. Copyright
1987 North Holland.)

24. B O C K R I S & C H A N D R A S E K A R A N Adsorption of Intermediates 363
can be seen that the r e l a t i v e concentrations of adsorbed

a c e t o n i t r i l e and CO2 on platinum decrease with p o t e n t i a l .
The information obtained can be used to give interesting
information upon the CO2 reduction mechanism. Because the r a d i c a l
anion increases i n concentration i n the negative d i r e c t i o n , i t
cannot be i n equilibrium with the electrode. The increase i n anion
concentration at cathodic potentials may, however, be explained i f
CO2" i s formed as an intermediate r a d i c a l . Thus from equations 5-7
P 8
*co -H> co
2 2 <>
and with equation 6 i n equilibrium
V F R T
. - k,k P_e" / (9)
CO2 6 5 C0
c
2
where V i s the electrode potential, k5 and kg are equilibrium

constants for equations 5 and 6, respectively. Thus, g _ increases Q
increasing negative value of V With equation 7 rate determining

the current density, i ,
F / R T
< -^7»0O -^ 2 <">
Thus, i t i s possible to obtain information on the rate determining

step by i d e n t i f y i n g the r a d i c a l and following the surface coverage
with p o t e n t i a l .
OXIDATION OF METHANOL TO COo
The oxidation of methanol was c a r r i e d out at a p o t e n t i a l range of

0.0 to +0.8V. The spectrum at a p o t e n t i a l of 0.3V i s shown i n
Figure 5a, while the spectrum at 0.8V i s shown i n Figure 5b.
Some interesting changes are shown with p o t e n t i a l . Broad water
peaks are observed at the p o t e n t i a l of 0.3V, and these are
considerably reduced at a p o t e n t i a l of 0.8V. However, the most
interesting change i s that i n the p o t e n t i a l region at more negative
than 0.2, the spectrum at about 2150 i s equivalent to that of the
-OO.
By the p o t e n t i a l corresponding to about 0.6 V, the -CÔ
spectrum has transformed to one corresponding to about 1750 wave
numbers, which i s t y p i c a l of JC-O. Willsau et a l (18) contends that
COH i s the intermediate i n this reaction, however C-H vibrations
were not detected f o r the adsorbed species. Further, three
electrons per s i t e are required f o r oxidation of this species to
carbon dioxide whereas the experimentally observed value i s 1.2-1.5.
The plot of the various reactants i s most revealing. It is
compared i n Figure 6 with the radiotracer and potentiodynamic
methods. I t w i l l be seen that there i s a rough kind of agreement
between the data here obtained and the radiotracer method data,
though the potent iodynamic method i s evidently less sensitive. On
the other hand, the FTIR data distinguishes between the two, CO i n
the t r i p l e bond form and CO i n the double bond form.
The most important information this gives us i s on the
mechanism of oxidation of CO2.



0.0 0.2 0.4 0.6 0.8

V/NHE
Figure 6 . Comparison of various in situ techniques f o r the

chemisorption of methanol on platinum.

One possible mechanism that f i t s the data herewith revealed by

the spectroscopy. I t i s as follows:
CH3OH
+
* C0 a d + 4H + 4e" (12)
+
H 0 * 0H
2 a d + H + e" (13)
C0 a d + 0H a d zt COOH RDS (14)
+
COOH « C0 + H + e" 2 (15)
These various reactions can then be portrayed from the point of

view of electrochemical parameters as follows:
*C0 - k exp(4VF/RT) 12 (16)

*0H - k exp(VF/RT) 13 (17)
i - Fk 1 4 0 c o 0 O H (18)
(Langmuir) slope - 60mV
ln k ln +
ln i = In F k 1 4 0 c o "1 13 " 7 —r fVF/RT (20)
H
2°
(Tempkin) slope - 120mV
The rate-determining step i s the surface combination of C 0 a d s
with OH to give a carboxylic group. The remarkable slope of 120 mv,

so e a s i l y confused with a discharge mechanism, can be interpreted i f
these adsorptions are Tempkin i n type, i n terms of the mechanism
equations 12-15, i f the 0 dependence i s r e l a t i v e l y small (equation
16).
Thus, these studies again stress the m u l t i p l e p o s s i b i l i t i e s
which a r i s e from the use of FTIR spectroscopy and the analysis of
r e a c t i o n rates.
FUTURE APPLICATIONS OF FTIR SPECTROSCOPY
I t has been shown i n t h i s paper p a r t i c u l a r l y that the FTIR

spectroscopy can i d e n t i f y r a d i c a l s and chemical reactions, and by
t h e i r p o t e n t i a l and concentration dependence give considerable
information upon the mechanism of reactions and the d e t a i l e d
mechanism of electrochemical reactions, i n c l u d i n g t h e i r rate-
determining step. The analysis of intermediate r a d i c a l s has always
been a need i n electrochemical research, and i s c l e a r l y now here.
The absolute determination of coverage i s much more d i f f i c u l t .
The formalism i s w e l l known, i . e . , i t i s possible to go from the
i n t e n s i t y of a s p e c t r a l ion to the concentration material on the
surface, but t h i s can only be worked out i f the t r a n s i t i o n dipole
moment i s known. A very rough order of magnitude v e r s i o n of t h i s
can, however, u s u a l l y be obtained by analogy (rather than by quantum
mechanical c a l c u l a t i o n ) so that somewhat better than an order of
magnitude c a l c u l a t i o n of the coverage of the surface r a d i c a l s can be
given.

Other aspects of FTIR spectroscopy have not y e t been put into

practice. One could study the k i n e t i c s , and i n p a r t i c u l a r the
build-up and decay of intermediate r a d i c a l s . This l a t t e r aspect
would provide useful information to determine the mechanism of the
reaction being studied.
At present time, these studies cannot be c a r r i e d out, due to
the short l i f e t i m e s involved, but with more intense sources of l i g h t
i t may be possible to reduce the measurement time enabling the
measurement of 9 i n the m i l l i s e c o n d range with FTIR ellipsometry.
ACKNOWLEDGMENTS
The authors wish to thank the Gas Research I n s t i t u t e f o r

f i n a n c i a l support and Dr. Kevin K r i s t f o r several discussions.
LITERATURE CITED
1. Hansen, W.N. In Advance

chemical Engineering
Wiley: New York 1973; V o l . 9, p 1.
2. Hansen, W.W., Kuwana, T. and Osteryoung, R.A. A n a l y t i c a l
Chemistry 1966, 38, 1809.
3. Bewick, A. and Robinson, J . J. Electroanal. Chem. 1975, 60,
163.
4. Bewick, A., Mellor, J.M. and Pons, S. Electrochim. Acta 1980,
35, 931.
5. Bewick, A. and Pons, S. In Advances i n IR and Raman
Spectroscopy; Hexter, R.E. and Clarke, R., Eds.; Heyden: London
1984.
6. Pons, S., Davidson, T., Bewick, A. and Schmidt, P.P. J .
7. Pons, S., J. Electroanal. Chem. 1983, 150, 495.
8. Habib, M.A. and Bockris, J.O'M. J. Electrochem. Soc. 1985, 132,
108.
9. Habib, M.A. and Bockris, J.O'M. J. Electroanal. Chem. 1984,
180, 287.
10. Greenler, R.B. J. Chem. Phys. 1966, 44, 310.
11. Chandrasekaran, K. and Bockris, J.O'M. Surf. S c i . 1987, 185,
495.
12. Flitt, H.J. and Bockris, J.O'M. I n t . J. Hydrogen Energy 1981,
6, 119;
13. Bockris, J.O'M., Carbajal, J.L., Scharifker, B.R. and
Chandrasekaran, K. J. Electrochem. Soc. 1987, 134, 1957.
14. Golden, W.G., Kunimatsu, K. and Seki, H. J. Phys. Chem. 1984,
88, 1275.
15. Paik, W., Anderson, T.N. and Eyring, H. Electrochim. Acta 1969,
14, 1217.
16. Amatore, C. and Saveant, J.M. J. Amer. Chem. Soc. 1981, 103,
5021.
17. Hartman, K.O. and Hisatsune, I.C. J. Chem. Phys. 1966, 44,
1913.
18. Willsau, J . , Walter, O. and Heitbaum, J . J. Electroanal. Chem.
1985, 185, 163.

Chapter 25
Vibrational Spectroscopic Studies of Adsorbate

Competition During Carbon Monoxide
Adsorption on Platinum Electrodes
1 2
R e n éR. Rodriguez , Wade J. Tornquist , Francis Guillaume,
3
and Gregory L. Griffin
Department of Chemica
Department of Chemistry, y , Minneapolis,
MN 55455
We have compared the effect of various nitrile com-
pounds and Sn adatoms on the vibrational frequency and
oxidation kinetics of CO adsorbed on Pt electrodes.
Both types of species adsorb competitively with CO,
leading to a decrease in the amount of adsorbed CO and
a shift of v(CO) to lower frequency. The latter
effect is consistent with the decrease in dynamic
coupling expected for a uniformly reduced CO coverage.
There is no evidence for significant direct inter-
action between CO and either co-adsorbed species.
Adsorbed n i t r i l e s are able to block CO from entering
i t s linear configuration when the adsorption step i s
performed at 0.05 V(SHE). Adsorbed Sn atoms behave in
a manner which supports previous models for their
catalytic enhancement of CO oxidation rates.
Competitive adsorption of CO contributes to a loss of
Sn adatoms from the Pt surface during CO oxidation
cycles.
V i b r a t i o n a l s p e c t r o s c o p y i s the e x p e r i m e n t a l i s t ' s most p o w e r f u l
t o o l f o r s t u d y i n g the e f f e c t s of changes i n l o c a l environment on
i n d i v i d u a l chemical bonds. S t u d i e s o f s i m p l e a d s o r b a t e s l i k e CO
w h i c h have s t r o n g c h a r a c t e r i s t i c a b s o r p t i o n bands have c o n t r i b u t e d
g r e a t l y to our understanding of a d s o r p t i o n processes at surfaces
(1). A s shown h e r e and i n o t h e r p a p e r s i n t h i s s y m p o s i u m , r e c e n t
e x p e r i m e n t a l developments have l e d to a renewed e f f o r t to use the
v i b r a t i o n a l s p e c t r o s c o p y o f a d s o r b a t e s as a probe f o r u n d e r s t a n d i n g
the p h y s i c a l chemistry of m e t a l / e l e c t r o l y t e i n t e r f a c e s .
1
C u r r e n t address: Department of Chemistry, University of Idaho, Moscow, I D 83843
2
C u r r e n t address: Department of Chemistry, Eastern Michigan University, Ypsilanti, M I 48197
3
C u r r e n t address: Department of Chemical Engineering, Louisiana State University, Baton
Rouge, L A 70803
0097-6156/88/0378-0369$06.00/0
c

Overviev of CO Adsorption Studies
The adsorption of CO on Pt i s perhaps the most throughly studied

system using v i b r a t i o n a l spectroscopy. Studies have been made
using both supported c a t a l y s t s (2-5) and single c r y s t a l s (5-10).
Sample environments have included gas phase, vacuum, and aqueous
s o l u t i o n (11-13). The s i m i l a r i t i e s between many of these r e s u l t s
have led to a remarkably u n i f i e d understanding of CO adsorption
phenomena i n a l l three environments. Features which are relevant
to further studies of the metal/electrolyte interface are
summarized b r i e f l y :
Configuration of Adsorbed CO. Under most conditions, CO i s

p r e f e r e n t i a l l y adsorbed i n a l i n e a r configuration. This means that
the CO molecule i s bound to a single Pt atom on the electrode
surface through a Pt-C bond that i s colinear with the CO bond a x i s .
The v(C0) frequency generally l i e s i n the region 2050-2110 cm" ,
s l i g h t l y below the gas phas
a t t r i b u t e d to charge transfe
A simple description of the charge transfer process i n molecular
o r b i t a l terms i s thatêlectron density i s back-donated from metal
d-bands into the CO IT o r b i t a l , which i s anti-bonding i n character
(14). The r e l a t i v e l y small size of the frequency s h i f t implies
that the extent of charge transfer i s small. As a r e s u l t , the C-0
bond order i s s t i l l close to 3.0 for l i n e a r l y adsorbed molecules.
Molecular CO can also be adsorbed i n a bridging configuration.
This means that the molecule i s bound to the surface through Pt-C
bonds with two or more adjacent Pt atoms. The value of v(C0) i n
the bridging species i s 1900 cm" or l e s s , which indicates that the
C-0 bond order i s reduced below 2.5. In terms of the back-donation
d e s c r i p t i o n , t h i s means tjjat a much larger amount of charge i s
transferred into the CO TT o r b i t a l . An alternate description i s
that the CO a molecular o r b i t a l s are p a r t i a l l y rehybridized to
place greater s£ vs. s£ character on the C and 0 atoms. This
allows more charge to be located i n the lone p a i r o r b i t a l s on the 0
atom. Conditions which lead to formation of the bridging species
include high CO coverage, the presence of electron donating species
co-adsorbed on the surface, and the a p p l i c a t i o n of r e l a t i v e l y
negative potentials to a Pt electrode i n a non-acidic s o l u t i o n .
The l a t t e r two observations support the concept that formation of
bridging CO can be enhanced by increasing the a b i l i t y of the
surface to donate charge to adsorbates.
Frequency Dependence of Adsorbed CO. The exact value of v(C0) i s

effected by several f a c t o r s , including CO coverage, electrode
p o t e n t i a l , and e l e c t r o l y t e composition. The coverage dependence
has been studied p r i m a r i l y under vacuum conditions, using mixtures
of v i b r a t i o n a l l y distinguishable CO and CO. These studies have
shown that the coverage dependence i s mainly due to dynamic
coupling between neighboring CO molecules (3,15). Recently
Severson et. a l . showed that dynamic coupling i s also responsible
for the coverage dependent component of the frequency s h i f t under
electrochemical conditions, but with a coupling constant about
twice as large as the value observed under vacuum conditions (16).

25. RODRIGUEZ ETAL. Spectroscopic Studies of Adsorbate Competition 371
We have independently observed larger values for the coverage

dependence i n various e l e c t r o l y t e s , but also f i n d evidence that the
composition of the e l e c t r o l y t e a f f e c t s the magnitude of the
frequency s h i f t (17).
The p o t e n t i a l dependence of v(CO) has been reported for
several e l e c t r o l y t e s . Values of 9(v(CO))/3E measured near pH = 1
a r e ^ t y p i c a l l y around +30 cm /V (11-13). Recently a s h i f t of +80
cm /V has been reported for CO adsorbed on Au electrodes i n NaOH
s o l u t i o n (18). The p o s i t i v e sign of these c o e f f i c i e n t s indicates
that v(C0) increases as the p o t e n t i a l i s made more anodic. The
o r i g i n of the p o t e n t i a l dependence i s s t i l l being discussed.
Russell et. a l . o r i g i n a l l y proposed that the s h i f t i s due to an
increase i n the extent of inter-molecular charge transfer between
the metal and the adsorbed CO as the p o t e n t i a l i s increased (12).
In contrast, Lambert has proposed that the s h i f t i s due to the
Stark e f f e c t exerted by the e l e c t r i c f i e l d at the inner Helmholtz
plane on the intra-molecular charge d i s t r i b u t i o n of the adsorbed CO
molecule (19).
The influence of e l e c t r o l y t
spectrum presents a complex problem which has only recently
received experimental a t t e n t i o n . Early studies using d i f f e r e n t
acid e l e c t r o l y t e s reported that the i d e n t i t y of the anion has a
measurable e f f e c t on the p o t e n t i a l dependence of v(C0) (12), but
l a t e r r e s u l t s seemed to discount t h i s (13). In contrast, we
recently studied CO spectra using several non-acidic e l e c t r o l y t e s
and observed a very pronounced dependence on pH, e s p e c i a l l y at low
CO coverages (17). In 0.5 M K S0, at -0.350 V(S£E), the extra-
2
polated zero coverage l i m i t of y(C0) i s 1963 cm"" and the satura-

t i o n coverage l i m i t i s 2062 cm" - This can be compared to the
corresponding l i m i t s of 2030 cm" and 2090 cm that are measured i n
1
0.5 M H-SOât 0.150 V(SCE), and also to the l i m i t s of 2065 cm"
and 2100 cm" that are measured on the same sample under vacuum
conditions. These comparisons show that the apparent coverage
dependence of v(C0) increases as a function of sample environment,
i n the order neutral e l e c t r o l y t e > acid e l e c t r o l y t e > vacuum. To
account for the difference i n the r e s u l t s for neutral and acid
solutions, we proposed that the larger value of the coverage
dependence under e l e c t r o l y t e conditions i s due to adsorption of
p o s i t i v e counterions on the Pt surface atoms that are not occupied
by adsorbed CO.
Competitive adsorption. In the experiments which f o l l o w , we

examine the influence of two other types of co-adsorbed species,
namely organic n i t r i l e compounds and Sn adatoms. We selected
n i t r i l e compounds because they might be expected to competitively
adsorb on the surface with CO without s i g n i f i c a n t l y a f f e c t i n g the
e l e c t r o n i c properties of the surface. I t i s also possible that the
v(CN) band of the adsorbed n i t r i l e might be observed i n the IRRAS
spectrum. N i t r i l e compounds i n s o l u t i o n phase have a v(CN)
frequency i n the range 2240-2260 cm" . Sexton et. a l . reported
that CH-CN adsorbed on P t ( l l l ) under UHV conditions has a strongly
s h i f t e d band at 1615 c m , which they a t t r i b u t e d to CH CN adsorbed
3
i n a -rr-bonded configuration (20). This band would l i e beyond the

low frequency cutoff of the InSb detector on our present apparatus.

Loo et. a l . have recorded surface enhanced Raman spectra of
CH (CN) and NC(CH > CN adsorbed on Cu electrodes (21-22). For
2 2 2 2
both molecules, the authors observed two bands i n the regions

2200-2300 cm and 2080-2120 cm that they assigned to non-
degenerate v(CN) modes of free and adsorbed n i t r i l e f u n c t i o n a l
groups, r e s p e c t i v e l y . We can test whether s i m i l a r bands might be
observed on Pt electrodes.
The experiments using Sn adatoms are intended to test f o r a
c o r r e l a t i o n between the a c t i v i t y of these species as promoters f o r
CO oxidation k i n e t i c s and t h e i r influence on the CO v i b r a t i o n a l
spectrum. Watanabe et. a l . have proposed an "adatom o x i d a t i o n "
model f o r the c a t a l y t i c a c t i v i t y of these adatoms (23). They
propose that the function of the Sn adatoms i s to catalyze the
generation of adsorbed 0 or OH species at a lower p o t e n t i a l than
would be required on unpromoted Pt (23). The l a t t e r species then
react with neighboring adsorbed CO molecules to accomplish the
o v e r a l l oxidation reaction
mechanism i s that the adsorbe
i f any, d i r e c t i n t e r a c t i o n with the adsorbed CO reactant partner.
V i b r a t i o n a l spectroscopy can be used to test f o r such an i n t e r -
action.
Experimental
V i b r a t i o n a l spectra were recorded using the polarization-modulated

infrared r e f l e c t i o n absorbance technique (PM-IRRAS). The spectro-
meter, the electrochemical c e l l , and the sample preparation and
cleaning procedures are a l l described elsewhere (17). A l l of the
measurements were performed using 0.5 M H S0^ s o l u t i o n s , e i t h e r
2
with or without an added n i t r i l e compound or SnCl,. The solutions

were saturated with CO by bubbling the gas through t h e i r storage
reservoirs before admitting them into the sample c e l l .
Results for co-adsorbed N i t r i l e s
In Figure 1 we show the PM-IRRAS spectra for a Pt electrode exposed

to saturated C0/H S0^ solutions which contain various concentra-
2
tions of d i f f e r e n t organic n i t r i l e s . For comparison, we have also

included a spectrum recorded i n saturated C0/H S0^ with no added2
n i t r i l e . The adsorption step was accomplished by p u l l i n g the

electrode back into the bulk s o l u t i o n and c y c l i n g the p o t e n t i a l
from 0.55 V(SHE) up to 1.15 V, down to 0.0 V, and back to 0.55 V.
The spectra were recorded a f t e r r e - p o s i t i o n i n g the electrode
against the c e l l window while the p o t e n t i a l was held at 0.55 V.
The top curve shows the spectrum of adsorbed CO that i s
observed when no n i t r i l e compound i s added Jo the e l e c t r o l y t e . The
C-0 stretching frequency occurs at 2085 cm" , which i s character-
i s t i c of a saturated CO adlayer at t h i s p o t e n t i a l . The next three
spectra were recorded i n solutions which contain 1.0 M CH-CN, 0.2 M
C H.CN, and 0.1 M H00CCH CN, r e s p e c t i v e l y . The i n t e n s i t y of the
2 2
v f c o ) band i s reduced about 50% i n each case. This indicates that

the amount of CO adsorbed on the electrode i s reduced by the

25. R O D R I G U E Z E T A L . Spectroscopic Studies of Adsorbate Competition 373
Li I 12QI2 L _
2125 2100 2075 2050
WAVENUMBER (cm ) 1
Figure 1. PM-IRRAS spectra of CO adsorbed on Pt i n 0.5 M H S0 2
at 0.55 V(SHE) i n the presence of d i f f e r e n t added n i t r i l e

compounds.

presence of the n i t r i l e s . _The v(CO) frequency i s also s h i f t e d

downward to around 2078 cm" . The magnitude and d i r e c t i o n of t h i s
s h i f t are s i m i l a r to those expected for the decrease i n e l e c t r o -
dynamic coupling due to the reduced CO coverage, provided that the
decrease occurs uniformly on a molecular scale. Thus we propose
that a p a r t i a l coverage of competitively adsorbed n i t r i l e molecules
are uniformly d i s t r i b u t e d over the surface, thereby preventing
formation of a f u l l y saturated CO adlayer.
The bottom curve shows the spectrum recorded when a d i -
functional n i t r i l e , CH (CNK, i s added to the e l e c t r o l y t e . The
i n t e n s i t y of the adsorbed CO stretching band i s decreased further
and the frequency s h i f t s lower, to 2072 cm" . Taken together,
these observations suggest that the coverage of CO i s smaller than
i n the previous experiments, and that the coverage of CH (CN)„ i s
greater than for the other n i t r i l e s . The l a t t e r e f f e c t may be due
to the presence of two -CN funcational groups i n CH^CN)^* which
might be expected to increase the adsorption energy of t n i s
molecule by as much as a
_^ We were unable to
cm" that could be a t t r i b u t e d to v (CN) of the adsorbed n i t r i l e s .
A band was observed at 2260 cm" which did not s h i f t as a function
of p o t e n t i a l , which we assign to v(CN) of s o l u t i o n phase CH^(CH)^
neaj the electrode surface. We were unable to look f o r the 1615
cm" band reported by Sexton et. a l . (20), since t h i s frequency
l i e s beyond the lower energy l i m i t of the InSb detector i n our
spectrometer, and i n a s p e c t r a l region where there i s severe
background absorbance by the ^ 0 solvent.
Oxidation k i n e t i c s . We next measured the CO oxidation k i n e t i c f o r

each of these spectroscopically characterized systems. One cycle
of the voltammogram was recorded for each system, working with the
electrode exposed to bulk s o l u t i o n and s t a r t i n g and ending the
p o t e n t i a l sweep at 0.55 V. The r e s u l t s are shown i n Figure 2. The
CO oxidation peak occurs at 0.95 V during the anodic sweep, as seen
i n the voltammogram recorded i n saturated CO s o l u t i o n with no added
n i t r i l e . The remaining curves show the r e s u l t s for the solutions
with n i t r i l e s added. The area under the CO oxidation peak i s
markedly reduced i n a l l cases. The magnitude of the decrease
appears to vary i n proportion to the concentration of the added
n i t r i l e . A comparison of the bottom two curves suggests that the
d i - f u n c t i o n a l n i t r i l e , C^CCN^* may be somewhat more e f f e c t i v e at
blocking the surface than an equal concentration of a mono-nitrile.
Combining the r e s u l t s of the spectroscopic and k i n e t i c experi-
ments allows us to p a r t i a l l y confirm one aspect of the mechanism
for CO oxidation. The IRRAS r e s u l t s showed that the n i t r i l e
molecules are able to disrupt the continuity of the CO adlayer at
the molecular scale by blocking a f r a c t i o n of the surface Pt atoms.
This i s i n contrast to the procedure of preparing a p a r t i a l CO
adlayer by c o n t r o l l i n g the exposure to bulk s o l u t i o n , which
produces a uniformly d i s t r i b u t e d CO layer without blocking Pt atoms
by a second adsorbate (12). The fact that there i s no evidence f o r
enhanced CO oxidation k i n e t i c s i n the solutions with added n i t r i l e s
indicates that the presence of an exposed Pt atom next to the

25. RODRIGUEZ ETAL. Spectroscopic Studies ofAdsorbate Competition 375
I0.1mA/cm 2
RATE = 5 0 m V / S
I 1 1 I I I I
0.0 0.2 0.4 0.6 0.8 1.0 1.2
POTENTIAL (Volts ( S H E ) )
Figure 2. C y c l i c voltammograms of CO oxidation i n 0.5 M H S0^ 2
i n the presence of d i f f e r e n t added n i t r i l e compounds.

adsorbed CO molecule i s an e s s e n t i a l part of the "reactant-pair"

mechanism for the electrochemical oxidation of CO (24).
Adsorption k i n e t i c s . We can also study the adsorption k i n e t i c s of

the n i t r i l e component. This i s i l l u s t r a t e d by the IRRAS spectra
shown i n Figure 3, which demonstrate the influence of electrode
p o t e n t i a l on the competitive adsorption of CO and C H-CN. Curves a 2
and b show the c o n t r o l experiments, i n which spectra were recorded

at d i f f e r e n t p o t e n t i a l s i n saturated CO e l e c t r o l y t e with no n i t r i l e
added. A saturated CO layer i s produced i n both cases, but the
frequency i s d i f f e r e n t at the two p o t e n t i a l s ; i . e . , v(CO) * 2085
cm" at 0.55V, vs. v(C0) - 2070 cm at 0.05 V. The magnitude of
t h i s s h i f t i s i n agreement with the p o t e n t i a l dependence of v(C0)
discussed above.
The lower two spectra were recorded i n CO saturated s o l u t i o n
which contained 0.1 M C„H CN. The adsorbate layers were produced
5
by c y c l i n g the p o t e n t i a l with the electrode pulled away from the

window as described above
was chosen to end each
p o t e n t i a l of 0.05 V. At t h i s point no v(C0) band i s observed.
Spectrum d was recorded at a f i n a l p o t e n t i a l of 0.55 V ( c f . Figure
1), and shows the band at v(C0) - 2078 cm" that we assigned to a
p a r t i a l coverage of adsorbed CO. We can show that t h i s change i n
the spectrum i s i r r e v e r s i b l e by returning the p o t e n t i a l to 0.05 V.
The v(C0) band i s s t i l l observed with the same peak area, and the
frequency i s s h i f t e d by only the amount predicted by the known
p o t e n t i a l dependence.
Next we demonstrate that both CO and C«H_CN are i r r e v e r s i b l y
adsorbed under these conditions. To prove that CO adsorption i s
i r r e v e r s i b l e , we prepared a saturated CO adlayer i n a s o l u t i o n
without the n i t r i l e , and then replaced the c e l l contents with the
s o l u t i o n containing 0.2 M C H_CN. The v(C0) band of the saturated
2
adlayer remained unchanged, which shows that adsorbed CO i s not

displaced by s o l u t i o n phase C H-CN. I t now follows that n i t r i l e
2
adsorption i s also i r r e v e r s i b l e , based on the fact that the p a r t i a l

CO layer observed i n Figure 3 i s stable i n d e f i n i t e l y . I f a mixed
adsorbate layer i s observed i n the presence of both s o l u t i o n phase
components simultaneously, then i t i s impossible for one species to
be i r r e v e r s i b l y adsorbed without the adsorption of the other also
being i r r e v e r s i b l e .
The r e s u l t s i n Figure 3 can now be interpreted. The n i t r i l e
molecules are able to compete with CO for Pt adsorption s i t e s .
When the p o t e n t i a l i s s u f f i c i e n t l y negative, the adsorbed CO
molecules do not enter t h e i r l i n e a r configuration. Two of our
e a r l i e r studies have shown that co-adsorbed species can displace CO
out of i t s l i n e a r configuration under appropriate conditions. For
p a r t i a l coverages of CO studied at low temperature under vacuum
conditions, we showed that co-adsorbed adsorbed H 0 i s able to 2
displace CO away from i t s normally preferred l i n e a r configuration

(25). In electrochemical studies using K S0^, we showed that the
2
bridging configuration becomes more favorable at negative

p o t e n t i a l s (17) . In those studies, we proposed that adsorbed H 0 2
and a l k a l i cations, r e s p e c t i v e l y , donate electron density into the

CO / 5 % H S 0
y^Ô.55
2 4
g
/v=0.05
b
.o
v.
a 2085 \ /
2070
</) V = 0.05
o: + 0.1MC H CN
2 5 1.5x
UJ
H
UJ
- /
V=0.55
<
a: d
2078
i
2125 2100 2075 2050
W A V E N U M B E R (cm ) 1
Figure 3. PM-IRRAS spectra of CO adsorbed on Pt i n 0.5 M ^SO^

+ 0.2 M C2H^CN solutions as a function of electrode p o t e n t i a l
during the adsorption step (see t e x t ) .

metal and thereby help to convert CO into i t s bridging configura-

tion.
Under the present conditions, we propose that the -CN group i n
the n i t r i l e molecules acts i n a s i m i l a r fashion. The n i t r i l e
molecules are adsorbed on a f r a c t i o n of the Pt surface atoms, and
t h e i r presence forces the co-adsorbed CO molecules on the remaining
s i t e s to assume the bridging configuration. When the p o t e n t i a l i s
increased, part of the d r i v i n g force f o r t h i s conversion i s removed
and the CO molecules convert back to t h e i r l i n e a r configuration.
This conversion i s i r r e v e r s i b l e when the p o t e n t i a l i s lowered a
second time. The reason for t h i s i r r e v e r s i b i l i t y i s uncertain and
should be explored further.
The fact that l i n e a r CO species are observed at 0.05 V i n the
absence of C„H CN ( c f . spectrum a) indicates that HJD molecules at
the inner Helmnoltz plane are not able to displace CO out of i t s
l i n e a r configuration at the same p o t e n t i a l . This may be due to a
r e - o r i e n t a t i o n of the adsorbed H 0 as a function of p o t e n t i a l with
the p o s i t i v e end of th
surface as the electrod
would reduce the a b i l i t y of the 1^0 molecule to donate electron
density from i t s oxygen atom, and would also increase the a b i l i t y
of i t s hydrogen atoms to compete for accepting electron density
from the metal.
Results for co-adsorbed Sn atoms
Figure 4 shows a sequence of c y c l i c voltammograms recorded i n a CO

saturated s o l u t i o n of 0.5 M H S0, which contained 10
2 M SnCl^.
These voltammograms were recorded by increasing the upper l i m i t of
the p o t e n t i a l during successive cycles. The major feature i s the
CO oxidation peak at 0.6 V(SCE) that i s observed i n the l a t e r
scans. For cycles with an upper l i m i t below t h i s p o t e n t i a l , there
i s a second, smaller oxidation feature at about 0.4 V. Control
experiments using an SnCl^/H^SO^ s o l u t i o n without CO show that t h i s
feature can be assigned to the oxidation of adsorbed Sn atoms. We
note that the Sn oxidation step does not produce a well-resolved
current maximum i n the curves i n Figure 4. We i n t e r p r e t t h i s to
indicate that adsorbed CO molecules are r a p i d l y oxidized by newly
generated Sn cations, thus regenerating the Sn adatoms and allowing
further oxidation current to flow.
As the upper l i m i t of the cycles approaches 0.5 V, the s i z e of
the Sn oxidation feature gradually decays. Cycles with an upper
l i m i t above 0.6 V are v i r t u a l l y i n d i s t i n g u i s h a b l e from those
recorded i n CO saturated H SO, without added SnCl,. This indicates
that the Sn atoms leave the surface i n t h e i r oxidized state during
the anodic stage of the cycle and are unable to readsorb during the
cathodic stage.
Figure 5 shows the IRRAS spectra recorded for three dosing
conditions chosen to demonstrate the nature of the Sn adsorption
k i n e t i c s . A l l three spectra were recorded at 0.0 V. The upper
spectrum i s the c o n t r o l curve recorded i n CO saturated H S0^,. The 2
v(C0) band occurs at 2083 cm" , which i s c h a r a c t e r i s t i c of a

saturated CO adlayer at t h i s p o t e n t i a l .

25. RODRIGUEZ ETAL. Spectroscopic Studies of Adsorbate Competition 379
3.0 ~
Potential ( V SCE )
Figure 4. C y c l i c voltammograms of CO oxidation i n 0.5 M H^SO^

+ 10"" M SnCl, f o r progressively larger upper p o t e n t i a l l i m i t s .


The middle spectrum i s recorded i n CO-saturated SnCl^/H^SO^

a f t e r c y c l i n g the electrode p o t e n t i a l through 1.2 V and tnen
returning to 0.0 V. The spectrum i s v i r t u a l l y indistinguishable
from the f i r s t curve, which shows that the CO adlayer i s s t i l l
saturated. This confirms that l i t t l e , i f any, adsorption of Sn
adatoms occurs even a f t e r the i n i t i a l l y adsorbed CO layer i s
removed by oxidation. Instead, competitive adsorption of new CO
molecules blocks the surface.
The bottom spectrum was obtained by c y c l i n g the electrode i n
CO-free SnCl^/^SO^ s o l u t i o n to ensure formation of a p a r t i a l Sn
adlayer and then replacing the c e l l contents with CO-saturated
s o l u t i o n . The v(C0) band i s s t i l l observed, which shows that the
Sn adatoms do not saturate the surface even i n the absence of
competitive CO adsorption. The i n t e n s i t y and frequency of the
v(C0) band have both decreased, which confirms that the CO adlayer
i s only p a r t i a l l y complete. There i s no evidence f o r a change i n
v(C0) beyond that expected f o r the coverage dependence expected i n
acid s o l u t i o n . This show
between adsorbed CO molecule
support of the assumptions used i n the adatom oxidation model
discussed above.
Summary
The v i b r a t i o n a l spectroscopy of CO adsorbed on Pt electrodes has

proven to be a valuable t o o l f o r probing the physical chemistry of
the metal/electrolyte i n t e r f a c e . The exact value of the v i b r a -
t i o n a l frequency and the r e l a t i v e i n t e n s i t y of the l i n e a r and
bridging bands both provide an i n d i c a t i o n of the a b i l i t y of the
electrode surface to donate charge into adsorbed species. Band
i n t e n s i t i e s provide a d i r e c t , q u a l i t a t i v e method to monitor surface
coverages i n experiments using co-adsorbed species. Future experi-
ments should focus on measuring the e f f e c t s of co-adsorbed species
more q u a n t i t a t i v e l y , using other conventional electrochemical
techniques to accurately determine surface coverages.
Acknowledgment s
We r e s p e c t f u l l y acknowledge both the encouragement to undertake

t h i s research and also the many contributions to the f i e l d of
v i b r a t i o n a l spectroscopy that were made by the l a t e Professor John
Overend.
This work was sponsored by the Corrosion Research Center at
the University of Minnesota, which i s supported by the U.S. Depart-
ment of Energy, through Grants DE-FG02-84ER45173 and DE-79ER10450.
References
1. V i b r a t i o n a l Spectroscopy of Adsorbed Species; Bell, A. T.;

Hair, M. L., Eds.; ACS Symposium Series No. 137; American
Chemical Society; Washington, DC, 1980.
2. Eischens, R. P.; Francis, S. A.; Pliskin, W. A. J. Phys. Chem.
1956, 60, 194.

3. Hammaker, R. M . ; Francis, S. A . ; Eischens, R. P. Spectrochem.

Acta 1965, 21, 1295.
4. Primet, M . ; Basset, J . M . ; Mathieu, M. V . ; Prettie, M.
J. Catal. 1973, 29, 213.
5. Sheppard, N . ; Nguyen, T. T. In Advances IR and Raman Spectro
scopy; Hester, R. E . ; Clark, R. J. H . , Eds.; Heyden: London,
1978.
6. Shigeishi, R. A . ; King, D. A. Surf. S c i . 1976, 58, 379.
7. Horn, K . ; Pritchard, J . J . Physique, Colloq. 1977, 38,
C4-164.
8. Krebs, H. J.; Luth, H. Appl. Phys. 1977, 14, 337.
9. Hayden, B. E . ; Bradshaw, A. M. Surf. S c i . 1983, 125 787.
10. Severson, M. W.; Tornquist, W. J.; Overend, J . J . Phys. Chem.
1984, 88, 469.
11. Beden, B . ; Bewick, A . ; Kunimatsu, K . ; J. Electroanal Chem.
1982, 142 345.
12. Russel, J. W.; Severson M . ; Scanlon K . ; Overend J.;
Bewick, A. J. Phys
13. Kunimatsu, K . ; Seki
Philpott, M. R. Langmuir 1986, 2, 464.
14. Blyholder, G.; J. Phys. Chem. 1964, 68, 2772.
15. Crossley, A . ; King, D. A. Surf. Sci 1977, 68, 528.
16. Severson, M. W.; Russell, A . ; Cambell, D.; Russell, J . W.
Langmuir 1987, 3, 202.
17. Tornquist, W. J.; Guillaume, F . ; Griffin, G. L. Langmuir
1987, 3, 477.
18. Nakajima, H . ; Kita, H . ; Kunimatsu, K . ; Aramata, A. J .
19. Lambert, D. K. Solid State Commun. 1983, 30, 59.
20. Sexton, B. A . ; Avery, N. R. Surf. S c i . 1983, 129, 21.
21. Loo, B. H . ; Lee, Y. G.; Frazier, D. O. Chem. Phys. Lett.
1985, 119, 312.
22. Loo, B. H . ; Lee, Y. G.; Frazier, D. O. J . Phys. Chem. 1985,
89, 4672.
23. Watanabe, M . ; Shibata, M . ; Motoo, S. J. Electroanal. Chem.
1985, 187, 161.
24. Gilman, S. J . Phys. Chem. 1964, 68, 70.
25. Tornquist, W. J.; Griffin, G. L. J. Vac. Sci. Technol. A
1986, 4, 1437.

Chapter 26
Surface-Enhanced Raman Study

Effect of pH and Electrode Potential
on the Interfacial Behavior
of Some Substituted Pyridines
1 2
Mark R. Anderson and Dennis H. Evans
1
Department of Chemistry, University of Utah, Salt Lake City,
2
Department of Chemistr
Newark, DE 19716
The surface-enhanced Raman spectra (SERS) provide
information about the extent of protonation of the
species adsorbed at the silver/aqueous solution
interface. The compounds investigated were 4-pyridyl-
carbinol (1), 4-acetylpyridine (2), 3-pyridine-
carboxaldehyde (3), isonicotinic acid (4),
isonicotinamide (5), 4-benzoylpyridine (6), 4-
(aminomethyl)pyridine (7) and 4-aminopyridine (8). For
1, the fraction of the adsorbed species which was
protonated at -0.20 V vs. SCE varied with pH in a
manner indicating stronger adsorption of the neutral
than the cationic form. The fraction protonated
increased at more negative potentials. Similar results
were obtained with 3. For all compounds but 4, bands -1
due to the unprotonated species near 1600 cm and for -1
the ring-protonated species near 1640 cm were seen in
the SERS spectra.
In 1974 Fleischmann e t a l . demonstrated t h a t Raman s p e c t r a o f
p y r i d i n e adsorbed a t a s i l v e r e l e c t r o d e from an aqueous s o l u t i o n
c o u l d be o b t a i n e d w i t h e x c e l l e n t s i g n a l - t o - n o i s e a t a roughened
s i l v e r surface Q). Subsequently, Jeanmaire and Van Duyne (2) as
w e l l as A l b r e c h t and C r e i g h t o n (3) demonstrated t h a t the Raman
spectrum o f adsorbed p y r i d i n e a t the s i l v e r s u r f a c e r e p r e s e n t e d a 10
enhancement o f the s i g n a l expected c o n s i d e r i n g t y p i c a l Raman
parameters. Such a d i s c o v e r y was very e x c i t i n g because i t p r e s e n t e d
a r e l a t i v e l y s i m p l e means o f o b t a i n i n g i n s i t u the v i b r a t i o n a l
s p e c t r a o f m o l e c u l e s adsorbed onto a s u r f a c e . S i n c e t h a t t i m e ,
c o n s i d e r a b l e e f f o r t has been devoted t o s t u d y i n g t h i s phenomenon.
Much o f t h i s r e s e a r c h e f f o r t has been d i r e c t e d t o the study o f
the fundamental b a s i s o f surface-enhanced Raman s c a t t e r i n g (SERS), i n
o r d e r t o understand the u n d e r l y i n g p r i n c i p l e s . There have a l s o been
many a p p l i c a t i o n s o f SERS t o s i t u a t i o n s i n which i n s i t u v i b r a t i o n a l
0097-6156/88/0378-0383$06.00/0
c

s p e c t r a would p r o v i d e v a l u a b l e i n f o r m a t i o n . An e l e c t r o c h e m i c a l
e n v i r o n m e n t i s o n e s u c h s y s t e m w h e r e SERS h a s b e e n p a r t i c u l a r l y
valuable. SERS h a s b e e n u s e d t o s t u d y a number o f e l e c t r o c h e m i c a l
phenomena, i n c l u d i n g the a d s o r p t i o n o f s i m p l e a n i o n i c a d s o r b a t e s and
t h e mechanisms o f e l e c t r o d e r e a c t i o n s ( 4 , 5 ) . It i s a l s o p o s s i b l e to
s t u d y p r o p e r t i e s o f s u r f a c e s p e c i e s by s y s t e m a t i c a l l y a l t e r i n g t h e
c o n d i t i o n s under which s p e c t r a are o b t a i n e d . In t h i s manner,
s p e c t r o s c o p i c c h a n g e s may b e c o r r e l a t e d w i t h t h e e n v i r o n m e n t a l
p e r t u r b a t i o n s and i n f o r m a t i o n about the p r o p e r t i e s o f the m o l e c u l e a t
t h e s u r f a c e may b e d e d u c e d .
I n a p r e v i o u s s t u d y ( 6 ) we i n v e s t i g a t e d t h e s p e c t r a o f a d s o r b e d
4 - p y r i d i n e c a r b o x a l d e h y d e as a f u n c t i o n o f a p p l i e d e l e c t r o d e p o t e n t i a l
and as a f u n c t i o n o f b u l k s o l u t i o n pH. T h i s s t u d y demonstrated t h a t
t h e s p e c t r u m o f 4 - p y r i d i n e c a r b o x a l d e h y d e was d r a m a t i c a l l y d e p e n d e n t
upon t h e s e e x p e r i m e n t a l v a r i a b l e s . Separate spectroscopic features
w e r e i d e n t i f i e d w h i c h c o u l d be a t t r i b u t e d t o t h e p r o t o n a t e d a n d t h e
unprotonated 4-pyridinecarboxaldehyde species. Interestingly, in
s o l u t i o n s n e a r pH 7 , w h e r
pyridinecarboxaldehyde i
t o the p r o t o n a t e d s p e c i e s on the s u r f a c e appeared i n the s p e c t r u m a t
negative potentials. T h i s b e h a v i o r was t h o u g h t t o be c a u s e d l a r g e l y
by t h e p o t e n t i a l dependence o f t h e a d s o r p t i o n c o e f f i c i e n t s , t h a t o f
t h e c a t i o n b e i n g r e l a t i v e l y l a r g e r a t more n e g a t i v e p o t e n t i a l s . A
s m a l l e r c o n t r i b u t i o n a r i s e s f r o m l o w e r i n g o f t h e s o l u t i o n pH i n t h e
r e g i o n l o c a l to the e l e c t r o d e s u r f a c e . S u c h a phenomenon h a d
p r e v i o u s l y b e e n o b s e r v e d i n a SERS s t u d y o f p h o s p h a t e s p e c i e s ( 7 ) a n d
i s s u p p o r t e d by e l e c t r o c h e m i c a l t h e o r y . In a d d i t i o n , as the
e l e c t r o d e p o t e n t i a l was made more n e g a t i v e , t h e c a r b o n y l f e a t u r e
g r a d u a l l y d i m i n i s h e d i n s i z e and e v e n t u a l l y d i s a p p e a r e d . This
o b s e r v a t i o n was a t t r i b u t e d t o a n i n c r e a s i n g d e g r e e o f h y d r a t i o n o f
t h e 4 - p y r i d i n e c a r b o x a l d e h y d e a s t h e e l e c t r o d e p o t e n t i a l was made m o r e
n e g a t i v e , i n consonance w i t h the f a c t t h a t the c a r b o n y l group o f
p r o t o n a t e d 4 - p y r i d i n e c a r b o x a l d e h y d e i s 94? h y d r a t e d i n s o l u t i o n .
T h e s e i n t e r p r e t a t i o n s d i f f e r e d somewhat f r o m t h o s e o f B u n d i n g a n d
B e l l ( 8 ) i n a s i m i l a r SERS s t u d y o f 4 - p y r i d i n e c a r b o x a l d e h y d e . These
w o r k e r s c o n c l u d e d t h a t e l e c t r o n w i t h d r a w a l by t h e e l e c t r o d e f r o m t h e
adsorbed 4-pyridinecarboxaldehyde induced the t o t a l h y d r a t i o n o f the
formyl substituent. S u p p o r t f o r t h i s i n t e r p r e t a t i o n was g a i n e d b y
c o n s i d e r i n g t h e s p e c t r o s c o p i c b e h a v i o r o f s i m i l a r compounds w i t h i n
the c o n t e x t o f the 4-pyridinecarboxaldehyde o b s e r v a t i o n s . Bunding
and B e l l , however, o n l y i n v e s t i g a t e d the s p e c t r o s c o p i c b e h a v i o r a t a
single, negative potential. I t i s the purpose o f the c u r r e n t study
t o i n v e s t i g a t e s y s t e m a t i c a l l y the s p e c t r o s c o p i c b e h a v i o r o f o t h e r
p y r i d i n e d e r i v a t i v e s as a f u n c t i o n o f e l e c t r o d e p o t e n t i a l and b u l k
s o l u t i o n pH a n d t o c o m p a r e t h e o b s e r v a t i o n s t o t h o s e p r e v i o u s l y
presented for 4-pyridinecarboxaldehyde.
R e s u l t s and D i s c u s s i o n
Compounds 1-8 h a v e b e e n i n v e s t i g a t e d . 4 - P y r i d y l c a r b i n o l , 1, i s o f
i n t e r e s t b e c a u s e i t i s one o f t h e e l e c t r o c h e m i c a l r e d u c t i o n p r o d u c t s
o f 4 - p y r i d i n e c a r b o x a l d e h y d e , the species f o r which surface
p r o t o n a t i o n r e a c t i o n s were d i s c o v e r e d and c h a r a c t e r i z e d i n e a r l i e r
work ( 6 ) .

26. ANDERSON AND EVANS Interfacial Behavior of Substituted Pyridines 385
Characterization of Surface Species by SERS. Before presenting the

results obtained with 1, the spectral features which have proven to
be useful in identifying surface species w i l l be reviewed. Both in
solution and by SERS, pyridines show a ring mode in the Raman
spectrum near 1600 cm"'. When the ring nitrogen i s protonated, thi;
band disappears and i s replaced by a band near 1640 cm" . The
R 1 : R = -CH 0H 2
7 :R •NH2
1-2, 4-8 3 8 : R •COC6H5
r e l a t i v e intensities of these two bands provide information about the

extent of protonation. If one assumes that the scattering cross
sections for unprotonate
species (1640 cm band
compound which is protonated is given by Ii640 ( 1640 ^600) where
a n d a r e t n e
11600 11640 heights of the two bands.
In the present research, i t was confirmed for compounds 1-3
that, in the normal Raman spectra of aqueous solutions of various pH,
a band near 1600 cm appears for the neutral pyridine and a band
near 1640 cm"' exists for the ring-protonated species.
In cases where the substituent on the pyridine ring contains a
carbonyl group, a weak band for the C-0 stretch can be detected in
1
the SERS spectra, generally near 1700 cm" .
The SERS spectra of pyridines contain many other bands but those
mentioned above have proven to be particularly useful in
characterizing the surface species.
4-Pyridylcarbinol, 1. This compound has been investigated previously

(8) and i t was noted that i t s SERS spectra were almost i d e n t i c a l to
those of 4-pyridinecarboxaldehyde. SERS spectra in the 1500-1700
1
cm" region are shown in Figure 1. Buffers with pH bracketing the
pK of 4-pyridylcarbihol (5.76 (9)) were employed and i t can be seen
a
that the band for the unprotonated species near 1600 cm" i s
predominant at pH 6.88 but decreases as the band due to the
protonated species (near 1640 cm" ) grows in when the pH i s lowered.
A variety of buffers was used and the intensity r a t i o was measured
from SERS spectra obtained at -0.20 V vs. SCE. As mentioned above,
t h i s intensity ratio is a measure of the fraction of the surface
compound which i s protonated. The fraction i s plotted in Figure 2
along with the fraction protonated in solution (calculated from the
pK ).
a It i s apparent that the fraction protonated at the surface
lags the fraction protonated in solution as the pH i s lowered. This
may be caused by r e l a t i v e l y stronger adsorption of the neutral
pyridine compared to the protonated species at this potential.
Considering competitive adsorption of two species according to the
Langmuir isotherm at close-to-saturation surface coverage, the
fraction of the surface species which i s protonated, ( X ) , w i l l be p s
given by Equation 1, where [H*] i s the hydronium ion concentration

Figure 1. SERS spectra of 0.050 M 4-pyridylcarbinol in solutions

of various pH. A l l spectra were obtained at -0.20 V vs. SCE.

pH
Figure 2. Surface mole fraction of protonated 4-pyridylcarbinol
vs. pH. Points are from SERS spectra obtained at -0.20 V vs.

SCE. Dashed: mole fraction of the protonated form i n solution.
S o l i d : mole fraction of protonated form on surface from Equation
1 with K = 30.
+ +
(Xp) s = [H ]/([H ] + K K) a (1)
in solution, K i s the acid dissociation constant in solution and K =

a
w n e r e a n d
rn,s&n/rp Bp
> s ^s B are saturation coverages and adsorption
c o e f f i c i e n t s , respectively, for the neutral (n) and protonated (p)
species. At the concentration used in this work, close-to-saturation
coverage i s expected based on adsorption studies of other pyridines
at a mercury electrode (10, 11). Equation 1 i s plotted in Figure 2
( s o l i d curve) for K = 30 which matches the experimental data
reasonably well. Introduction of interaction parameters through the
Frumkin isotherm brought a perceptible improvement in the agreement
but, in view of the scatter in the experimental data, this refinement
i s probably not meaningful.
Thus, at -0.20 V, the adsorption coefficient of the neutral form
of 4-pyridylcarbinol i s about 30 times that of the protonated form
(assuming equal saturation coverages). This quantity i s dependent
upon the electrode potential, however. In Figure 3 are shown SERS
spectra obtained at constan
electrode potential. A
(weak feature at 1640 cm ) but the fraction increases substantially
as the potential i s made more negative u n t i l at the most negative
potential (-0.60 V) i t decreases again. The same trend was observed
with 4-pyridinecarboxaldehyde (6) and can be explained by r e l a t i v e l y
stronger adsorption of the cation (protonated form) which i s expected
at more negative potentials. A smaller contributor to the effect i s
the increase in the effective pH in the i n t e r f a c i a l region as the
potential i s made more negative (6 7). The intensity r a t i o i s given
t
in Table I along with the solution pH which would be necessary to

cause the same fraction of 1 to be protonated as i s present on the
surface.
Table I. Fraction of 4-Pyridylcarbinol which i s

a
Protonated as Calculated from SERS Spectra
Potential ( V vs. S C E ) (x )
p s
pH b
-0.20 0.15 6.6

-0.30 0.22 5.0
-0.40 0.36 4.7
-0.50 0.36 4.7
*Data from Figure 3, pH 6.88.

pH in solution which produces fraction protonated equal to that seen
on the surface.
4-Acetylpyridine 2. Relatively intense SERS spectra were obtained

t
for 2 using 0.10 M KC1 (8) but there was l i t t l e dependence of the
r e l a t i v e intensities of the bands on potential. A band due to the
unprotonated pyridine was seen near 1600 cm" and, at pH < 6, a band
due to the protonated compound appeared near 1640 cm and increased
at the expense of the 1600 cm"' band u n t i l only the protonated
species could be detected at pH = 1.3. The pK of 2 i s 3.51 (9), a

ANDERSON AND EVANS Interfacial Behavior of Substituted Pyridines 389
Figure 3. SERS spectra of 0.050 M 4-pyridylcarbinol i n pH 6.88

buffer at various electrode potentials (vs. SCE).

about two units smaller than 1, and correspondingly lower pH values

are required to generate large populations of the protonated form of
2 on the surface. Unlike 1 and 4-pyridinecarboxaldehyde, the
f r a c t i o n protonated at constant pH hardly changes with p o t e n t i a l .
In 0 . 1 0 M K C 1 , the SERS spectra of 2 show a small band a t about
1690 cm" , attributable to the carbonyl stretch. Allen and Van Duyne
( 1 2 ) have considered orientational effects on band i n t e n s i t i e s and
have concluded that the r e l a t i v e i n t e n s i t i e s should be given by
Equation 2 , where the intensity of the carbonyl band
dôîoooJsERs I I
= ( I69O/ IOOO)NRS # C O S 0 2
< >
i s expressed r e l a t i v e to the intense symmetrical ring-breathing band

near 1 0 0 0 cm"', i n both the SERS and normal Raman solution spectra
(NRS). 0 i s the angle of the carbonyl group with respect to the
surface normal.
For v e r t i c a l orientation of 4-acetylpyridine (adsorption v i a the
rine nitrogen atom), 0 w i l
T
cm" bands i n the SERS an
to Equation 2 and gave 0 = 6 1 , 5 9 and 6 3 for - 0 . 2 0 , - 0 . 4 0 and - 0 . 6 0
V, respectively. Thus, the results are consistent with a v e r t i c a l
orientation which i s independent of p o t e n t i a l .
3-Pyridinecarboxaldehyde 3 . Possible hydration of the aldehyde

t
group makes the aqueous solution chemistry of 3 p o t e n t i a l l y more

complex and interesting than the other compounds. Hydration i s l e s s
extensive with 3 than 4-pyridinecarboxaldehyde but upon protonation,
about 80% w i l l e x i s t as the hydrate (gem-diol). The calculated
d i s t r i b u t i o n of species as a function of pH i s given i n Figure 4
based on the equilibrium constants determined by Laviron ( 9 ) .
In comparison to 1 and 2 , the SERS spectra of 3-pyridine-
carboxaldehyde ( 3 ) are r e l a t i v e l y featureless ( 8 ) . The spectra are
dominated by the symmetrical ring-breathing mode at 1 0 3 0 cm" but the
features associated with the unprotonated species (about 1 6 0 0 cm" )
and the protonated species (about 1 6 4 0 cm"') are d e f i n i t e l y present
along with a weak carbonyl band at about 1 7 1 0 cm" . The v a r i a t i o n i n
the r e l a t i v e population of protonated species i s as expected (Figure
5 ) though a detailed analysis reveals some surprises. As can be seen
in Figure 5 , about equal i n t e n s i t i e s of the 1 6 0 0 and 1 6 4 0 cm" bands1
are obtained at pH = 3 . 8 6 , near the pK ( 3 . 7 3 ( 9 ) ) . However, the

a
band associated with the unprotonated pyridine persists at pH = 1 . 3 ,

where less than \% of the solution species remains unprotonated.
When the intensity ratios are measured for a variety of buffers, and
the values are plotted vs. pH, the values approach 0 . 8 at low pH
(Figure 6 ) , the same as the f r a c t i o n of 3 e x i s t i n g i n solution as the
protonated, hydrated form ( c f . Figure 4 ) . This could mean that the
residual 1 6 0 0 cm" band seen at low pH i s due to protonated,
unhydrated 3 on the surface.
As seen with 4-acetylpyridine, the r e l a t i v e i n t e n s i t i e s of the
1600 and 1 6 4 0 cm features, at constant solution pH, are i n s e n s i t i v e
to electrode potential. Again, t h i s behavior may be associated with
the r e l a t i v e l y weaker b a s i c i t y of 3 and 2 (pK = 3 . 5 1 and 3 . 7 3 ,
a
respectively) compared to 1 ( 5 . 7 6 ) and 4-pyridinecarboxaldehyde

( 4 . 7 8 ) though the exact reason i s not known. The l a t t e r two show

Figure 5. SERS spectra of 0.050 M 3-pyridinecarboxaldehyde i n

solutions o f various pH. A l l spectra were obtained a t -0.20 V
vs. SCE.

1. O -
1 2 3 4 5 6 7 8 9 10 11 12 13 14

pH
/ I
F i g u r e 6. Experimental i n t e n s i t y r a t i o ( I i 6 4 0 ( 1 6 4 0 + *1600))
f r o m SERS s p e c t r a o f 0 . 0 5 0 M 3 - p y r i d i n e c a r b o x a l d e h y d e o b t a i n e d a t
- 0 . 2 0 V v s . S C E . Curve i s mole f r a c t i o n o f p r o t o n a t e d / h y d r a t e d

species present i n s o l u t i o n .
r e l a t i v e l y higher populations of protonated pyridine in the SERS

spectra as the potential i s made more negative.
At the most negative potentials, the protonated form of 3
appears to desorb as seen also with 1 and 2. For 4-pyridine-
carboxaldehyde, this desorption has been correlated with the
desorption of chloride (6) suggesting that the cation and chloride
ion are coadsorbed.
Isonicotinic Acid, 4. It i s d i f f i c u l t to obtain a spectrum of 4

because the neutral form i s not very soluble. At low pH, however,
the ring nitrogen i s protonated (J3) and the cationic i s o n i c o t i n i c
acid i s s u f f i c i e n t l y soluble to obtain SERS spectra. A r e l a t i v e l y
intense spectrum was obtained at -0.20 V with 0.050 M i s o n i c o t i n i c
acid, 0.10 M KC1 and 0.10 M HC1. Many of the spectral features seen
with other pyridines are present but the i n a b i l i t y to vary solution
pH made i t impossible to investigate the relative surface populations
of protonated and unprotonated forms.
Isonicotinamide, 5. Thi
SERS spectra to be obtained at the 50 mM level in 0.10 M KC1 and 0.10
M KC1 + 0.10 M HC1 at -0.20 V. The spectra resembled those seen with
other pyridines. In particular, an intense band at 1600 cm was
seen with the neutral electrolyte and i t was replaced by a band at
1640 cm"' i n the acidic electrolyte. Of the two basic s i t e s , only
the ring nitrogen w i l l be protonated in 0.10 M HC1 (J_3) so, with this
compound also, the 1640 cm band appears to be due to the protonated
pyridine. No carbonyl band was seen in either spectrum.
4-Benzoylpyridine, 6. Of possible interest here i s the fact that 6

contains both a pyridyl and a phenyl group. Pyridine and benzene
have very similar vibrational modes which should produce bands due to
both aromatic groups at approximately the same positions in the
spectra of 6. Like isonicotinic acid, 6 was r e l a t i v e l y insoluble i n
water but i t was s u f f i c i e n t l y soluble i n 50 % (v/v) ethanol/water to
allow spectra to be obtained at the 50 mM l e v e l . Again, spectra were
recorded at -0.20 V i n 0.10 M KC1 and i n 0.10 M KC1 + 0.10 M HC1
(Figure 7). Under both conditions, strong bands, characteristic of
the aromatic ring systems, are seen near 1000, 1200 and 1600 cm" . A
carbonyl band appears at approximately 1660 c m . The main
difference between the spectrum obtained at low pH and that recorded
from neutral solution, i s the band near 1640 cm which i s again
attributed to the protonated pyridyl ring. In this case, the strong
band remaining at about 1600 cm"' i s probably due to the phenyl
group.
4-(Aminomethyl)pyridine, 7. The SERS spectra of most pyridines show

a broad, r e l a t i v e l y featureless background over the range of 1200-
1700 cm" . This background scattering i s immense for 7 i n 0.10 M KC1
1
at -0.20 V. Atop the background i s the strong band near 1600 cm" ,
characteristic of the neutral pyridyl ring. The spectrum obtained in
1
0.10 M KC1 + 0.10 M HC1 has no band at 1600 cm" but, instead, a very
1
strong band at about 1640 cm" i s seen. In a l l of the other
pyridines this band i s associated with the protonated pyridyl ring.
The aminomethyl group i s the more basic s i t e on 7 so the appearance

ANDERSON AND EVANS Interfacial Behavior of Substituted Pyridines 395
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
1
Raman S h i f t , cm"
Figure 7. SERS spectra of 0.050 M 4-benzoylpyridine obtained at
-0.20 V vs. SCE. 50J (v/v) ethanol/water. A: 0.10 M KC1. B:
0.10 M KC1 + 0.10 M HC1. (Sharp lines at 738, 1040 and 1060
1
cm" are from scattered argon ion emission).

1
of the band at 1640 cm" probably means that both the aminomethyl
group and the pyridyl nitrogen are protonated in the acidic medium.
4-Aminopyridine, 8. Like 4-(aminomethyl)pyridine, 8 has two basic

s i t e s . The pK of the ring nitrogen i s 9.12 while that of the amino
a
group i s estimated to be -6 (14, 15). The SERS spectrum in 0.10 M

1
KC1 has a very large background between 1200 and 1700 cm" ( l i k e that
seen with 7) with a weak band due to the unprotonated pyridine at
about 1600 c m . In this case, protonation of the pyridyl nitrogen
occurs readily so that even with a buffer of pH = 6.19, the 1600 cm" 1
band has been replaced by a band near 1640 cm" . (The broad back-
ground between 1200 and 1700 cm"' i s also much weaker). The spectrum
obtained with 0.10 M KC1 + 0.10 M HC1 i s almost identical to that
seen with the pH = 6.19 buffer. In view of the pK values for 8, a
protonation of the amino group i s not expected in 0.10 M HC1.
Experimental
4-Pyridylcarbinol, 4-acetylpyridine
aminomethylpyridine were obtained from Aldrich Chemical Company
(Milwaukee, Wisconsin) and were purified by d i s t i l l a t i o n at reduced
pressure. 4-Benzoylpyridine was recrystallized from ethanol.
4-Aminopyridine (G. Frederick Smith Chemical Company), i s o n i c o t i n i c
acid (Aldrich) and isonicotinamide (Aldrich) were used as received.
T r i p l y d i s t i l l e d water was used. A l l other reagents were a n a l y t i c a l
reagent grade.
Acetate buffers were used for pH values between 3.5 and 5.5
while phosphate buffers were used for pH 5.5-7. The pH of solutions
below pH 3.5 was adjusted with HC1. A l l solutions contained 0.10 M
KC1 and the ionic strength of the buffers was adjusted to 0.90 M by
addition of potassium nitrate.
A l l SERS experiments were conducted with a polycrystalline
s i l v e r working electrode prepared by p r e s s - f i t t i n g a 6 mm diameter
cylinder of s i l v e r into one end of a 0.375 inch diameter Teflon rod
through which a 6 mm diameter concentric hole had been d r i l l e d .
E l e c t r i c a l contact was made via a copper wire soldered to the s i l v e r .
The geometric area of the s i l v e r disk was 0.28 cm .
The SERS c e l l was b u i l t following the design of Brandt (16).
Prior to the experiment, the s i l v e r electrode was polished with 5,
0.3 and 0.05 mu alumina. After polishing, the electrode surface was
rinsed with copious amounts of t r i p l y d i s t i l l e d water followed by
sonication in t r i p l y d i s t i l l e d water. The SERS c e l l was then
assembled and f i l l e d with an analyte solution which had been
previously purged with nitrogen. The s i l v e r electrode was then
subjected to an oxidation-reduction cycle (ORC), v i z . , oxidation at
0.20 V for ten seconds followed by reduction of the generated s i l v e r
s a l t at -0.30 V u n t i l the current decreased to about zero.
The spectra were taken using the 488.0 nm l i n e of a Spectra
Physics model 164-00 argon ion laser with an incident power of 100 mW
at the electrode surface. The laser l i g h t was focused to a l i n e
image at the electrode with a c y l i n d r i c a l lens. The scattered l i g h t
was focused onto the entrance s l i t of a Spex model 1401 double
monochromator (2.0 cm resolution) and detection was by photon
counting (using an RCA model C31034-02 photomultiplier tube). Data

26. A N D E R S O N A N D E V A N S Interfacial Behavior of Substituted Pyridines 397
c o l l e c t i o n was performed with a microcomputer system. The intensity

of the SERS spectra varied considerably with changes in conditions.
A l l spectra have been plotted with an arbitrary scale for the
ordinate.
The electrode potential was controlled with an EG & G Princeton
Applied Research (PAR) model 173 potentiostat/galvanostat and i s
referenced to a saturated calomel electrode (SCE). A PAR model 276
current-to-voltage converter allowed monitoring of current during the
ORC and SERS experiments and i t also provided for positive feedback
iR compensation for accurate potential control.
Acknowledgment
This research was supported bv the National Science Foundation, Grant

CHE-8722764.
Literature Cited
1. Fleischmann, M.; Hendra

Lett. 1974, 26, 163-166.
2. Jeanmaire, D. L.; Van Duyne, R. P. J . Electroanal. Chem. 1977,
84, 1-20.
3. Albrecht, M. G.; Creighton, J . A. J . Am. Chem. Soc. 1977, 99,
5215-5217.
4. Weaver, M. J . ; Hupp, J. T.; Barz, F.; Gordon, J . G.; Philpott, M.
R. J. Electroanal. Chem. 1984, 160, 321-333.
5. Rubim, J . C. J. Electroanal. Chem. 1987, 220, 339-350.
6. Anderson, M. R.; Evans, D. H. (submitted to J . Am. Chem. Soc.)
7. Dorain, P. B.; Von Raben, K. U.; Chang R. K. Surf. S c i . 1984,
148, 439-452.
8. Bunding, K. A.; B e l l , M. I. Surf. S c i . 1983, 118, 329-344.
9. Laviron, E. B u l l . Soc. Chim. Fr. 1961, 2325-2349.
10. Barradas, R. G.; Conway, B. E. Electrochim. Acta 1961, 5, 319-
348.
11. Barradas, R. G.; Conway, B. E. Electrochim. Acta 1961, 5, 349-
361.
12. Allen, C. S.; Van Duyne, R. P. Chem. Phys. Lett. 1979, 63, 455-
459.
13. Jellinek, H. H. G.; Urwin, J . R. J . Phys. Chem. 1954, 58, 548-
550.
14. Fischer, A.; Galloway, W. J . ; Vaughan, J . J. Chem. Soc. 1964,
3591-3596.
15. Brignell, P. J . ; Johnson, C. D.; Katritzky, A. R.; Shakir, N.;
Tarhan, H. O.; Walker, G. J . Chem. Soc., B 1967, 1233-1235.
16. Brandt, E. S. Anal. Chem. 1985, 57, 1276-1280.
RECEIVED July 11,1988

Chapter 27
Effect of Underpotentially Deposited Lead

on the Surface-Enhanced Raman Scattering
of Interfacial Water at Silver
Electrode Surfaces
1
Jose C. Coria-Garcia and Jeanne E. Pemberton
Department of Chemistry, University of Arizona, Tucson,
The influence of underpotentiall

and submonolayers on the surface enhanced Raman
s c a t t e r i n g (SERS) of i n t e r f a c i a l H 0 at roughened Ag
2
electrodes i n aqueous chloride and bromide solutions i s

presented. With laser e x c i t a t i o n at 5145 Å, the SERS
i n t e n s i t y of thev(OH)v i b r a t i o n of i n t e r f a c i a l H 0 a t
2
-1 -1
3495 cm and 3505 cm in aqueous chloride and bromide,
respectively, decreases as the first monolayer of Pb is
deposited. The rate of the decrease is e s s e n t i a l l y
independent of the nature of the supporting e l e c t r o l y t e
anion and is s i g n i f i c a n t l y d i f f e r e n t than the rate of
- -
decrease of the v(Ag-X) (X=C1 , B r ) v i b r a t i o n s i n these
media. The presence of i n t e r f a c i a l H 0 at all coverages
2
of UPD Pb precludes i n t e r p r e t a t i o n of these r e s u l t s

strictly in terms of a decrease in adsorbate surface
coverage. The r e s u l t s are interpreted as a combination
of changes in electromagnetic enhancement r e s u l t i n g from
a l t e r a t i o n of the surface o p t i c a l properties of the
electrode in the presence of UPD Pb and decreased
e f f i c i e n c y of photoassisted charge transfer r e s u l t i n g
from a l t e r a t i o n of the Fermi l e v e l at microscopic surface
active s i t e s i n the presence of UPD Pb.
Several recent experimental investigations have been directed
towards i n v e s t i g a t i n g the influence of underpotentially deposited
foreign metal monolayers on the surface enhanced Raman s c a t t e r i n g
(SERS) a b i l i t y of Ag and Au electrodes.(1-16) These studies have
been undertaken with the intent of further e l u c i d a t i n g the mechanism
of the SERS phenomenon. SERS i s generally thought to r e s u l t from a
combination of two mechanisms. The f i r s t i s c l a s s i c a l
electromagnetic enhancement of the e l e c t r i c f i e l d at the interface
between an appropriately roughened metal substrate and another
medium. An a d d i t i o n a l mechanism i s a resonance-like enhancement
postulated to involve photoassisted charge transfer between the
1
Address correspondence to this author.
0097-6156/88/0378-0398$06.00/0
c

27. CORIA-GARCIA & PEMBERTON Effect of Underpotentially Deposited Lead 399
metal and the adsorbate at unique s i t e s on the metal surface known

as a c t i v e s i t e s . These a c t i v e s i t e s have been documented to involve
c l u s t e r s of adatoms at the surface.(17)
In general, the deposition of monolayer and submonolayer
amounts of nonenhancing foreign metals onto an enhancing metal
electrode through the underpotential deposition (UPD) process
r e s u l t s i n a decrease i n SERS i n t e n s i t y f o r a l l of the adsorbate
probes studied to date. This decrease has been recently interpreted
i n terms of two e f f e c t s , a change i n substrate o p t i c a l properties
causing a decrease i n the c l a s s i c a l electromagnetic enhancement
e f f e c t , and a l t e r a t i o n of the energy l e v e l s of the a c t i v e s i t e s
rendering the charge transfer process s i g n i f i c a n t l y l e s s
e f f i c i e n t . ( 1 4 ) One aspect of these studies which has yet to be
adequately addressed, however, i s the influence of the f o r e i g n metal
layer on the surface coverage of the adsorbate during the deposition
process. I t i s very l i k e l y that, i n a l l of the studies performed
thus f a r , the observed response represents a convolution of the
e f f e c t s noted above an
In f a c t , i n several studies
coverage was proposed as a major cause of the SERS i n t e n s i t y
decrease.(5-7,10) Although previous studies i n t h i s laboratory have
been undertaken with the intent of addressing t h i s issue using the
e x - s i t u probe of x-ray photoelectron spectroscopy as a measure of
adsorbate surface coverage (11), i t i s c l e a r l y more desirable to
probe such changes i n - s i t u to avoid complications r e s u l t i n g from
removing the i n t e r f a c e from the electrochemical environment.
The work reported here was designed to address the issue of
adsorbate surface coverage i n the e f f e c t on SERS of UPD Pb on Ag
electrodes i n aqueous chloride and bromide media using i n t e r f a c i a l
H 0 species as the probe molecule. No studies have been reported on
2
the e f f e c t of UPD layers on the SERS of i n t e r f a c i a l solvent

molecules previously. However, the solvent i s an i d e a l choice f o r
such studies, because i t w i l l always remain i n intimate contact with
the electrode surface. Moreover, the SERS of i n t e r f a c i a l H 0 has 2
been characterized quite extensively i n aqueous h a l i d e media (18-29)

and allows the possible influence of anion on the response of the
system to be assessed.
Experimental
The l a s e r Raman system used f o r these studies has been described i n

d e t a i l i n previous reports from t h i s laboratory.(8.9) A l l spectra
reported here were obtained with 5145 A e x c i t a t i o n from an A r +
l a s e r . Laser power at the sample was t y p i c a l l y 200 mW. Spectra of

1
CI" and Br" were acquired at 0.5 cm" increments over a 0.5 s
i n t e g r a t i o n period. Spectra of i n t e r f a c i a l H 0 were acquired at 1.0
2
1
cm" increments over a 0.5 s i n t e g r a t i o n period. A l l spectra were
1
acquired as s i n g l e scans with a 6 cm" bandpass. Peak areas were
d i g i t a l l y determined assuming a s t r a i g h t - l i n e background i n a l l
frequency regions.
In the low frequency region where the i/(Ag-Cl) and i/(Ag-Br)
v i b r a t i o n s are observed, s i g n i f i c a n t background i n t e n s i t y can
obscure these v i b r a t i o n a l features i f they are weak i n i n t e n s i t y .
In order to improve the s e n s i t i v i t y of these measurements, the
spectra acquired i n t h i s region before an oxidation-reduction cycle

(ORC) pretreatment were d i g i t a l l y subtracted from the spectra

acquired a f t e r the ORC. The r e s u l t i n g spectra i n t h i s frequency
region demonstrate a smaller influence from the background and allow
accurate q u a n t i t a t i o n of peak areas even at low i n t e n s i t y .
In the frequency region where the i/(0H) v i b r a t i o n s of
i n t e r f a c i a l H 0 are observed, the normal Raman s c a t t e r i n g from the
2
bulk s o l u t i o n can obscure the SERS of i n t e r f a c i a l H 0 i f appropriate 2
precautions are not taken. In the studies reported here, the SERS
of i n t e r f a c i a l H 0 was acquired with the electrode surface
2
positioned as close to the electrochemical c e l l window as possible

to minimize contributions from the bulk s o l u t i o n . When a l t e r i n g the
electrode p o t e n t i a l to deposit Pb onto the Ag electrode surface, the
electrode was p u l l e d away from the window several mm, the surface
allowed to e q u i l i b r a t e at the new conditions, and the electrode
repositioned near the c e l l window f o r s p e c t r a l a c q u i s i t i o n .
Electrochemical equipment and c e l l s used f o r these
investigations have also been described previously.(8.9)
P o l y c r y s t a l l i n e Ag (Johnso
polished with alumina (Buehler
t r i p l y d i s t i l l e d H 0 before each run. A l l p o t e n t i a l s were measured
2
and are reported versus a saturated calomel reference electrode

(SCE).
3
The solutions consisted of 5 x 10" M Pb(N0 ) i n e i t h e r 0.1 M3 2
KC1 or 0.1 M KBr made s l i g h t l y a c i d i c to pH 5.5 by the a d d i t i o n of

HC1 or HBr as appropriate, i n order to maintain the s o l u b i l i t y of
2+
the P b . A l l chemicals were reagent grade and were used as
received. A l l solutions were prepared from t r i p l y d i s t i l l e d ,
deionized H 0, the l a s t d i s t i l l a t i o n being from basic permanganate.
2
A l l solutions were deaerated by bubbling with N p r i o r to use. 2
The Ag electrodes were subjected to p o t e n t i a l sweep ORCs at 10

1
mV s" i n e i t h e r 0.1 M KC1 or 0.1 M KBr from an i n i t i a l p o t e n t i a l of
2
-0.30 V to more p o s i t i v e p o t e n t i a l s . A f t e r ca. 30 mC cm" of anodic
charge was passed, the d i r e c t i o n of p o t e n t i a l sweep was reversed to
reduce the Ag halide surface to Ag metal. The roughened electrode
was then removed under p o t e n t i a l c o n t r o l at -0.30 V and immersed i n
2+
the P b - c o n t a i n i n g t e s t s o l u t i o n f o r SERS studies.
The f r a c t i o n a l Pb monolayer coverages were c a l c u l a t e d by
comparing the charge under the s t r i p p i n g wave obtained at d i f f e r e n t
p o t e n t i a l s with that obtained for a f u l l monolayer on a given
2
electrode surface. A value of 300 /iC cm" was used f o r a complete
Pb monolayer as reported by Dickertmann, Koppitz, and Schultze.(30)

2
SERS of HgO i n the Absence of Pb *. The SERS of H 0 at Ag 2
electrodes has been investigated thoroughly. (18-29) The i/(0H)

v i b r a t i o n can be e a s i l y seen i n electrochemical SERS studies i f the
electrode surface i s separated from the c e l l window by only a t h i n
f i l m of s o l u t i o n . Using t h i s approach, the SERS spectra of H 0 at 2
Ag electrodes i n 0.1 M KC1 and 0.1 M KBr were obtained. The i/(0H)
1 1
v i b r a t i o n i s observed at 3495 cm" and 3505 cm' i n CI" and Br",
r e s p e c t i v e l y . The r e l a t i v e l y high p o s i t i o n of t h i s symmetric 0-H
v i b r a t i o n has been observed previously and has been interpreted as
evidence f o r d i s r u p t i o n of hydrogen bonding between water molecules
by these anions, and weak hydrogen bonding between the H 0 and the 2

anion.(18-20.26) Such interactions between the anion and the H 0 2
species give r i s e to a considerably narrower linewidth of t h i s

v i b r a t i o n than observed i n bulk solution. Moreover, the a c q u i s i t i o n
+
of these spectra i n K solutions, a low hydration energy cation,
implies that the H 0 molecules are p r e f e r e n t i a l l y aligned with t h e i r
2
0 ends facing the p o s i t i v e l y charged Ag electrode, as noted i n

e a r l i e r reports.(27)
I t has been previously observed that the nature of the anion
has a marked e f f e c t on the frequency of t h i s band. In 1.0 M and 4.0
1 1
M KC1, bands are observed at 3498 cm" and 3433 cm" ,
respectively.(29) In 1.0 M KBr and 1.0 M KI, bands are observed at
1 1
3523 cm" and 3553 cm" , respectively.(18) In 0.5 M KCN, t h i s band
1
i s observed at 3521 cm" .(18) These r e s u l t s show that at a s i m i l a r
h a l i d e concentration of 1.0 M, a decrease i n frequency of the band
1 1 1
i s observed from 3553 cm' to 3523 cm" to 3498 cm" f o r I " , Br",
and CI", respectively. The r e s u l t s obtained here show a s i m i l a r
1 1
decrease i n p o s i t i o n from 3505 cm' i n Br" to 3495 cm' i n CI"
These bands are also s h i f t e
solutions of these anions
r e s u l t s noted above.
Evidence that H 0 species also i n t e r a c t with the Ag electrode
2
independent of adsorbed anions comes from the p o t e n t i a l dependence

of the i/(0H) i n t e n s i t y as compared with the i/(Ag-X) (X=C1", Br")
i n t e n s i t i e s . The normalized i n t e n s i t i e s of the i/(Ag-X) (X=C1", Br")
v i b r a t i o n s i n 0.1 M KC1 and 0.1 M KBr are shown i n Figure l a , and
the corresponding i n t e n s i t i e s of the i/(0H) v i b r a t i o n shown i n Figure
l b . The observation that the i n t e n s i t y of the i/(0H) v i b r a t i o n
reaches a maximum at more negative potentials than the i/(Ag-X)
(X=C1", Br") v i b r a t i o n s has been interpreted as i n d i c a t i o n that the
H 0 molecules can become maximally adsorbed on the surface when the
2
p o s i t i v e charge has decreased to allow p a r t i a l desorption of the

anions.(23) Obviously, the p o t e n t i a l at which t h i s occurs depends
on the strength of i n t e r a c t i o n of the anion with the electrode.
The frequency of the y(0H) band i s also observed to decrease
with p o t e n t i a l i n both KC1 and KBr environments, as shown i n Figure
2. This e f f e c t can be interpreted i n terms of a weakening of the
i n t e r a c t i o n strength of the H 0 with the Ag electrode surface as the
2
p o t e n t i a l and the charge on the electrode are made more negative.

As the H 0 interacts less with the electrode, i t can hydrogen bond
2
more with other H 0 molecules, giving r i s e to the observed decrease

2
i n frequency of the i/(0H) v i b r a t i o n . This i n t e r p r e t a t i o n i s

+
consistent with the o r i e n t a t i o n of the H 0 molecule i n K solutions 2
discussed above.
SERS of H 2 O i n the Presence of Pb *. The presence of 5 x 10" M 2 3
2+
Pb i n 0.1 M KC1 and 0.1 M KBr i n the p o t e n t i a l region p o s i t i v e of
UPD has no e f f e c t on the frequency of the i/(0H) band i n these media.
1
The only e f f e c t s observed are that the 3495 cm" band i n CI" has
measurable i n t e n s i t y to more negative potentials than i n the absence
2+
of P b , and the absolute i n t e n s i t i e s of t h i s band are lower i n both
2+
h a l i d e solutions than i n the absence of P b . The f a c t that the
1
3495 cm' band i n CI" can be observed at p o t e n t i a l s where i t i s not
2+
observed i n the absence of P b can be explained i n terms of the
2+
Pb /X" (X=C1", Br") species present i n the interface. Previous
2+
work i n t h i s laboratory has demonstrated the existence of P b

T r
>V(Ag-CI)
0.8 - i 1
kO(Ag-Br)
0.6 -
I -
04 "
0.2
1
-a
0.0 J 1 » i
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
- E (VOLTS)vs S C E
—i 1
A 3495 cm" 1
• 3 5 0 5 cnrf 1
•
105
•b
OO
0.2 03 04 05 06 07 0.8 0.9
-E (Volts) vs SCE
Figure 1. Intensity as a function of p o t e n t i a l f o r a) i/(Ag-Cl)
-1 -1
band (238 cm ) and i/(Ag-Br) band (163 c m ) , and b) i/(0H)
1 1
bands i n CI' (3495 cm" ) and Br" (3505 cm" ).

27. CORIA-GARCIA & PEMBERTON Effect of Underpotentially Deposited Lead 4 0 3
halide complexes i n the i n t e r f a c e at p o t e n t i a l s more p o s i t i v e than

Pb UPD.(12) These complexes s t a b i l i z e the halides i n the i n t e r f a c e
such that they remain at more negative p o t e n t i a l s . The decrease i n
2+
absolute i n t e n s i t y of the H 0 band i n the presence of P b most
2
l i k e l y r e s u l t s from the f a c t that there are fewer free h a l i d e ions

i n the i n t e r f a c e with which the H 0 can i n t e r a c t .
2
The p o t e n t i a l regions w i t h i n which the UPD of Pb occur are

shown i n the c y c l i c voltammograms i n Figure 3. In CI" media, Pb UPD
occurs between -0.40 and -0.48 V. In Br" media, Pb UPD i s observed
at s l i g h t l y more negative p o t e n t i a l s between -0.43 and -0.52 V.
Considering a l l of the data discussed above, i t i s u n l i k e l y that
d r a s t i c decreases i n surface coverage by H 0 species occur i n these
2
r e l a t i v e l y narrow p o t e n t i a l regions. In f a c t , i t i s known that

during the UPD of Pb on Ag, the surface coverage of CI" and Br"
decreases. Therefore, the surface coverage of H 0 should a c t u a l l y
2
increase during Pb UPD as h a l i d e ions are p a r t i a l l y desorbed. These

considerations are c r i t i c a l i n understanding the SERS response of
the i/(0H) band during UP
Figure 4 shows th
1
i/(0H) band i n CI" media and the 3505 cm" band i n Br" media as a
function of Pb coverage from zero to one monolayer. Also shown are
the corresponding normalized i n t e n s i t i e s of the i/(Ag-Cl) and i/(Ag-
Br) v i b r a t i o n s as a function of Pb coverage f o r comparison. As
these data demonstrate, the i n t e n s i t y of the i/(0H) v i b r a t i o n
decreases as the Pb coverage increases i n both h a l i d e environments.
The i n t e n s i t i e s of the i/(Ag-X) (X-Cl", Br") v i b r a t i o n s also decrease
with increasing Pb coverage. These decreases are consistent with
the r e s u l t s of other studies i n v o l v i n g the e f f e c t of UPD t h i n f i l m s
on the SERS of other adsorbate probes i n t h i s (8-14) and other (1-
7.15.16) l a b o r a t o r i e s .
The data i n Figure 4 show d i f f e r e n t behavior i n three d i f f e r e n t
coverage regions. The f i r s t region occurs between zero coverage and
ca. 30% of a Pb monolayer. In t h i s region, the i n t e n s i t i e s of a l l
v i b r a t i o n s decrease. The rate of increase of the y(Ag-Br) i n t e n s i t y
i s greater than that f o r the i/(Ag-Cl) band. This r e s u l t has been
observed and explained previously.(13) The rate of i n t e n s i t y
decrease i n the i/(0H) band i n t h i s region i n both h a l i d e
environments i s s i g n i f i c a n t l y less than that of e i t h e r i/(Ag-X)
(X-Cl", Br") v i b r a t i o n . Moreover, the rate of decrease i s
independent of the anion. This l a t t e r observation i s f u r t h e r
evidence that the H 0 species being monitored are i n t e r a c t i n g with
2
the Ag electrode independent of the s p e c i f i c a l l y adsorbed h a l i d e

ions.
The second region of d i s t i n c t behavior occurs between ca. 40%
and 80% of a Pb monolayer. In t h i s region, the i n t e n s i t i e s of the
i/(Ag-X) (X=C1", Br") bands decrease to unmeasurable values. I n
contrast, the i n t e n s i t i e s of the i/(0H) v i b r a t i o n s remain e s s e n t i a l l y
constant i n both media. The t h i r d region of behavior occurs f o r Pb
coverages greater than 80% of a monolayer. The i n t e n s i t i e s of the
i/(Ag-X) (X*C1", Br") bands remain at unmeasurable l e v e l s . The
i n t e n s i t i e s of the y(0H) bands decrease r a p i d l y to unmeasurable
l e v e l s between 80% of a monolayer and one complete monolayer. The
behavior of the i/(0H) bands i n the second and t h i r d regions are
observed to depend only s l i g h t l y on the nature of the anion.

3506 i i i
i 1 r
•H 0/Br'
2
3502 •H o/cr 2
O 3498
CM
X
->
3494
3490
0.2 0.4 0.6 0.8
-E(VOLTS) vs S C E
Figure 2. Frequency of the i/(0H) v i b r a t i o n as a function of

p o t e n t i a l i n C l " and Br" media.
Q3 0.4 0.5 0.6 03 OA 0.5 0.6

-E(VOLTS)vs SCE
Figure 3. C y c l i c voltammetry of Pb UPD on Ag electrode i n a)

1
0.1 M KC1, and b) 0.1 M KBr. Sweep rate 10 mV s" ,
S = 47 /iA cm" .2

27. CORIA-GARCIA & PEMBERTON Effect ofUnderpotentially Deposited Lead 4 0 5
T i i i i i r~
,-1
3 4 9 5 cm" 1
PbClD/CI"
O 238 cm' 1
I 05 o j } .
o 1
0.2 0.4 0.6 08

9
100—i 1 1 1 1 1 r
3505 cm" 1
Pb(ll)/Br"
0 1 6 3 cm" 1
I 05-
'o o o o o
o *
b ° #
—I 1 1 1 1 1 1Ql Q l Q >
0.2 0.4 0.6 0.8 1.0
e
Figure 4. Normalized SERS i n t e n s i t y as a function of Pb
1 1
coverage f o r a) 3495 cm" i/(0H) band and 238 cm" y(Ag-Cl) band
1 1
i n 0.1 M KC1, and b) 3505 cm" i/(0H) band and 163 cm" i/(Ag-Br)
band i n 0.1 M KBr.

I t i s c l e a r from these H 0 r e s u l t s that the decreases i n SERS

2
i n t e n s i t i e s as UPD layers grow on electrodes cannot be s o l e l y

a t t r i b u t e d to decreases i n adsorbate coverage. This report
represents the f i r s t concrete evidence f o r t h i s f a c t i n the
electrochemical SERS environment.
I t i s l i k e l y that the decreases observed can be r a t i o n a l i z e d i n
terms of two contributions. Changes i n surface o p t i c a l properties
r e s u l t i n g from modification by the foreign metal have been shown to
decrease the electromagnetic enhancement c o n t r i b u t i o n to SERS.
However, f o r the case of Pb UPD on Ag, t h i s e f f e c t has been shown to
account f o r only ca. 40% of the decrease i n going from zero coverage
to one monolayer.(14) Moreover, t h i s model does not account f o r the
r e l a t i v e l y rapid decrease i n i n t e n s i t y observed with the deposition
of small ( i . e . , less than 20% of a monolayer) amounts of Pb on the
Ag surface.
The second contribution to these observed decreases that i s
proposed to be p a r t i c u l a r l y important at small Pb coverages i s
a l t e r a t i o n of the microscopi
presumably adatom c l u s t e r s
less e f f i c i e n t . ( 1 4 ) In t h i s model, the Fermi energy i s proposed to
increase as the Pb coverage increases so that, at a constant
e x c i t a t i o n energy, the charge transfer from the metal at s i t e s of
atomic scale roughness to acceptor l e v e l s of the adsorbate gradually
goes out of resonance. I t i s proposed that t h i s type of mechanism
i s responsible f o r the quenching of SERS of H 0 i n the f i r s t
2
coverage region reported here. Due to the f a c t that the H 0 species 2
remain at the surface, the quenching of the charge transfer process

i s not complete, and some atomic scale roughness remains, the SERS
i n t e n s i t y of the i/(OH) v i b r a t i o n i s retained at ca. 50% throughout
the second coverage region.
In the t h i r d region of coverage, most of the atomic scale
roughness has been proposed to be i r r e v e r s i b l y destroyed as the Pb
layer rearranges to assume the f i n a l hexagonal close packed
configuration of the monolayer.(9) This loss of atomic scale
roughness r e s u l t s i n the i r r e v e r s i b l e decrease i n i/(0H) i n t e n s i t y to
e s s e n t i a l l y unmeasurable l e v e l s . This observation further
emphasizes the importance of the chemical enhancement mechanism
c o n t r i b u t i o n to SERS i n electrochemical systems.
Conclusions
The e f f e c t of UPD Pb on the SERS of H 0 at Ag electrodes i s

2
presented i n t h i s report. The work reported here demonstrates that

a s i g n i f i c a n t decrease i n adsorbate coverage i s not responsible f o r
the quenching of SERS at electrodes i n the presence of UPD layers.
These r e s u l t s lend credence to a previously postulated model i n
which the quenching e f f e c t i s interpreted i n terms of both a
decrease i n the electromagnetic enhancement at these surfaces
r e s u l t i n g from a change i n the macroscopic o p t i c a l properties of the
surface as the UPD layer i s formed, and a decrease i n the e f f i c i e n c y
of photoassisted charge transfer r e s u l t i n g from a l t e r a t i o n of the
Fermi energy at microscopic active s i t e s on the surface at which
charge transfer occurs.

Acknowledgments
The authors g r a t e f u l l y acknowledge the f i n a n c i a l support of t h i s

work by the National Science Foundation (CHE-8614955).
1. Loo, B. H.; Furtak, T. E. Chem. Phys. L e t t . 1980, 71, 68.

2. Pettinger, B; Moerl, L. S o l i d State Commun. 1982, 43, 315.
3. Pettinger, B.; Moerl, L. J. Electron Spectrosc. Relat. Phenom.
1983, 29, 383.
4. Watanabe, T.; Yanigahara, H.; Honda, K.; Pettinger, B.; Moerl,
L. Chem. Phys. Lett. 1983, 96, 649.
5. Kester, J . J. J. Chem. Phys. 1983, 78, 7466.
6. Furtak, T. E.; Roy, D. Phys. Rev. Lett. 1983, 50, 1301.
7. Roy, D.; Furtak, T. E. J. Chem. Phys. 1984, 81, 4168.
8. Guy, A. L.; Bergami B. Pemberton J. E Surf S c i 1985 150,
226.
9. Guy, A. L.; Pemberton
10. Kellogg, D. S.; Pemberton, J . E. J. Phys. Chem. 1987, 91, 1127.
11. Guy, A. L.; Pemberton, J . E. Langmuir 1987, 3, 125.
12. Coria-Garcia, J . C.; Pemberton, J. E.; Sobocinski, R. L. J .
13. Pemberton, J. E.; Coria-Garcia, J . C.; Hoff, R. L. Langmuir
1987, 3, 150.
14. Guy, A. L.; Pemberton, J. E. Langmuir 1987, 3, 777.
15. Leung, L. H.; Weaver, M. J. J. Electroanal. Chem. 1987, 217,
367.
16. Fleischmann, M.; Tian, Z. Q. J. Electroanal. Chem. 1987, 217,
385.
17. Roy, D.; Furtak, T. E. Phys. Rev. B 1986, 34, 5111.
18. Fleischmann, M.; Hendra, P. J.; Hill, I . R.; Pemble, M. E. J.
19. Pettinger, B.; P h i l p o t t , M. R.; Gordon, J. G. J. Chem. Phys.
1981, 74, 934.
20. Chen, T. T.; Owen, J. F.; Chang, R. K.; Laube, B. L. Chem.
Phys. Lett. 1982, 89, 356.
21. Macomber, S. H.; Furtak, T. E.; Devine, T. M. Surf. S c i . 1982,
122, 556.
22. Owen, J. F.; Chen, T. T.; Chang, R. K.; Laube, B. L. Surf. Sci.
1983, 125, 679.
23. Owen, J. F.; Chen, T. T.; Chang, R. K.; Laube, B. L. J .
24. Fleischmann, M.; Hill, I . R. J. Electroanal. Chem. 1983, 146,
367.
25. Pettinger, B.; Moerl, L. J. Electroanal. Chem. 1983, 150, 415.
26. Owen, J. F.; Chang, R. K. Chem. Phys. Lett. 1984, 104, 510.
27. Chen, T. T.; Smith, K. E.; Owen, J. F.; Chang, R. K. Chem.
Phys. Lett. 1984, 108, 32.
28. Chen, T. T.; Chang, R. K. Surf. S c i . 1985, 158, 325.
29. Furtak, T. E. J. Electroanal. Chem. 1983, 150, 375.
30. Dickertmann, D.; Koppitz, F. D.; Schultze, J . W. Electrochim.
Acta 1976, 21, 967.
RECEIVED M a y 19, 1988

Chapter 28
Synthesis and Electrochemical Properties

of a Polythiophene—Viologen Polymer
Ching-Fong Shu and Mark S. Wrighton
Department of Chemistry Massachusetts Institute of Technology
This article reports the synthesis and electro-

chemical properties of poly(I) (I = 1-methyl-1'-(3-
thiophene-3-yl)-propyl-4,4'-bipyridinium bis-hexa-
fluorophosphate), a polymer with a conducting polymer,
polythiophene, as the backbone and a redox couple,
2+ '
viologen (V = N,N -dialkyl-4,4'-bipyridinium), as the
pendant group. Poly(I) can be grown by the oxidation of I
and thereby deposited onto the electrode surface. The
cyclic voltammetry of poly(I) in CH CN/0.1 M[n-Bu N]PF6
3
+
4
shows an oxidation wave at 0.6 V vs Ag /Ag and the 5

resistivity of the polymer declines by a factor of 10
upon changing the potential from 0.4 V to 0.8 V,
consistent with the behavior of polythiophene and its
derivatives. Poly(I) also exhibits two successive one– +
electron reduction waves at -0.6 V and -1.1 V vs. Ag /Ag,
as expected for the V2+ group. An array of eight closely–
spaced microelectrodes can be coated and connected by
poly(I). Analogous to generation and collection
experiments at a rotating ring/disk electrode, charge
transport occurs from one microelectrode (generator) to
another (collector)via charge transport in the polymer. 2+/+
The mechanism of charge transport via the V system is
consistent with the expectations from "redox conduction"
The value of the diffusion coefficient for charge
2+/+
transport, D , for the v
9 2
CT system is measured to be ~7 x
10 cm /s. The temperature dependence of the steady state
generator-collector current shows an Arrhenius activation
energy of 9.8 kcal/mole. A poly(I)-based microelectro-
chemical transistor gives an I - V characteristic with a
D G
2+ +
sharp maximum in I at VG = E°' of V / , and for V = 25
D D
mV the full width at half-height of the I -V curve is D G
only 56 mV. The transistor also shows turn on at VG

corresponding to oxidation of the polythiophene backbone,
as reported earlier for poly(3-methylthiophene)
0097-6156y88/0378-O408$06.75/0
c

28. S H U A N D W R I G H T O N Synthesis and Properties of Polythiophene Polymer 409
In t h i s a r t i c l e we r e p o r t t h e s y n t h e s i s and e l e c t r o c h e m i c a l
p r o p e r t i e s o f t h e polymer d e r i v e d from o x i d a t i o n o f L, p o l y ( I ) , and
t h e c h a r a c t e r i s t i c s o f a m i c r o e l e c t r o c h e m i c a l t r a n s i s t o r b a s e d on t h e
polymer. P o l y ( I ) , which i s formed by e l e c t r o c h e m i c a l o x i d a t i o n o f 1,
E q u a t i o n 1, c o n s i s t s o f a c o n d u c t i n g polymer backbone, p o l y t h i o p h e n e ,
CH
2 +
and a pendant v i o l o g e n redox group, V . An a r r a y o f e i g h t c l o s e l y -
s p a c e d m i c r o e l e c t r o d e s c o a t e d w i t h p o l y ( I ) can f u n c t i o n as a
m i c r o e l e c t r o c h e m i c a l t r a n s i s t o r . (1=2.)
Many e l e c t r o c h e m i c a l s t u d i e s have been d e v o t e d t o t h e
development o f new e l e c t r o d e c o a t i n g m a t e r i a l s . ( 3 - 4 ) I t has been
shown t h a t e l e c t r o p o l y m e r i z a t i o n can be u s e d t o s y n t h e s i z e c o n d u c t i n g
polymer f i l m s such as p o l y p y r r o l e c o n t a i n i n g c o n v e n t i o n a l redox
c o u p l e s l i k e v i o l o g e n , r u t h e n i u m complexes, f e r r o c e n e , and
quinone.(5=12) Recent s t u d i e s (13-14) show t h a t p o l y ( 3 -
m e t h y l t h i o p h e n e ) i s v e r y d u r a b l e i n aqueous s o l u t i o n and has a
s u p e r i o r t r a n s c o n d u c t a n c e compared t o t h a t o f p o l y p y r r o l e ( 1 ) o r
polyaniline.(1H) The c h e m i c a l ruggedness and h i g h c o n d u c t i v i t y make
p o l y ( 3 - a l k y l t h i o p h e n e ) a good backbone upon which t o a t t a c h
2+
c o n v e n t i o n a l redox c e n t e r s . The V group has been d e m o n s t r a t e d t o
be v e r y u s e f u l i n e l e c t r o c a t a l y s i s and p h o t o e l e c t r o c a t a l y s i s o f redox
r e a c t i o n s and i n e l e c t r o c h r o m i s m . ( 3
r 4,16-20) The e l e c t r o c h e m i c a l
o x i d a t i o n o f X produces a s u r f a c e - c o n f i n e d f i l m o f e l e c t r o a c t i v e
2 +
p o l y t h i o p h e n e c o n t a i n i n g one V redox c e n t e r p e r r e p e a t u n i t o f t h e
polymer. Studies of the c o n d u c t i v i t y of poly(I) vs. p o t e n t i a l reveal
fundamental i n f o r m a t i o n r e g a r d i n g t h e amount o f c h a r g e withdrawn p e r
2 + / +
r e p e a t u n i t t o a c h i e v e a g i v e n degree o f c o n d u c t i v i t y . The V
c e n t e r s r e p r e s e n t a k i n d o f i n t e r n a l c a l i b r a t i o n s i n c e t h e amount o f
2 +
V p r e s e n t can be a s s e s s e d e l e c t r o c h e m i c a l l y .
Recently, s e v e r a l molecule-based microelectrochemical devices
have been d e v e l o p e d by t h e Wrighton g r o u p . ( 1 4 1 5 21-22) A r r
microelectrode array coated with poly(I) r e s u l t s i n a

m i c r o e l e c t r o c h e m i c a l t r a n s i s t o r w i t h t h e unique c h a r a c t e r i s t i c t h a t
shows " t u r n on" i n two g a t e p o t e n t i a l , V , regimes, one a s s o c i a t e d
G
w i t h t h e p o l y t h i o p h e n e s w i t c h i n g from an i n s u l a t o r t o a c o n d u c t o r
2 + / +
upon o x i d a t i o n and one a s s o c i a t e d w i t h t h e V c o n v e n t i o n a l redox
centers.

Experimental Section
Chemicals. CH CN was d i s t i l l e d from CaH and s t o r e d under N .

3 2 [n- 2
Bu4N]PFg was p r e p a r e d by a d d i n g an aqueous s o l u t i o n o f [n-Bu4N]Br t o

an aqueous s o l u t i o n o f NH4PF6. The p r e c i p i t a t e was c o l l e c t e d and
p u r i f i e d by r e c r y s t a l l i z a t i o n from 95% EtOH. The [n-Bu^NjPFg was
d r i e d under vacuum a t 100°C o v e r n i g h t . 3-(Bromomethyl)thiophene (3-
t h e n y l b r o m i d e ) was p r e p a r e d v i a t h e method r e p o r t e d by Gronowitz and
1
Frejd.(22.) 2 , 2 - A z o b i s ( 2 - m e t h y l p r o p i o n i t r i l e ) , CH I, 4,4'-
3
b i p y r i d i n e , N-bromosuccinimide, d i e t h y l malonate, 3-methylthiophene,

PBr3, [Ru (NH ) ] C l 3 , and K P t C l 4 were used as r e c e i v e d from commercial
3 6 2
sources.
P r e p a r a t i o n of D i e t h y l 3-thenylmalonate. 2.3 g (0.1 mole) o f Na was
added t o 100 ml o f a b s o l u t e EtOH i n a 250 ml t h r e e - n e c k e d f l a s k .
When a l l t h e Na had r e a c t e d , 16.8 g (0.105 mole) o f d i e t h y l malonate
was added t h r o u g h an a d d i t i o n f u n n e l . T h i s was f o l l o w e d by t h e
d r o p w i s e a d d i t i o n o f 17.7 g (0.1 mole) o f 3 - t h e n y l bromide. The
m i x t u r e was r e f l u x e d unde
r e d u c e d t o about 50 ml b
t r e a t e d w i t h 40 ml o f H 0. The e s t e r was e x t r a c t e d w i t h E t 0 and
2 2
d r i e d o v e r Na S04 • The E t 0 was removed by r o t a r y e v a p o r a t i o n and

2 2
t h e p r o d u c t was p u r i f i e d by vacuum d i s t i l l a t i o n : y i e l d , 13 g; bp 74
°C (0.05 t o r r ) ; H NMR (60 MHz, CC1 ) 8 6.93 (m, 1 H), 6.70 (m, 2 H),
X
4
4.00 (q, 4H, J = 7 Hz), 3.47 ( t , 1 H, J = 7 Hz), 3.07 (d, 2H, J = 7

Hz), 1.16 ( t , 6 H, J = 7 H z ) .
Preparation of 3-(Thiophene-3-yl)propionic A c i d . 13 g (0.05 mole) o f
d i e t h y l 3 - t h e n y l m a l o n a t e was added dropwise t h r o u g h an a d d i t i o n
f u n n e l t o a s o l u t i o n o f 10 g o f NaOH i n 100 ml o f H 0. The m i x t u r e
2
was t h e n r e f l u x e d o v e r n i g h t . The r e s u l t i n g s o l u t i o n was c o o l e d w i t h

an i c e b a t h and c o n c e n t r a t e d HCl(aq) was added u n t i l t h e pH o f t h e
s o l u t i o n became 1. The p r o d u c t was e x t r a c t e d w i t h E t 0 and d r i e d 2
o v e r Na S04. The E t 0 was removed by r o t a r y e v a p o r a t i o n and t h e

2 2
white s o l i d 3 - t h e n y l m a l o n i c a c i d r e s u l t e d : y i e l d , 10 g; mp 137 °C;

X
H NMR (60 MHz, CD CN) 8 8.00 (br, 2 H) , 7.10 (m, 1 H) , 6.82 (m, 2
3
H), 3.58 ( t , 1 H, J = 7 Hz), 3.17 (d, 2 H, J = 7 H z ) .

3 - T h e n y l m a l o n i c a c i d (9.8 g) was d e c a r b o x y l a t e d by h e a t i n g a t a
t e m p e r a t u r e o f 140-150 °C i n an o i l b a t h . The r e a c t i o n was run
o v e r n i g h t under N . The s o l i d 3 - ( t h i o p h e n e - 3 - y l ) p r o p i o n i c a c i d i s
2
formed c l e a n l y : y i e l d , 7.5 g; mp 56 °C; H NMR (60 MHz, CDC1 ) 8

1
3
10.11 (br, 1 H), 7.01 (m, 1H), 6.77 (m, 2 H), 2.78 (m, 4 H).
P r e p a r a t i o n of 3-(Thiophene-3-yl)propanol. A s o l u t i o n o f 7.5 g (0.05
mole) o f 3 - ( t h i o p h e n e - 3 - y l ) p r o p i o n i c a c i d i n 50 ml o f d r y THF was
added dropwise t o a s o l u t i o n o f 2.8 g (0.075 mole) o f L i A l H i n 100 4
ml o f d r y THF. The r e s u l t i n g s o l u t i o n was r e f l u x e d f o r 4 h under N . 2
A f t e r c a r e f u l a d d i t i o n o f H 0, 7.5 ml o f c o n c e n t r a t e d H S04 i n 75 ml
2 2
o f H 0 was added t o t h e m i x t u r e .
2 The p r o d u c t was e x t r a c t e d w i t h
Et 0. 2 The E t 0 s o l u t i o n was washed s u c c e s s i v e l y w i t h aqueous NaHC03
2
T n e
s o l u t i o n and H 0 ,then d r i e d o v e r Na S04.
2 2 E t 0 was removed by2
r o t a r y e v a p o r a t i o n and t h e p r o d u c t was o b t a i n e d by vacuum

X
distillation: y i e l d , 6.19 g; bp 68 °C (0.05 t o r r ) ; H NMR (300 MHz,
CDCI3) 8 7.24 (m, 1 H), 6.94 (m, 2 H), 3.65 ( t , 2 H, J = 7.5 Hz),
2.72 ( t , 2 H, J = 7.5 Hz), 2.03 (br, 1 H), 1.88 ( q u i n t e t , 2 H, J =
7.5 H z ) .

28. SHU AND WRIGHTON Synthesis and Properties of Polythiophene Polymer 411
P r e p a r a t i o n o f 3 - ( T h i o p h e n e - 3 - y l ) p r o p y l Bromide. 2.5 g o f P B r was 3
added s l o w l y t o 3.55 g o f 3 - ( t h i o p h e n e - 3 - y l ) p r o p a n o l i n a 50 ml t h r e e
n e c k e d f l a s k w i t h s t i r r i n g a t 0°C. The r e s u l t i n g s o l u t i o n was
s t i r r e d a t room temperature o v e r n i g h t . The p r o d u c t was i s o l a t e d from
t h e r e a c t i o n m i x t u r e by vacuum d i s t i l l a t i o n : Y i e l d , 2.4 g; bp 60 °C
1
(0.05 t o r r ) ; H NMR (300 MHz, CD C1) 8 7.25 (m, 1 H), 6.98 (d, 1 H, J
3
= 3 Hz), 6.94 (d, 1 H, J = 5Hz), 3.39 ( t , 2 H, J = 7 Hz), 2.80 ( t , 2

H, J = 7 Hz, 2.15 ( q u i n t e t , 2 H, J = 7 H z ) .
Preparation of 1-(3-Thiophene-3-yl)propyl-4.4'bipyridinium
Hexafluorophosphate. A s o l u t i o n o f 1.45 g (7 mmol) o f 3 - ( t h i o p h e n e -
1
3 - y l ) p r o p y l bromide and 3.12 g (20 mmol) o f 4 , 4 - b i p y r i d i n e i n 50 ml
of C H 3 C N was r e f l u x e d o v e r n i g h t . The amount o f CH CN was r e d u c e d t o
3
5 ml by r o t a r y e v a p o r a t i o n and t h e B r ' s a l t was p r e c i p i t a t e d by

a d d i n g 100 ml o f Et20. The B r " s a l t was i s o l a t e d from t h e u n r e a c t e d
4 , 4 ' - b i p y r i d i n e by f i l t r a t i o n and c o n v e r t e d t o t h e PFg" s a l t by
d i s s o l v i n g i n H2O and a d d i t i o n t o a s o l u t i o n o f 2.28 g o f NH4PF6 i n
20 ml o f H2O. The PFg" s a l t p r e c i p i t a t e d and was i s o l a t e d by
filtration. The p r o d u c
1
mp 179 °C dec; H NMR (25
8.87 (dd, 2 H, J = 4.6 Hz, 1.6 Hz), 8.59 (d, 2 H, J = 7 Hz), 8.02
(dd, 2 H, J = 4.6 Hz, 1.6 Hz), 7.45 (dd, 1 H, J = 5 Hz, 3 Hz), 7.19
(dd, 1 H, J = 3 Hz, 1 Hz), 6.98 (dd, 1 H, J = 5 Hz, 1 Hz), 4.66 ( t , 2
H, J = 7.4 Hz), 2.65 ( t , 2 H, J = 7.5 Hz), 2.32 ( q u i n t e t , 2 H, J =
7.3 H z ) .
P r e p a r a t i o n o f Compound I . A s o l u t i o n o f 3.55 g o f C H I and 2.13 g 3
1
o f 1 - ( 3 - t h i o p h e n e - 3 - y l ) - 4 , 4 - b i p y r i d i n i u m h e x a f l u o r o p h o s p h a t e i n 50
ml o f CH3CN was r e f l u x e d o v e r n i g h t . The volume o f t h e s o l u t i o n was
r e d u c e d t o 5 ml by r o t a r y e v a p o r a t i o n and t h e I " s a l t was
p r e c i p i t a t e d by a d d i n g 100 ml o f Et20. The I " s a l t was i s o l a t e d from
t h e s o l u t i o n by f i l t r a t i o n and c o n v e r t e d t o t h e P F " s a l t by 6
d i s s o l v i n g i n H2O and a d d i n g t o NH PFg(aq) s o l u t i o n .

4 The p r o d u c t
p r e c i p i t a t e d and was i s o l a t e d by f i l t r a t i o n . The p r o d u c t was
r e c r y s t a l l i z e d from H 0: y i e l d , 2 . 3 g; mp 234 °C d e c ; H NMR (250
2
1
MHz, (CD ) SO) 8 9.35 (d, 2 H, J = 6.8 H z ) , 9.27 (d, 2 H, J = 6.8

3 2
Hz), 8.73 (d, 2 H, J = 6.8 Hz), 8.72 (d, 2 H, 6.8 Hz), 7.45 (dd, 1 H,
J = 5 Hz, 3 Hz), 7.19 (dd, 1 H, J = 3 Hz, 1 Hz) , 6.99 (dd, 1 H, J = 5
Hz, 1 Hz), 4.72 ( t , 2 H, J = 7.2 Hz), 4.42 (s, 3 H), 2.70 ( t , 2 H, J
+
= 7.2 Hz) 2.33 ( q u i n t e t , 2 H, J = 7.2 H z ) ; MS, ( M - P F ) 441.1012 6
+
(obsd), 441.0989 ( c a l c d ) , c o m p o s i t i o n C H o N S P F ; ( M - 2 P F ) 296.1354
18 2 2 6 6
(obsd), 296.1347 ( c a l c d ) , c o m p o s i t i o n Ci H oN2S. 8 2
E l e c t r o c h e m i c a l Equipment. E l e c t r o c h e m i c a l e x p e r i m e n t s were
p e r f o r m e d u s i n g e i t h e r a PAR Model 175 u n i v e r s a l programmer and a PAR
Model 363 p o t e n t i o s t a t / g a l v a n o s t a t , o r a P i n e I n s t r u m e n t s RDE-4
1
b i p o t e n t i o s t a t , c o u p l e d w i t h a K i p p and Zonen BD 91 X-Y-Y r e c o r d e r .
The c u r r e n t - t i m e response f o r t h e chronoamperometry e x p e r i m e n t s was
r e c o r d e d w i t h a N i c o l e t 4094 d i g i t a l o s c i l l o s c o p e . A l l potentials
2 +
were measured v s . a Ag/10" M A g r e f e r e n c e e l e c t r o d e .
Preparation of Microelectrode Arrays. The m i c r o e l e c t r o d e a r r a y s used
i n t h e work were a r r a y s o f m i c r o e l e c t r o d e s each -80 |Xm l o n g , 2.3 Jim
wide and 0.1 Jim t h i c k and spaced 1.7 urn a p a r t . F a b r i c a t i o n and
e n c a p s u l a t i o n o f t h e m i c r o e l e c t r o d e a r r a y s has been d e s c r i b e d
previously.(14,15,21-22) P r i o r t o use, a r r a y s o f m i c r o e l e c t r o d e s
were c l e a n e d by an r f O2 plasma e t c h t o remove r e s i d u a l p h o t o r e s i s t ,
f o l l o w e d by c y c l i n g t h e p o t e n t i a l o f each e l e c t r o d e between -1.5 V

and -2.0 V v s . SCE i n 0.1 M. aqueous K HP0 t o e v o l v e H . 2 4 2 The

m i c r o e l e c t r o d e s were t h e n t e s t e d by e x a m i n i n g t h e i r e l e c t r o c h e m i c a l
3 +
b e h a v i o r i n aqueous 0.1 M. L i C l c o n t a i n i n g 5 mM R u ( N H ) . 3 6 Such a
t e s t r e v e a l s , f o r a good m i c r o e l e c t r o d e , a s i g m o i d a l c u r r e n t - v o l t a g e
c u r v e w i t h a p l a t e a u c u r r e n t o f ~25nA.
The Pt m i c r o e l e c t r o d e s were m o d i f i e d by e l e c t r o c h e m i c a l
d e p o s i t i o n o f Pt onto t h e i r s u r f a c e t o " a c t i v a t e " t h e e l e c t r o d e s and
reduce t h e i n t e r - e l e c t r o d e gap.(21-22,24) The Pt was d e p o s i t e d from
aqueous 0.1 M. K HP0 c o n t a i n i n g 2mM K P t C l 4 . The e l e c t r o d e s were
2 4 2
p l a t i n i z e d one a t a t i m e by h o l d i n g a l l e l e c t r o d e s not t o be p l a t e d
a t 0.2 V v s . SCE w h i l e the one t o be p l a t e d was h e l d a t a n e g a t i v e
p o t e n t i a l to deposit Pt. Two d i f f e r e n t arrangements o f p l a t i n i z e d
e l e c t r o d e s were u s e d . As shown i n Scheme 1 ( a ) , one arrangement i s
t h a t a l l e i g h t e l e c t r o d e s i n an a r r a y were l i g h t l y p l a t i n i z e d and the
d e p o s i t i o n of t h e Pt t y p i c a l l y i n v o l v e d -150 nC. The a r r a y s t h u s
f a b r i c a t e d had a s p a c i n g o f -1.3 urn between m i c r o e l e c t r o d e s . The
second arrangement, as shown i n Scheme 1(b), i s t h a t e l e c t r o d e s #2,4,
6, and 8 were l i g h t l y p l a t i n i z e
heavily platinized. Th
charge p e r h e a v i l y p l a t i n i z e d e l e c t r o d e . The s p a c i n g o f
m i c r o e l e c t r o d e s by t h i s p r o c e d u r e i s -0.2 um.
E l e c t r o c h e m i c a l Growth o f P o l y ( I ) . P o l y ( I ) can be grown onto
e l e c t r o d e s u r f a c e s by o x i d i z i n g X i n CH3CN/O.I M. [n-Bu N]PF 4 6
solution. The t y p i c a l p r o c e d u r e i n v o l v e s c y c l i n g (200 mV/s) the

p o t e n t i a l o f an e l e c t r o d e t o be d e r i v a t i z e d between 0.0 V and 1.5 V
+
v s . Ag /Ag i n t h e p r e s e n c e o f 0.2 MX- The d e p o s i t e d polymer
e x h i b i t s c y c l i c voltammetry waves a t 0.6 V, -0.6 V and -1.1 V vs
+
Ag /Ag.
T h i c k n e s s Measurement. The t h i c k n e s s o f p o l y ( I ) a t d i f f e r e n t
c o v e r a g e s was o b t a i n e d u s i n g a Tencor a l p h a - s t e p 100 s u r f a c e p r o f i l e
m e a s u r i n g system. E l e c t r o d e s u s e d were g l a s s s l i d e s c o a t e d w i t h Pt
by e l e c t r o n beam e v a p o r a t i o n . In o r d e r t o produce a " s t e p " a c r o s s
which t h e s t y l u s o f t h e s u r f a c e p r o f i l e r was drawn, A p i e z o n N g r e a s e
was a p p l i e d t o p a r t o f the e l e c t r o d e s u r f a c e and was removed w i t h
CH C1 a f t e r d e r i v a t i z a t i o n with p o l y ( I ) .
2 2
S y n t h e s i s o f Compound I . As shown i n Scheme I I , 3 - ( t h i o p h e n e - 3 -

y l ) p r o p y l bromide can be p r e p a r e d by a two-carbon h o m o l o g a t i o n (25.) of
3 - t h e n y l bromide v i a r e a c t i o n w i t h d i e t h y l malonate t o form d i e t h y l
3-thenylmalonate. T h i s i s f o l l o w e d by s a p o n i f i c a t i o n ,
d e c a r b o x y l a t i o n , r e d u c t i o n of a c i d t o a l c o h o l , (2£L) and replacement of
t h e h y d r o x y l group w i t h bromide by r e a c t i n g w i t h PBr .(21) 3 Compound
X i s s y n t h e s i z e d by m o n o - q u a t e r n i z a t i o n o f an e x c e s s o f 4,4'-
b i p y r i d i n e with 3-(thiophene-3-yl)propyl bromide f o l l o w e d by N-
m e t h y l a t i o n w i t h C H I . A l l t h e i n t e r m e d i a t e s i n Scheme I I have been
3
i d e n t i f i e d by NMR s p e c t r o s c o p y . X has been c h a r a c t e r i z e d by NMR and

h i g h r e s o l u t i o n mass s p e c t r o s c o p y and by e l e c t r o c h e m i s t r y .
P r e p a r a t i o n and E l e c t r o c h e m i c a l B e h a v i o r o f M a c r o e l e c t r o d e s Modified
w i t h P o l y ( I ) . The e l e c t r o c h e m i c a l b e h a v i o r o f X was i n v e s t i g a t e d i n
CH CN/0.1 M. [n-Bu N]PF v i a c y c l i c voltammetry a t a Pt e l e c t r o d e .
3 4 6
There a r e two r e v e r s i b l e waves due t o the s u c c e s s i v e , r e v e r s i b l e one-

2+ 2 + / + + / o
e l e c t r o n r e d u c t i o n s o f V , E°' ( V ) = -0.72 V, E°' ( V = -1.15 V
+
v s . Ag /Ag. In a d d i t i o n t h e r e i s one a n o d i c wave a t -1.5 V v s .

28. SHU AND WRIGHTON Synthesis and Properties ofPolythiophene Polymer 4 1 3
(a) Array of eight lightly platinized microelectrodes.
Pt Platinized poly(l)
1 2 3 4 5 6 7 8
SJ3N 4 ^
(b) Array of eight alternating heavily and lightly platinized microelectrodes
Platiniz
1 2 3 4 5 6 7 8
^ Si N 3 4 ^
Scheme I . Arrangements o f p l a t i n i z e d m i c r o e l e c t r o d e a r r a y s used
f o r experimentation i n t h i s work.
N B S
, <Q> NaCH(COOEt) 2 l ^ KOH/H Q 2 i ^
CHg CH Br2 CHgCHfCOOEt);, CHgCHfCOOH);,
J - C0 2
S
S
( 1 ) N
D"C N
sK PBr 3 > S
S LIAIH 4 ,K
P F
*~ ' (P^NHPF M — Q ^ 1
Q
(CH ) - V
2 3
+ 4 6
(CH ) Br 2 3 (CH ) OH2 3 CH CH CO0H
2 2
(1) C H I / C H C N3 3
(2) N H P F / H 0 4 6 2 w + + ' = =
\ / = =
\
Q 2 PF«-
(Cl
^ I( C H ) - V
2 3
2 +
-CH, V 2 +
--V } - J V-
Scheme I I . S y n t h e t i c p r o c e d u r e u s e d t o p r e p a r e compound I_.

Ag+/Ag, i n t h e range o f t h e o x i d a t i o n p o t e n t i a l o f 3 -
m e t h y l t h i o p h e n e (14.) due t o t h e i r r e v e r s i b l e o x i d a t i o n o f t h e
f
monomeric t h i o p h e n e u n i t . F i g u r e 1 shows t h e t y p i c a l c y c l i c
voltammetry upon r e p e a t e d l y s c a n n i n g t h e p o t e n t i a l o f a Pt e l e c t r o d e
+
between 0.0 V and 1.5 V v s . Ag /Ag i n a s o l u t i o n o f 0.2 Ml.
Repeated scanning r e s u l t s i n a continuous i n c r e a s e i n the s i z e of the
+
wave a t 0.6 V v s . Ag /Ag, which i s b e l i e v e d t o be t h e o x i d a t i o n wave
o f t h e p o l y t h i o p h e n e backbone o f p o l y ( I ) . The amount o f polymer
p r o d u c e d p e r u n i t o f c h a r g e i n t h e d e p o s i t i o n has not been measured,
but i s q u a l i t a t i v e l y s i m i l a r t o p o l y t h i o p h e n e i t s e l f . A f i l m of
p o l y ( I ) on t h e Pt e l e c t r o d e can be seen w i t h t h e naked eye. After
d e p o s i t i o n of p o l y ( I ) , the polymer-modified e l e c t r o d e i s t r a n s f e r r e d ,
a f t e r thorough r i n s i n g , to c l e a n e l e c t r o l y t e f o r f u r t h e r
characterization.
The c y c l i c voltammetry o f a p o l y ( I ) - c o a t e d Pt e l e c t r o d e w i t h a
8 2
c o v e r a g e o f ~8 x 10' mol cm i n CH CN/0.1 M [ n - B u N ] P F as a f u n c t i o n
3 4 6
o f sweep r a t e i s shown i n F i g u r e 2 As e x p e c t e d there i s a c y c l i c

v o l t a m m e t r y wave i n t h e rang
p o l y t h i o p h e n e , a t about
a n o d i c peak v a r i e s l i n e a r l y w i t h sweep r a t e a t l e a s t up t o 200 mV/s.
2+
In t h e r e g i o n e x p e c t e d f o r t h e r e d u c t i o n o f V ' t h e r e a r e two
2 + 0 f
s u c c e s s i v e o n e - e l e c t r o n waves a s s o c i a t e d w i t h t h e V centers, E
2+ 0 1 + / o +
(V /+) = -0.62 V, E ( V ) = -1.11 V v s . Ag /Ag. The peak h e i g h t s
of t h e c y c l i c voltammetry waves do not v a r y l i n e a r l y w i t h sweep r a t e
1 2
or w i t h (sweep r a t e ) / . R a t h e r , f o r t h e sweep r a t e s shown, t h e
sweep r a t e dependence i s i n t e r m e d i a t e between s q u a r e - r o o t and l i n e a r .
2 + / + / o
These d a t a s u g g e s t t h a t t h e redox c y c l i n g o f t h e v system i s
s l u g g i s h compared t o o x i d a t i o n / r e d u c t i o n o f t h e p o l y t h i o p h e n e
2 + / + / o
backbone. F o r t h e p o t e n t i a l regime where v redox c y c l i n g i s
found, t h e p o l y t h i o p h e n e i s n o n - c o n d u c t i n g and cannot a s s i s t t h e r a t e
2 + / + / o
o f redox c y c l i n g o f t h e v . Therefore, charge t r a n s p o r t v i a
2+/+/o £
v ge x p e c t e d t o be as i n o t h e r v i o l o g e n - b a s e d p o l y m e r s ; i . e .
v i a redox conduction.(28-30)
The r a t i o o f t h e i n t e g r a t e d c u r r e n t s f o r t h e f i r s t r e d u c t i o n
2 +
wave o f V and t h e o x i d a t i o n wave o f t h e p o l y t h i o p h e n e from 0.4 V t o
+
1.0 V v s . Ag /Ag i s about 4. T h i s v a l u e means t h a t upon o x i d a t i o n o f
p o l y ( I ) one e l e c t r o n i s withdrawn from f o u r r e p e a t u n i t s i n t h e
+
backbone o f t h e polymer upon s c a n n i n g t o +1.0 V v s . Ag /Ag. At t h i s
p o t e n t i a l , t h e p o l y t h i o p h e n e a c h i e v e s i t s maximum c o n d u c t i v i t y ( v i d e
infra). The l e v e l o f o x i d a t i o n t o a c h i e v e maximum c o n d u c t i v i t y i s
c o n s i s t e n t w i t h t h e r e s u l t r e p o r t e d by G a m i e r and co-workers (31-
22) t h a t t h e d o p i n g l e v e l o f o x i d i z e d p o l y t h i o p h e n e i s about 25%, but
t h e G a m i e r work d i d not e s t a b l i s h t h a t t h e 25% d o p i n g l e v e l
c o r r e s p o n d s t o maximum c o n d u c t i v i t y . Scheme I I I i l l u s t r a t e s t h e
e l e c t r o c h e m i c a l p r o c e s s e s o f p o l y ( I ) showing r e v e r s i b l e o x i d a t i o n o f
t h e p o l y t h i o p h e n e backbone and r e v e r s i b l e r e d u c t i o n o f t h e pendant
2 +
V centers.
P r e p a r a t i o n and E l e c t r o c h e m i c a l B e h a v i o r o f M i c r o e l e c t r o d e s Modified
w i t h P o l y ( I ) . A m i c r o e l e c t r o d e a r r a y c o n s i s t i n g o f e i g h t Pt
m i c r o e l e c t r o d e s i s c l e a n e d and p l a t i n i z e d as d e s c r i b e d i n t h e
Experimental Section. P o l y ( I ) i s d e p o s i t e d on t h e p l a t i n i z e d
m i c r o e l e c t r o d e a r r a y by s c a n n i n g t h e p o t e n t i a l o f t h e e l e c t r o d e ( s )
+
f r o m 0 V t o 1.5 V v s . Ag /Ag i n a s o l u t i o n o f 0.2 M l i n CH3CN/O.I M.
[H-Bu N]PF . 4 The r e s u l t i n g a r r a y i s i l l u s t r a t e d i n Scheme I .
6 The

SHU AND WRIGHTON Synthesis and Properties of Polythiophene Polymer 415
"I 1
I 1
I 1
I 1
Anodic Polymerization
0.2 M ( I ) i n C H C N / 0 . I M [ n - B u N ] P F
3 4 6
-o
o
- <
c
c
a>
3 —
U "O
o
a
u
0.0 0.4 0.8 1.2

P o t e n t i a l , V vs. A g * / A g
F i g u r e 1. C y c l i c voltammetry ( 2 0 0 mV/s) accompanying r e p e a t e d

scanning o f t h e p o t e n t i a l o f a P t e l e c t r o d e between 0 . 0 V and
1 . 5 V v s . Ag /Ag i n a s o l u t i o n o f 0 . 2 M I i n C H C N / 0 . 1 M [n-
+
3
Bu N]PF .
4 6

1
i 1
i 1
i • i 1
i •—r-r
-1.2 -0.8 -0.4 0.0 0.4 0.8

P o t e n t i a l , V vs. A g / A g
+
F i g u r e 2. C y c l i c voltammetry as a f u n c t i o n o f s c a n r a t e o f a
8 2
p o l y ( I ) - c o a t e d P t e l e c t r o d e w i t h a c o v e r a g e o f 8 x 10" mol/cm
2 +
of V c e n t e r s i n CH CN/0.1 M [ n - B u N ] P F .
3 4 6

28. SHU AND WRIGHTON Synthesis and Properties ofPolythiophene Polymer 417
c y c l i c voltammogram o f t h e p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e shows w e l l -
d e v e l o p e d c y c l i c voltammetry waves. The c y c l i c voltammograms f o r a
p a i r o f a d j a c e n t , p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e s i n C H 3 C N / O . I M [n-
B u N ] P F i n t h e range o f t h e o x i d a t i o n p o t e n t i a l o f p o l y t h i o p h e n e a r e
4 6
shown i n F i g u r e 3. The e s s e n t i a l f e a t u r e s o f t h e c y c l i c voltammetry

waves f o r t h e d e r i v a t i z e d m i c r o e l e c t r o d e s a r e t h e same as f o r
macroscopic e l e c t r o d e s coated with p o l y ( I ) . The i m p o r t a n c e o f t h e
d a t a i n F i g u r e 3 i s t h a t i t shows t h e two m i c r o e l e c t r o d e s a r e
e l e c t r i c a l l y c o n n e c t e d w i t h p o l y ( I ) when t h e p o t e n t i a l o f t h e
e l e c t r o d e s a r e i n t h e range o f t h e o x i d a t i o n p o t e n t i a l o f
polythiophene. The key f a c t i s t h a t t h e c y c l i c voltammograms have
n e a r l y t h e same a r e a when w i r e A a l o n e i s d r i v e n , when w i r e B a l o n e
i s d r i v e n , and when w i r e s A and B t o g e t h e r a r e d r i v e n . These f a c t s
a r e c o n s i s t e n t w i t h t h e c o n c l u s i o n t h a t w i r e s A and B a r e c o n n e c t e d
by p o l y ( I ) and t h a t a l l o f t h e polymer i s a c c e s s i b l e by a d d r e s s i n g A
o r B o r by a d d r e s s i n g A and B t o g e t h e r . I f t h e w i r e s were not
c o n n e c t e d by p o l y ( I ) , o r i f charge t r a n s p o r t were slow on t h e
t i m e s c a l e o f t h e p o t e n t i a l sweep, t h e c y c l i c voltammogram from
d r i v i n g w i r e s A and B t o g e t h e
from A a l o n e p l u s t h e a r e
In c o n t r a s t , t o t h e positiv potentia ,
when t h e p o t e n t i a l o f t h e e l e c t r o d e s i s moved t o t h e range o f t h e
2 +
f i r s t one-electron reduction of V , the electrodes are apparently
not e l e c t r i c a l l y c o n n e c t e d . The c y c l i c voltammograms f o r a p a i r o f
a d j a c e n t , p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e s i n CH3CN/O.I H [ n - B u N ] P F
4 6
2 +
i n the v i c i n i t y of the f i r s t one-electron reduction p o t e n t i a l of V
a r e shown i n F i g u r e 4. The i n t e g r a l o f t h e c y c l i c voltammetry wave
o f w i r e s A and B d r i v e n t o g e t h e r i s e q u a l t o t h e sum o f t h e i n t e g r a l s
f o r w i r e A and w i r e B d r i v e n i n d i v i d u a l l y . This result indicates
t h a t t h e m i c r o e l e c t r o d e s a r e not e l e c t r i c a l l y c o n n e c t e d on t h e
2 +
t i m e s c a l e o f t h e p o t e n t i a l sweep and t h a t o n l y t h e V near a g i v e n
microelectrode i s detected. The i n a b i l i t y t o r a p i d l y a c c e s s a l l o f
2 +
t h e polymer-bound V using a single microelectrode i s a
m a n i f e s t a t i o n o f t h e low v a l u e o f t h e d i f f u s i o n c o e f f i c i e n t f o r
c h a r g e t r a n s p o r t , DQT, f o r t h e redox polymer, as shown r e c e n t l y f o r a
microelectrode array coated with ferrocyanide-loaded, protonated
poly(4-vinylpyridine).(34)
2+/+
Charge T r a n s p o r t from One M i c r o e l e c t r o d e t o A n o t h e r v i a P e n d a n t _ V
Subunits. J u s t as charge t r a n s p o r t o c c u r s i n g e n e r a t o r and c o l l e c t o r
e x p e r i m e n t s a t a r o t a t i n g r i n g / d i s k , (35.) i t can o c c u r from one
m i c r o e l e c t r o d e t o a n o t h e r i n a m i c r o e l e c t r o d e a r r a y c o a t e d w i t h redox
polymer. T h i s phenomenon has been r e c e n t l y i l l u s t r a t e d f o r
m i c r o e l e c t r o d e s c o a t e d w i t h p o l y v i n y l f e r r o c e n e (21) o r w i t h
f e r r o c y a n i d e - l o a d e d , protonated poly(4-vinyl-pyridine).(3-4.) Figure 5
shows r e p r e s e n t a t i v e d a t a f o r an a r r a y l i k e t h a t i l l u s t r a t e d i n
Scheme l a . E l e c t r o d e #4 o f t h e a r r a y i s r e g a r d e d as t h e " g e n e r a t o r "
(analogous t o t h e d i s k e l e c t r o d e ) , and t h e p a i r s #3 and 5, #2 and 6,
and #1 and 7 a r e r e g a r d e d as " c o l l e c t o r s " (analogous t o t h e r i n g
electrode). The p o t e n t i a l o f t h e c o l l e c t o r e l e c t r o d e s i s h e l d
+
c o n s t a n t a t 0.0 V v s . Ag /Ag w h i l e t h e p o t e n t i a l o f t h e g e n e r a t o r
+
e l e c t r o d e i s swept l i n e a r l y i n time, from 0.0 V t o -0.9 V v s . Ag /Ag.
2 +
The p o l y ( I ) i s t h u s i n i t i a l l y a l l a t t h e V s t a t e and has no
2 +
e l e c t r o n t r a n s p o r t . When t h e g e n e r a t o r i s c a p a b l e o f r e d u c i n g V to
+ 2 + / +
V , c h a r g e p a s s e s t o t h e c o l l e c t o r v i a t h e polymer-bound V redox
system. The c u r r e n t a t t h e c o l l e c t o r i n c r e a s e s t o a p l a t e a u f o r

conducting polymer backbone
-+, i, i/,+-"- .;: 4 10v

^s^âae
pendant redox groups
4 , I, I, •+, I, I,
I 0-*-0.8 V
L2+12+12+ 12+
0.8 -»-1.2 v| f
+ 46' I- 46"
xo x o x o
Scheme I I I . E l e c t r o c h e m i c a l processes o f p o l y ( I ) showing

r e v e r s i b l e o x i d a t i o n o f the polythiophene backbone and
r e v e r s i b l e reduction o f the pendant v i o l o g e n c e n t e r s .
I ' I • I -T—I—I—|—r I ' I 1

I 1
wire A alone wire B alone wires A and B
200 n A
JL J i L .L JL
0.0 0.4 0.8 0.0 0.4 0.8 0.0 0.4 0.8
P o t e n t i a l , V vs. A g / A g
+
F i g u r e 3. C y c l i c voltammetry o f a d j a c e n t e l e c t r o d e s o f a
p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e a r r a y d r i v e n i n d i v i d u a l l y and
t o g e t h e r a t 200 mV/s i n t h e r e g i o n o f t h e o x i d a t i v e p o t e n t i a l
o f p o l y t h i o p h e n e i n CH CN/0.1 M [n-Bu N]PF .
3 4 6

SHU AND WRIGHTON Synthesis and Properties of Polythiophene Polymer 419
-0.8 -0.6 -0.4
F i g u r e 4. C y c l i c voltammetry o f a d j a c e n t e l e c t r o d e s o f a
p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e a r r a y d r i v e n i n d i v i d u a l l y and
t o g e t h e r a t 200 mV/s i n t h e r e g i o n o f t h e f i r s t r e d u c t i o n
potential of V 2 +
i n C H C N / 0 . 1 M. [n-Bu N]PF .
3 4 6
1 1
I I I T
_L I I 1 I I JL
-0.8 -0.6 -0.4 -0.8 -0.6 -0.4 -0.8 -0.6 - 0 . 4
Potential, V vs. A g / A g +
F i g u r e 5. G e n e r a t i o n / c o l l e c t i o n experiment w i t h p o l y ( I ) - c o a t e d
m i c r o e l e c t r o d e s i n CH3CN/O.I M [n-Bu N]PF a t 10 mV/s. The
4 6
l o w e r c y c l i c voltammograms a r e f o r t h e g e n e r a t o r e l e c t r o d e a s
i t s p o t e n t i a l i s swept between - 0 . 2 V and - 0 . 9 V v s . Ag /Ag +
while the p o t e n t i a l o f the c o l l e c t o r e l e c t r o d e s i s h e l d a t

0.0 V v s . Ag /Ag. +

2 + / +
g e n e r a t o r p o t e n t i a l s s i g n i f i c a n t l y n e g a t i v e o f E°' ( V ) . Thus, t h e
maximum r a t e o f charge t r a n s p o r t o c c u r s a t t h e maximum c o n c e n t r a t i o n
g r a d i e n t when [ V ] = 0 a t t h e g e n e r a t o r and [V ] = 0 a t the
2+ +
collector. A l s o , t h e p o t e n t i a l o f t h e g e n e r a t o r f o r half-maximum
2 + / + + 2+
c u r r e n t i s a t E°' ( V ) , when [V ] and [V ] a t t h e g e n e r a t o r a r e
equal.
The second f e a t u r e o f t h e d a t a i n F i g u r e 5 i s t h a t t h e maximum
c u r r e n t a t t h e c o l l e c t o r f a l l s as t h e c o l l e c t o r i s moved
g e o m e t r i c a l l y f a r t h e r from t h e g e n e r a t o r and t h e magnitude o f t h e
c u r r e n t i s i n v e r s e l y p r o p o r t i o n a l t o t h e d i s t a n c e a c r o s s which the
charge must be t r a n s p o r t e d . The f i n a l f e a t u r e i n F i g u r e 5 i s t h e
i n c r e a s e i n t h e h y s t e r e s i s o f t h e c u r v e s and t h e i n c r e a s e i n t h e time
r e q u i r e d t o a c h i e v e a s t e a d y s t a t e g e n e r a t o r - c o l l e c t o r c u r r e n t as the
d i s t a n c e between g e n e r a t o r and c o l l e c t o r i n c r e a s e s . These r e s u l t s
a r e c o n s i s t e n t w i t h t h e f a c t t h a t t h e s t e a d y - s t a t e charge t r a n s p o r t
from g e n e r a t o r t o c o l l e c t o r i s by a s u c c e s s i o n o f s e l f - e x c h a n g e
e l e c t r o n t r a n s f e r r e a c t i o n s between n e i g h b o r i n g o x i d i z e d and r e d u c e d
s i t e s i n t h e redox polymer,(3£) d th charg transport b
t r e a t e d as a d i f f u s i o n o
laws. (28-30)
The c u r r e n t as a f u n c t i o n o f g e n e r a t o r p o t e n t i a l a t d i f f e r e n t
f i x e d c o l l e c t i o n p o t e n t i a l s i s shown i n F i g u r e 6 which f u r t h e r
i l l u s t r a t e s t h e f a c t t h a t charge t r a n s p o r t i s d r i v e n not by t h e
e l e c t r i c a l p o t e n t i a l g r a d i e n t but by t h e l i n e a r c o n c e n t r a t i o n
g r a d i e n t between t h e c o l l e c t o r and g e n e r a t o r e l e c t r o d e s . When t h e
p o t e n t i a l o f t h e c o l l e c t o r e l e c t r o d e s i s h e l d a t 0.0 V o r -0.5 V v s .
+
Ag /Ag, the e l e c t r o n f l o w a c r o s s t h e f i l m b e g i n s as t h e g e n e r a t i o n
2+ +
p o t e n t i a l i s scanned near E°' ( V / ) and r e a c h e s a p l a t e a u a t a
f 2 + / +
generator p o t e n t i a l s i g n i f i c a n t l y negative of E° (V ) . I f the
0 , 2 + / +
c o l l e c t o r p o t e n t i a l i s moved c l o s e t o o r e q u a l t o E ( V ),
e l e c t r o n s f l o w s from g e n e r a t o r t o c o l l e c t o r o r from c o l l e c t o r t o
g e n e r a t o r depending on whether t h e g e n e r a t o r p o t e n t i a l i s more o r
l e s s p o s i t i v e than the c o l l e c t o r p o t e n t i a l . When t h e c o l l e c t o r
0 1 2+ +
p o t e n t i a l i s s i g n i f i c a n t l y negative of E ( V / ) , n e a r l y a l l of the
+
polymer i n c o n t a c t w i t h c o l l e c t o r i s i n t h e V (reduced) s t a t e and
e l e c t r o n f l o w o c c u r s o n l y from c o l l e c t o r t o g e n e r a t o r . In a l l c a s e s ,
+ +
[V ] near t h e c o l l e c t o r does not change, and t h e net change o f [V ]
near t h e g e n e r a t o r w h i l e i t i s b e i n g scanned from 0 V t o - 0 . 9 V vs.
Ag /Ag i s t h e same: from 0 t o 100% V .
+ +
So t h e net change o f
+
c o n c e n t r a t i o n g r a d i e n t o f V between g e n e r a t o r and c o l l e c t o r i s t h e
same f o r a l l c o l l e c t i o n p o t e n t i a l s w i t h i n t h e l i m i t s o f t h e g e n e r a t o r
p o t e n t i a l e x c u r s i o n , and t h e net c u r r e n t change i s c o n s t a n t . To
summarize, t h e d a t a i l l u s t r a t e d i n F i g u r e s 5 and 6 a r e q u a l i t a t i v e l y
i n a c c o r d w i t h e x p e c t a t i o n f o r "redox c o n d u c t i o n " (28-30) a s s o c i a t e d
2 + / +
w i t h t h e pendant v centers.
A m i c r o e l e c t r o d e a r r a y c o a t e d w i t h redox polymers has r e c e n t l y
been u s e d t o measure D CT f o r t h e p o l y m e r s . (13,37) U s i n g t h i s method,
DCT can be c a l c u l a t e d from t h e d a t a o f t h e t o t a l amount o f t h e redox
c o u p l e on t h e e l e c t r o d e s and t h e l i m i t i n g c u r r e n t i n
g e n e r a t i o n / c o l l e c t i o n experiments with the polymer-coated
m i c r o e l e c t r o d e a r r a y . The c y c l i c voltammetry o f an a r r a y o f e i g h t
p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e s i n CH CN/0.1 M [ n - B u N ] P F i s
3 4 6
p r e s e n t e d i n F i g u r e 7a. The t o t a l charge c a l c u l a t e d from t h e

7
i n t e g r a t i o n o f t h e c u r r e n t o f t h e voltammogram i s about 3.3 x 10~ C.
The c y c l i c voltammetry o f g e n e r a t o r and c o l l e c t o r i n t h e

-0.8-0.4 0 -0.8 -0.4 0 -0.8 -0.4 0 -0.8-0.4 0 -OB -0.4 0
Potential, V vs. Ag / A g
F i g u r e 6. G e n e r a t i o n / c o l l e c t i o n e x p e r i m e n t s f o r d i f f e r e n t
f i x e d c o l l e c t o r p o t e n t i a l s i n an i n t e r d i g i t a t e d a r r a y o f
m i c r o e l e c t r o d e s c o a t e d w i t h p o l y ( I ) i n CH CN/0.1 M [ n - B u N ] P F .
3 4 6
The p o t e n t i a l o f t h e c o l l e c t o r e l e c t r o d e s i s h e l d a t 0.0 V,
+
-0.50 V, -0.59 V, -0.62 V, o r -0.80 V v s . Ag /Ag w h i l e t h e
p o t e n t i a l o f t h e g e n e r a t o r e l e c t r o d e s i s swept between 0.0 V
+
and -0.9 V v s . Ag /Ag a t 20 mV/s.

Potential, V vs. AgvAg
F i g u r e 7. C y c l i c voltammetry o f an i n t e r d i g i t a t e d a r r a y o f
m i c r o e l e c t r o d e s c o a t e d w i t h p o l y (I) i n CH CN/0.1 M. [n.-Bu N] P F
3 4 6
(a) The p o t e n t i a l o f a l l e i g h t e l e c t r o d e s i s scanned t o g e t h e r

a t 10 mV/s. (b) The p o t e n t i a l o f e l e c t r o d e s #2 4,6 and 8 i s
f f
s c a n n e d a t 10 mV/s w h i l e t h e p o t e n t i a l o f e l e c t r o d e s #1,3,5,
+
and 7 i s h e l d a t 0 V v s . Ag /Ag.

i n t e r d i g i t a t e d a r r a y m i c r o e l e c t r o d e s i s shown i n F i g u r e 7b. The

S t e a d y - s t a t e c u r r e n t i s 40 nA. From t h e r a t i o o f t h e s t e a d y - s t a t e
c u r r e n t , t h e t o t a l c h a r g e , and t h e d i s t a n c e s between two e l e c t r o d e s ,
9 2
we f i n d a v a l u e o f D CT -7 x 10" cm /s f o r c h a r g e t r a n s p o r t v i a t h e
2 + / +
pendant V i n p o l y ( I ) a t 298 °K i n CH CN/0.1 M [ n - B u N ] P F .
3 For
4 6
2 + / +
c o m p a r i s o n , t h e v a l u e o f DCT o f t h e v has a l s o been measured by
1 / 2
p o t e n t i a l s t e p chronoamperometry. The v a l u e o f D T C from
C
7 2 1 / 2
chronoamperometry i s 1.6 x 10" m o l / c m s . The v a l u e o f C, t h e
c o n c e n t r a t i o n o f redox c e n t e r s i n t h e polymer, can be d e t e r m i n e d by
m e a s u r i n g t h e polymer c o v e r a g e f r o m e l e c t r o c h e m i c a l d e t e r m i n a t i o n and
t h e f i l m t h i c k n e s s as measured by a s u r f a c e p r o f i l e m e a s u r i n g d e v i c e .
The t h i c k n e s s o f 3.0 x 10~ mol/cm o f p o l y (I) i s -1.3 urn a t 0.0 V
7 2
v s . A g / A g i n CH3CN/O.I M [ n - B u N ] P F .
+
4 6 The d r y t h i c k n e s s o f t h e same
f i l m o f p o l y ( I ) i s -1.2 Jim. There i s a l i n e a r r e l a t i o n s h i p between
8
c o v e r a g e and t h i c k n e s s f o r c o v e r a g e s i n t h e range 4-30 x 10"
2
mol/cm ,and t h e i n t e r c e p t i s z e r o f o r a p l o t o f t h i c k n e s s a g a i n s t
coverage. From t h e s l o p e o f t h e s t r a i g h t l i n e , t h e v a l u e o f C can be
c a l c u l a t e d and i s -2.4 M
p o t e n t i a l step data i s thu
t h a t o b t a i n e d w i t h s t e a d y - s t a t e c u r r e n t i n an i n t e r d i g i t a t e d
microelectrode array. A s i m i l a r d i f f e r e n c e between p o t e n t i a l s t e p
and s t e a d y s t a t e d a t a has been o b s e r v e d f o r p o l y - [ O s ( b p y ) 2 ( v p y ) 2 ] -
(C10 )4 2 f i l m s . (31)
Charge t r a n s p o r t v i a a redox polymer i s t r e a t e d as a t h e r m a l l y
activated diffusion.(22) F i g u r e 8 i l l u s t r a t e s the temperature
dependence f o r t h e g e n e r a t o r - c o l l e c t o r e x p e r i m e n t showing t h a t t h e
l i m i t i n g c u r r e n t i n c r e a s e s s i g n i f i c a n t l y at higher temperatures. The
l o g a r i t h m o f t h e l i m i t i n g c u r r e n t i s l i n e a r w i t h 1/T, as shown i n
F i g u r e 9. The s l o p e o f t h e s t r a i g h t l i n e g i v e s an A r r h e n i u s
a c t i v a t i o n e n e r g y o f 9.8 k c a l / m o l , which i s s l i g h t l y l a r g e r t h a n t h e
v a l u e o f 8.9 k c a l / m o l r e p o r t e d f o r a v i o l o g e n b a s e d p o l y s i l o x a n e . (3iL=.
M)
P o l y ( I ) - b a s e d M i c r o e l e c t r o c h e m i c a l T r a n s i s t o r s . Research i n the
W r i g h t o n group has a l r e a d y d e m o n s t r a t e d some o f t h e p r i n c i p l e s o f
m i c r o e l e c t r o c h e m i c a l d e v i c e s b a s e d on redox a c t i v e m a t e r i a l s . These
m a t e r i a l s i n c l u d e c o n d u c t i n g polymers,(1.14.15) e l e c t r o a c t i v e
o x i d e s (41-42) and c o n v e n t i o n a l redox polymers.(34.43-44)
f Scheme I V
i l l u s t r a t e s the o p e r a t i o n of a m i c r o e l e c t r o c h e m i c a l t r a n s i s t o r based
on p o l y ( I ) . T h i s d e v i c e combines c h a r a c t e r i s t i c s t h a t have
p r e v i o u s l y been d e m o n s t r a t e d f o r d e v i c e s b a s e d on c o n d u c t i n g p o l y m e r s
and d e v i c e s b a s e d on redox p o l y m e r s . A change i n t h e g a t e v o l t a g e ,
V , r e s u l t s i n a change i n t h e s t a t e o f c h a r g e o f t h e e l e c t r o a c t i v e
G
m a t e r i a l c o n n e c t i n g t h e two m i c r o e l e c t r o d e s c a l l e d s o u r c e and d r a i n .
Thus, t h e d r a i n c u r r e n t , IQ, a t a f i x e d s o u r c e - d r a i n p o t e n t i a l , V , D
can be t u r n e d on o r o f f by v a r i a t i o n o f V , because f o r some redox G
s t a t e t h e e l e c t r o a c t i v e m a t e r i a l i s i n s u l a t i n g and f o r some o t h e r
redox s t a t e the e l e c t r o a c t i v e m a t e r i a l i s c o n d u c t i n g . The d a t a i n
F i g u r e s 1, 2, and 3 a r e c o n s i s t e n t w i t h t h e f a c t t h a t t h e backbone o f
p o l y ( I ) i s s i m i l a r to that of poly(3-methylthiophene). The
r e s i s t a n c e o f p o l y ( I ) c o n n e c t i n g m i c r o e l e c t r o d e s as a f u n c t i o n o f V G
i n t h e regime o f t h e o x i d a t i o n p o t e n t i a l o f p o l y t h i o p h e n e i s shown i n
F i g u r e 10. The m i c r o e l e c t r o d e a r r a y u s e d i s l i k e t h a t shown i n
Scheme l b where m i c r o e l e c t r o d e s #1, 3, 5, and 7 a r e r e g a r d e d as t h e
" s o u r c e " and m i c r o e l e c t r o d e s #2, 4, 6, and 8 a r e r e g a r d e d as t h e

'1,3,5.7 - 2,4,6,8
v s E
0 E|,3,5,7 = 0 V vs. A g / A g +
T40nA
o O-
36.0°C 29.0°C 24.0°C I9.0°C I4.3°C 8.0°C 4.0°C

O-
^ j40nA
'2,4,6,8 v s
- 2,4,6,
E
E
l,3,5,7 = o v v s
- Ag /Ag
+
I——I I—f"1
I '—I
— I——I
1
I—r- r
1—r-
-0.8 - 0 . 4 -0.8 -0.4 -0.8 -0.4 -0.8 -0.4 -0.8 -0.4 -0.8 -0.4 -0.8 -0.4
P o t e n t i a l , V vs. A g / A g +
F i g u r e 8. G e n e r a t i o n / c o l l e c t i o n e x p e r i m e n t s a s a f u n c t i o n o f
t e m p e r a t u r e a t an i n t e r d i g i t a t e d a r r a y o f m i c r o e l e c t r o d e s
c o a t e d w i t h p o l y ( I ) a t 50 mV/s i n CH CN/0.1 M [ n - B u N ] P F . 3 4 6
2 1 1 I 1 I 1 I 1 I 1 I
3.2 3.3 3.4 3.5 3.6 3.7
l/T, x I0 3
F i g u r e 9. L o g o f t h e l i m i t i n g s t e a d y - s t a t e g e n e r a t o r / c o l l e c t o r
c u r r e n t o f an i n t e r d i g i t a t e d a r r a y o f m i c r o e l e c t r o d e s coated
with poly(I) v s . l / T .

VQ—jPotentiostat fcs>
00
I i ^ K T ^ Counterelectrode
Reference
Device "Off" Device "On" Device "ofT Device "On"
Scheme I V . A p o l y ( I ) - b a s e d microelectrochemical t r a n s i s t o r I
that turns on when V Q i s moved from V Q 3 (ie + 0 . 4 V v s .
+ 4
Ag /Ag) where polythiophene i s reduced and i n s u l a t i n g t o V Q 1
+
(ie + 0 . 7 V vs. Ag /Ag) where polythiophene i s oxidized and
conducting. This t r a n s i s t o r also turns on t o a smaller

0 / 2 + + 1 +
extent at E ( V / ) , V Q = - 0 . 6 3V vs. Ag /Ag. At V G

significantly (>0.2 V ) more negative 2
( V Q < - 0 . 8 V vs.
I
St
+ 3 +
%
Ag /Ag) or p o s i t i v e ( + 0 . 4 V > V Q > - 0 . 4 V vs. Ag /Ag) of

2 + +
E ° ' ( V / ) only the reduced or o x i d i z e d form o f viologen
i
redox centers i s present, respectively, and t h i s device i s i
off.

28. SHU AND WRIGHTON Synthesis andProperties ofPolythiophene Polymer 4 2 7
"drain". I n t h e r e d u c e d s t a t e , p o l y ( I ) i s i n s u l a t i n g and t h e d e v i c e
i s " o f f " ; i n t h e o x i d i z e d s t a t e , p o l y ( I ) i s c o n d u c t i n g and t h e d e v i c e
5
i s "on". The r e s i s t a n c e o f t h e p o l y ( I ) d e c l i n e s b y a f a c t o r o f 1 0
+
upon c h a n g i n g t h e v a l u e o f V from 0 . 4 V t o 0 . 8 V v s . Ag /Ag.
G
M i c r o e l e c t r o c h e m i c a l t r a n s i s t o r s b a s e d on c o n v e n t i o n a l redox
p o l y m e r s , i n c o n t r a s t t o t h o s e b a s e d on c o n d u c t i n g p o l y m e r s , w i l l
f
g i v e an I Q - V Q c h a r a c t e r i s t i c w i t h a s h a r p maximum i n I a t V = E ° o f D G
the redox polymer. T h i s c h a r a c t e r i s t i c a r i s e s because t h e

c o n d u c t i v i t y o f t h e c o n v e n t i o n a l redox polymer i s due t o e l e c t r o n
s e l f - e x c h a n g e between o x i d i z e d and r e d u c e d s i t e s (2£) and t h e r a t e o f
s e l f - e x c h a n g e i s p r o p o r t i o n a l t o [ox] and [ r e d ] . S i n c e [ox] + [ r e d ]
i s f i x e d i n t h e polymer and [ o x ] / [ r e d ] changes s t e e p l y w i t h v a r i a t i o n
i n p o t e n t i a l o f t h e polymer, a c o n v e n t i o n a l redox polymer w i l l show a
narrow r e g i o n o f c o n d u c t i v i t y w i t h i t s maximum c o n d u c t i v i t y when [ox]
e q u a l s [ r e d ] , which o c c u r s when t h e p o t e n t i a l o f t h e polymer i s h e l d
0 1
a t E . The c o n d u c t i v i t y w i l l f a l l s h a r p l y when t h e p o t e n t i a l o f t h e
T V
p o l y m e r i s moved away f r o m E ° . ( 2 8 - 3 0 ) F i g u r e 1 1 shows t h e I D ~ G
c h a r a c t e r i s t i c of a p o l y
the f i r s t one-electron r e d u c t i o
m i c r o e l e c t r o c h e m i c a l t r a n s i s t o r shows o n l y a narrow r e g i o n o f V G
where t h e d e v i c e i s "on". F o r V = 2 5 mv, t h e w i d t h a t h a l f - h e i g h t

D
f
i s o n l y 5 6 mV w i t h t h e peak i n I D o c c u r r i n g v e r y c l o s e t o t h e E ° o f
2 + / +
t h e polymer-bound V . The h e i g h t and w i d t h become g r e a t e r f o r
larger VQ. Whenever V exceeds - 0 . 3 V t h e maximum I does n o t
D D
2 +
i n c r e a s e , because t h e maximum d i f f e r e n c e i n c o n c e n t r a t i o n o f V and
+
V i s no l o n g e r i n f l u e n c e d by V . D
Conclusions
E l e c t r o c h e m i c a l o x i d a t i o n o f i produces a polymer f i l m with

p o l y t h i o p h e n e as t h e backbone and v i o l o g e n c e n t e r s as pendant redox
groups. The e l e c t r o c h e m i c a l p r o p e r t i e s o f t h e p o l y m e r a r e t h e
c o m b i n a t i o n o f p o l y t h i o p h e n e and v i o l o g e n . Using viologen subunits
as t h e i n t e r n a l s t a n d a r d (one p e r r e p e a t u n i t o f t h e p o l y m e r ) , t h e
" d o p i n g l e v e l " o f t h e o x i d i z e d p o l y t h i o p h e n e backbone a t i t s maximum
c o n d u c t i v i t y c a n be measured and i s about 2 5 % . The c h a r g e t r a n s p o r t
2 + / +
v i a t h e pendant v o f p o l y ( I ) has been s t u d i e d by
g e n e r a t i o n / c o l l e c t i o n experiments u s i n g p o l y ( I ) - c o a t e d m i c r o e l e c t r o d e
2 + / +
arrays. The redox c o n d u c t i o n a s s o c i a t e d w i t h t h e V redox system
can be t r e a t e d as a d i f f u s i o n o f e l e c t r o n s which f o l l o w s F i c k ' s
2 + / +
d i f f u s i o n laws. The D of v
C T o f p o l y ( I ) has been measured t o be
9 2
4 - 7 x 1 0 ~ cm /s, somewhat l a r g e r t h a n f o r a v i o l o g e n - b a s e d
polysiloxane.(39-40)
The p o l y ( I ) - b a s e d t r a n s i s t o r i s t h e f i r s t i l l u s t r a t i o n o f a
m i c r o e l e c t r o c h e m i c a l t r a n s i s t o r b a s e d on a c o m b i n a t i o n o f a
c o n d u c t i n g and a c o n v e n t i o n a l redox polymer as t h e a c t i v e m a t e r i a l .
The t r a n s i s t o r " t u r n s on" a t V c o r r e s p o n d i n g t o o x i d a t i o n o f t h e
G
p o l y t h i o p h e n e backbone. The r e s i s t i v i t y o f p o l y ( I ) d e c l i n e s by a
5 +
f a c t o r o f 1 0 upon c h a n g i n g V from 0 . 4 V t o 0 . 8 V v s . Ag /Ag.
G When
2 + / +
VG i s moved c l o s e t o t h e o n e - e l e c t r o n r e d u c t i o n p o t e n t i a l o f V ,
t h e c o n v e n t i o n a l redox c o n d u c t i v i t y g i v e s a s m a l l d e g r e e o f " t u r n
on". A s h a r p I D ~ V c h a r a c t e r i s t i c r e s u l t s , w i t h an I ( p e a k ) a t V =
g D G
2 + / +
E°' ( V ). Though t h e m i c r o e l e c t r o c h e m i c a l d e v i c e s b a s e d on
c o n v e n t i o n a l redox c o n d u c t i o n have b o t h slow s w i t c h i n g s p e e d and a

F i g u r e 11. D r a i n c u r r e n t , IQ, VS. g a t e v o l t a g e , V , f o r

G
various drain voltages, V D (25, 50, 100 mV) f o r a p o l y ( I ) - b a s e d

microelectrochemical transistor. The g a t e v o l t a g e , V
G was
scanned a t 1 mV/s.

28. SHU AND WRIGHTON Synthesis and Properties of Polythiophene Polymer 4 2 9
s m a l l v a l u e o f Ip, i n comparison t o d e v i c e s b a s e d on s o - c a l l e d
c o n d u c t i n g polymers, t h e narrow r e g i o n o f VQ where t h e d e v i c e i s
t u r n e d on i s an advantage t h a t may p r o v e u s e f u l i n s e n s o r
applications.(41,46) A l s o s m a l l e r m i c r o e l e c t r o d e s , more c l o s e l y
spaced w i l l y i e l d m i c r o e l e c t r o c h e m i c a l devices having b e t t e r
electrical characteristics.(47)
Acknowledgments
We w i s h t o thank t h e O f f i c e o f N a v a l R e s e a r c h and t h e D e f e n s e
Advanced R e s e a r c h p r o j e c t s Agency f o r p a r t i a l s u p p o r t o f t h i s
research.
Literature Cited
1. White, H.S.; Kittlesen, G.P.; Wrighton, M.S. J. Am. Chem. Soc.,

1984, 106, 5375.
2. Kittlesen, G.P.; White
1984, 106, 7389.
3. Murray, R.W. in Electroanalytical Chemistry, Bard, A.J. Ed.;
Marcel Dekker: New York, 1984; Vol. 13, p 191.
4. Wrighton, M.S. Science, 1986, 231, 32.
5. Bidan, G.; Deronzier, A.; Moutet, J.C. J. Chem. Soc. Chem.
Commun., 1984, 1185.
6. Coche, L.; Deronzier, A.; Moutet, J.C. J. Electroanal. Chem.,
1986, 198, 187.
7. Coche, L.; Moutet, J. C. J. Electroanal, Chem., 1987, 224, 111.
8. Coche, L.; Moutet, J . C. J . Am. Chem. Soc., 1987, 109, 6887.
9. Bidan, G.; Deronzier, A.; Moutet, J. C. Nouv. J. Chim., 1984, 8,
501.
10. Eaves, G.; Munro, H.S.; Parker, D. Inorg. Chem., 1987, 26, 644.
11. Haimerl, A.; Merz, A. Angew. Chem. Int. Ed. Engl., 1986, 25, 180.
12. Audebert, P.; Bidan, G.; Lapkowski, M. J . Chem. Soc. Chem
Commun., 1986, 887.
13. Waltman, R.J.; Bargon, J.; Diaz, A.F. J. Phys.Chem., 1983, 87,
1459.
14. Thackeray, J.W.; White, H.S.; Wrighton, M.S. J. Phys. Chem.,
1985, 89, 5133.
15. Paul, E.W.; Ricco, A.T.; Wrighton, M.S. J. Phys. Chem., 1985, 81,
1441.
16. Lewis, N.S.; Wrighton, M.S. Science, 1981, 211, 944.
17. Elliott, C.M.; Martin, W.S. J. Electroanal.Chem., 1982, 137, 377.
18. Bruce, J.A.; Murahashi, T.; Wrighton, M.S. J. Phys. Chem., 1982,
86, 1552.
19. Dominey, R.N.; Lewis, N.S.; Bruce, J.A.; Bookbinder, D.C.;
Wrighton, M.S. J. Am. Chem. Soc., 1982, 104, 467.
20. Bookbinder, D.C.; Wrighton, M.S. J. Electrochem. Soc., 1983, 130,
1080.
21. Kittlesen, G.P.; White, H.S.; Wrighton, M.S. J. Am. Chem. Soc.,
1985, 107, 7373.
22. Kittlesen, G.P.; Wrighton, M.S. J. Mol. Electron., 1986, 2, 23.
23. Gronowitz, S.; Frejd, T. Synth. Commun., 1976, 6, 475.
24. Kittlesen, G.P.; Ph.D. Thesis, Massachusetts Institute of
Technology, Cambridge, MA, 1985.

25. Marvel, C.S. Qrg. Synth., Coll. Vol. 3, 705.

26. Blicke, F.F.; Sheet, D.J. J. Am. Chem. Soc., 1949, 71, 2857.
27. Noller, C.R.; Dinsmore, R. Org. S y n t h . , C o l l . Vol 2, 358.
28. Pickup, P.G.; Murray, W.R. J. Am. Chem. Soc., 1983, 105, 4510.
29. Pickup, P. G.; Kutner, W.; Leidner, C. R.; Murray, R.W. J. Am.
Chem. Soc., 1984, 106, 1991.
30. Pickup, P.G.; Murray, R.W. J. Electrochem. Soc., 1984, 131, 833.
31 Tourillon, G.; Garnier, F. J. Electroanal. Chem., 1982, 135, 173.
32. Touillon, G.; Garnier, F. J. Phys. Chem., 1983, 87, 2289.
33. Tourillon, G.; Garnier, F. J . Electoanal. Chem., 1984, 161, 407.
34. Belanger, D.; Wrighton, M.S. Anal. Chem., 1987, 59, 1426.
35. Bard, A . J . ; Faulkner, L.R. Electrochemical Methods; Wiley: New
York, 1980.
36. Kaufman, F.B.; Engler, E.M. J. Am. Chem. Soc., 1979, 101, 547.
37. Chidsey, C.E.; Feldman, B.J.; Lundgren, C.; Murray, R. W. Anal.
Chem., 1986, 58, 601.
38. Daum, P.; Lenhard, J.R.; Rolison, D.; Murray, R.W. J. Am. Chem.
Soc., 1980, 102, 4649
39. Lewis, T . J . ; White,
106, 6947.
40. Lewis, T . J . ; Ph.D. Thesis, Massachusetts Institute of Technology,
Cambridge, MA, 1984.
41. Natan, M.J.; Mallouk, T.E.; Wrighton, M.S. J. Phys. Chem., 1987,
91, 648.
42. Natan, M.J.; Belanger, D.; Carpenter, M.S.; Wrighton M.S. J.
Phys. Chem., 1987, 91, 1834.
43. Smith, D.K.; Lane, G.A.; Wrighton, M.S. J. Am.Chem.Soc., 1986,
108, 3522.
44. Smith, D.K.; Lane, G.A.; Wrighton, M.S. J. Phys. Chem., 1988, 92,
2616.
45. Thackeray, J.W.; Wrighton, M.S. J. Phys. Chem., 1986, 90, 6674.
46. Wrighton, M.S.; Thackeray, J.W.; Natan, M.J.; Smith, D.K.; Lane,
G.A.; Belanger, D.; Phil. Trans. Royal Soc. Lond., 1987, B316,
13.
47. Jones, E.T.T.; Chyan, O.M.; Wrighton, M.S. J. Am. Chem Soc.,
1987, 109, 5526.
RECEIVED M a y 1 9 , 1988

Chapter 29
Electroactive Bipyridiniums in Self-Assembled

Octadecylmercaptan Monolayers
on Gold Electrodes
H. O. Finklea, J. Fedyk, and J. Schwab
Department of Chemistry, West Virginia University, Morgantown,

WV 26506
N-Octadecyl-n'-methy
the n'-ethyl analog are co-deposited with octadecyl
mercaptan onto a gold substrate during self-assembly
of an organized monolayer from a chloroform/methanol
s o l u t i o n . Surface redox waves are observed in aqueous
e l e c t r o l y t e corresponding to the reduction of the
bipyridiniums. The bipyridiniums also assemble from
aqueous e l e c t r o l y t e to form an e l e c t r o a c t i v e monolayer
on both bare gold and gold coated with a mercaptan
monolayer. The electrochemical behavior suggests that
i n both cases the bipyridiniums reside on but not i n
the mercaptan monolayer. Evidence is given f o r penetration
of the mercaptan monolayer by bipyridiniums.
Long chain alkylmercaptans and d i s u l f i d e s r e a d i l y self-assemble on

gold surfaces to form compact organized monolayers i n which the
s u l f u r i s chemisorbed to the gold and the hydrocarbon t a i l i s
extended away from the surface 0.-5). The mercaptan monolayers
strongly i n h i b i t gold oxidation i n d i l u t e s u l f u r i c acid and also
2 1 3 3
block d i f f u s i o n of aqueous ions (e.g. Fe , Fe(CN) ~ > 6
2 + 3 +
R u ( N H ) ' ) t o the gold surface (4-5)• The unique anisotropy of
3 6
the organized monolayer provides an opportunity to explore the

e f f e c t of both o r i e n t a t i o n and distance on electron transfer between
a molecule and a metal electrode (6-9).
Our strategy i s to incorporate a prolate redox molecule i n t o
the hydrocarbon phase of the organized monolayer. Steric
r e s t r a i n t s imposed by a close-packed monolayer would presumably
force the redox molecule to adopt an o r i e n t a t i o n p a r a l l e l to the
hydrocarbon t a i l s . Spacing can then be controlled by a short
hydrocarbon chain between the redox center and the metal. A class
of molecules f i t t i n g these requirements are the assymetric
4,4'-bipyridiniums:
0097-6156/88/0378-0431$06.00/0
c

R i s the spacer group which should also terminate i n an anchor e.g.

a mercaptan. We report here intermediate r e s u l t s i n which R i s the
methyl and e t h y l moiety; the case of R^H i s the subject of a
separate paper (K. A. B. Lee, R. Mowry, G. McLennan and H. 0.
F i n k l e a , i n press). Our primary concern i s whether the
bipyridiniums are incorporated i n t o the mercaptan monolayer and
whether they are located at a f i x e d distance r e l a t i v e to the gold
surface.
Experimental
Synthesis. N-0ctadecyl-4-pyridinium-4•-pyridyl iodide (mp 125°C)

was synthesized by s t i r r i n g stoichiometric amounts of 4,4'-bipyri-
dine and 1-iodooctadecane i n acetone f o r several days. The
p r e c i p i t a t e was c o l l e c t e d and r e c r y s t a l l i z e d from methanol/ether.
N-Methyl-n'-octadecy1-4,4*-bipyridinium d i i o d i d e [(C bpyMe)I ] (mp
t8 2
270°C with decomposition) and N-ethyl-n'-octadecy1-4,4'-bipy

ridinium d i i o d i d e [(C b p y E t ) I
18
synthesized by r e f l u x i n
iodide i n methanol. The iodide was replaced with chloride by
d i s s o l v i n g the biipyridiniums i n a minimum amount of b o i l i n g water
and adding excess saturated KC1 s o l u t i o n . A f t e r c h i l l i n g the yellow
s o l i d was c o l l e c t e d and subjected to a second metathesis step to
remove the l a s t traces of iodide.
Deposition of the mixed monolayer. Deposition solutions were

prepared by d i s s o l v i n g octadecylmercaptan [C SH] and the respective
18
bipyridinium i n a mixture of chloroform and methanol. The electrode

was cleaned by heating i t i n a gas-air flame. A f t e r cooling, the
electrode was immersed i n the deposition s o l u t i o n f o r 1 5 - 3 0
minutes, withdrawn, and rinsed i n clean methanol or chloroform.
Q u a l i t a t i v e l y the most reproducible surface redox waves and lowest
charging currents during c y c l i c voltammetry were obtained with a
freshly-prepared deposition s o l u t i o n containing 50 mM C i e S H and
10 mM of the bipyridinium i n a 1:1 volume r a t i o of chloroform and
methanol.
Electrochemistry. C y c l i c voltammetry was performed using gold f l a g

2
electrodes (area 0.7 cm ) and a SCE reference electrode. The
e l e c t r o l y t e was 0.1 M KC1 buffered to pH8 with 0.01 M Na HP0*. Data 2
a c q u i s i t i o n , manipulation and p l o t t i n g were performed using a Zenith

computer interfaced to a potentiostat v i a a Metrabyte DASH-16 board
and running MacMillan ASYSTANT+ software.
Mixed monolayers. An electrode coated with a mixed monolayer of

2+
C SH and C b p y M e e x h i b i t s a surface redox wave assignable to the
18 18
reduction of the bipyridinium to the r a d i c a l cation (Figure 1) ( i n

a l l 3 figures the c y c l i c voltammograms at 0.1 V/s ( s o l i d l i n e ) , 1
V/s (dashed l i n e ) and 10 V/s (dotted l i n e ) are plotted with the
current axis scaled i n proportion to the scan r a t e ) . A second
reduction wave at -0.9 V (not shown) i s obscured by increasing
background currents. The electrochemical parameters f o r the surface

29. F I N K L E A ET AL. Bipyridiniums in Octadecylmercaptan Monolayers 433
redox wave given i n Table I along with t y p i c a l values f o r the

2 +
surface redox wave of a mixed monolayer containing d b p y E t . At 8
scan rates less than 0.1 V/s the redox wave obeys the normal
r e l a t i o n s h i p s f o r a surface bound species i . e . peak s p l i t t i n g (AE )
i s close to zero, peak currents are proportional to scan r a t e , and
the peak f u l l width at h a l f maximum ( A E ^ ^ J i s close to the
t h e o r e t i c a l 90 mV. The coverage represents ca. 10% of a close
packed monolayer ( 3 x l 0 ~ " mol/cm assuming 50 A per bipyridinium).
xo 2
At higher scan rates the peaks broaden ( p a r t i c u l a r l y the anodic

peak), the peak currents are not proportional to scan r a t e , and the
apparent coverage decreases.
Table I . Electrochemical Parameters f o r the F i r s t Redox Wave

of Deposited or Adsorbed Bipyridiniums
Al
Scan .
0 1
Coating Rate E A
P 2 1 0 2
(V/s) ( mV ) (yA/cm ) ( x l O " mol/cm )
mixed .10 -471 24 116 126 2.3 2.2 .30 .30

monolayer
Ci bpyMe2+
8 1.0 -470 61 147 181 15 16 .24 .31
+ C SH 1 8 10. -475 63
- - 56 63 .08 .09
mixed .10 -480 30 110 120 3.1 2.9 .36 .31

monolayer
Ci bpyEt
8
2
+ C SH 1 8
adsorbed .10 -459 4 124 116 15 14 1.8 1.2

C bpyMe
18
2+
clean gold 1.0 -461 16 119 112 164 163 1.9 1.6
10. -467 86 123 134 1300 1270 1.5 1.4
adsorbed .10 -445 9 153 153 17 17 2.0 2.0

C bpyMe
18
2
C SH-
1 8 1.0 -458 54 128 170 180 114 1.9 1.5
coated gold 10.
- - 185 - 890
- 1.2
-
The f i r s t two e n t r i e s refer to mixed monolayers deposited p r i o r to
the electrochemical measurements; the l a s t two e n t r i e s refer to
bipyridinium monolayers adsorbed from the e l e c t r o l y t e . J i s the
peak current i n the cathodic and anodic d i r e c t i o n s f o r t h i f i r s t
redox wave of the bipyridiniums; T i s the coverage found by
i n t e g r a t i o n of the respective cathodic and anodic peaks. The other
headings have been defined i n the preceding text. Data i s omitted
where the surface wave i s not well-defined r e l a t i v e to the
background current.

I f the bipyridiniums are located at a f i x e d distance from the

electrode surface, the surface coverage would be independent of the
scan rate. The loss of apparent coverage at fast scan rates
indicates that the bipyridiniums are not r i g i d l y f i x e d near the
electrode surface. Daifuku et. a l . (10) have also observed an
apparent loss of coverage at fast scan rates f o r a Langmuir-Blodgett
monolayer of surfactant osmium b i p y r i d i n e complexes. They
postulated that parts of the monolayer were not i n contact with the
electrode and that the remote 0s(bpy) complexes were oxidized or
3
reduced v i a l a t e r a l e l e c t r o n exchange i n the monolayer.

Further experiments with the coated electrode suggests that the
surfactant bipyridiniums are mobile w i t h i n the mercaptan monolayer.
I f the electrode i s transferred to a f r e s h e l e c t r o l y t e , the coverage
(measured at 0.1 V/s) g r e a t l y diminishes. Likewise r i n s i n g the
coated electrode with a stream of pure water between c y c l i c
voltammograms removes most of the e l e c t r o a c t i v e bipyridiniums.
These treatments do not remove the mercaptan monolayer (5)
We therefore hypothesiz
contact with water, the surfactan
the mercaptan monolayer but adsorbed to i t s e x t e r i o r . The adsorbed
bipyridiniums communicate with the electrode by a small f r a c t i o n of
bipyridiniums which penetrate the monolayer. A short-chain analog,
1 1
methyl viologen (N,N -dimethy1-4,4 -bipyridinium d i c h l o r i d e ) , can
penetrate the mercaptan monolayer at s i t e s not accessible to the
f e r r i c ion or other inorganic ions (3,5). For example, i n a 1 mM
methyl viologen s o l u t i o n the cathodic peak current on a
C SH-coated electrode i s attenuated only by 30% r e l a t i v e to the
18
peak current on a clean electrode (0.1 V/s). In a more d i l u t e

s o l u t i o n (0.05 mM) the cathodic peak currents are i d e n t i c a l f o r
clean and coated electrodes. Yet the same coated electrode i s
3
strongly blocking to F e reduction i n d i l u t e s u l f u r i c a c i d ; the
cathodic peak current i s reduced by a f a c t o r of 500 i n the presence
of the monolayer.
A d d i t i o n a l support f o r the preceding model i s found i n
experiments i n which the surfactant bipyridinium i s dissolved i n the
e l e c t r o l y t e rather than co-deposited with the mercaptan monolayer.
Adsorbed bipyridiniums. Surfactant bipyridiniums adsorb onto bare

gold from aqueous s o l u t i o n ; saturation i s reached at concentrations
of 10 M or greater f o r Ciz,bpyMe (11,12). Figure 2 i l l u s t r a t e s
u 2+
2
the c y c l i c voltammogram of a 1x10 * M s o l u t i o n of CiebpyMe using a
clean gold electrode; Table I contains the electrochemical
parameters of the f i r s t redox wave near -0.46 V. The data i n Table
I c l e a r l y indicates that the currents are due to an adsorbed
monolayer of C i b p y M e . The peak currents due to d i f f u s i o n of the
8
2+
bipyridinium to the electrode are predicted (based on a d i f f u s i o n

6 2 2
c o e f f i c i e n t of 7 x l 0 " cm /s (13) to be 23, 71 and 230 yA/cm at the
three scan rates. As expected, the coverage i s constant with
increasing scan rate (0.1 and 1.0 V/s). At 10 V/s the coverage
decreases, possibly because the monolayer i s not f u l l y re-assembled
a f t e r desorption at the p o s i t i v e p o t e n t i a l l i m i t (see below).
Analysis of the cathodic peak at 10 V/s assuming i r r e v e r s i b l e
reduction of an adsorbed reactant (14) y i e l d s values of 70/s f o r the
standard rate constant and 0.6 f o r the t r a n s f e r c o e f f i c i e n t .

29. FINKLEA ET AL. Bipyridiniums in Octadecylmercaptan Monolayers 435
Reduction to the neutral r a d i c a l appears as an i r r e v e r s i b l e

wave at -0.9 V. Neither anodic peak e x h i b i t s the shape
c h a r a c t e r i s t i c of s t r i p p i n g a s o l i d coating from the electrode;
hence p r e c i p i t a t i o n of the r a d i c a l cation or neutral r a d i c a l on the
electrode i s not evident (11-13). The sharp peaks at +0.46 V are
t e n t a t i v e l y assigned to desorption and adsorption of the
2
CiebpyMe ; there are no anticipated redox reactions at that
potential. +
2 4
The voltammetry of CiebpyMe ( l x l 0 ~ M) i n the presence of a
CisSH monolayer i s s t r i k i n g (Figure 3 and Table I ) . The mercaptan
monolayer displaces e l e c t r o l y t e from the e l e c t r o d e / e l e c t r o l y t e
i n t e r f a c e ; consequently the i n t e r f a c i a l capacitance and charging
current decrease dramatically. For comparison, the i n t e r f a c i a l
2
capacitance at 0.0 V i s 120, 100, and 10 yf/cm f o r clean g o l d i n +
2
the KC1 e l e c t r o l y t e , gold with the adsorbed layer of C bpyMe and 18
gold with the mercaptan monolayer. The adsorption/desorption wave

at +0.46 _jf i s no longer v i s i b l e Most notably, a monolayer
2
CiebpyMe i s absorbed o
peak of Figure 3 with th
current scales are i d e n t i c a l ) . At 0.1 V/s the coverage on the
mercaptan-coated electrode i s i d e n t i c a l to that obtained on the
clean electrode (Table I ) . I t i s l i k e l y that the bipyridinium
monolayer assembles on the e x t e r i o r of the mercaptan monolayer to
form a b i l a y e r structure (15). At 0.1 V/s the bipyridiniums
penetrate the C SH monolayer at a s u f f i c i e n t rate that the e n t i r e
18
adsorbed Ci bpyMe monolayer i s reduced. At faster scan rates

8
2+
2
transportation of charge to the remote CiebpyMe monolayer l i m i t s
the current and the surface coverage apparently decreases.
The fate of the bipyridinium r a d i c a l cation i n the mercaptan
monolayer i s not c l e a r . The second reduction wave (Figure 3)
possesses structure suggesting a p r e c i p i t a t e d phase; s i m i l a r sharp
peaks are seen during the reductive p r e c i p i t a t i o n of C i 4 b p y M e 2+
(11). Yet at 0.1 V/s the anodic peak due to the oxidation of the
r a d i c a l cation does not e x h i b i t the shape c h a r a c t e r i s t i c of
s t r i p p i n g of a s o l i d phase. At f a s t e r scan rates the anodic peak
broadens considerably and s p l i t s into two peaks; the same behavior
i s noticeable i n Figure 1. We do not have an explanation f o r t h i s
phenomenon. A recent t h e o r e t i c a l treatment of redox molecules
attached to electrode surfaces predicts that under c e r t a i n
conditions an anodic surface wave can broaden and s p l i t with
increasing scan rate i n a manner shown i n Figure 3 (16). However
the same theory predicts that the corresponding cathodic peak
normalized to constant scan rate w i l l increase with increasing scan
rate. The l a t t e r p r e d i c t i o n i s not observed i n our system.
Conclusion. Our major conclusion i s that surfactant bipyridinium

dications do not remain at a f i x e d l o c a t i o n w i t h i n a mercaptan
monolayer. In order to c o n t r o l the spacing and o r i e n t a t i o n of the
bipyridiniums i n the monolayer, i t w i l l be necessary to anchor them
w i t h i n the monolayer or to the electrode. We are currently pursuing
that goal by synthesizing a bipyridinium with a terminal mercaptan.

E 0
4.00
2.00
.000-
-2.00-
-4.00-
.700 .500 .300 -.100 .100
E 0
Figure 1. C y c l i c voltammograms of a mixed monolayer of C SH + 18
(C bpyMe)Cl .
18 2
-1.00 -.600
Figure 2 . C y c l i c voltammograms of C bpyMe i8 adsorbed from

s o l u t i o n on a clean gold electrode.
E 0
2.00
1.00
.000
-1.00
-2.004
-1.00 -.600 .200 .200 .600
E 0
Figure 3 . C y c l i c voltammograms of CiebpyMe 2

adsorbed from
s o l u t i o n on a gold electrode coated with a C I B S H monolayer.

29. FINKLEA ET AL. Bipyridiniums in Octadecylmercaptan Monolayers 437
Acknowledgments
Acknowledgement i s made to the donors of the Petroleum Research

Fund, administered by the American Chemical Society, f o r support of
t h i s research.
1. Nuzzo, R. G.; Allara, D. L. J . Am. Chem. Soc. 1983, 105,

4481.
2. Nuzzo, R. G.; Fusco, F. A . ; Allara, D. L. J . Am. Chem. Soc.
1987, 1 0 9 , 2358.
3. Porter, M. D.; Bright, T. B . ; Allara, D.; Chidsey, C. E. D.
J. Am. Chem. Soc. 1987, 109, 3559.
4. Sabitini, E . ; Rubinstein, I . ; Maoz, R.; Sagiv, J .
5. Finklea, H. O.; Avery S.; Lynch M . ; Furtsch T Langmuir
1987, 3, 409.
6. Lane, R. F . ; Hubbard
7. Bravo, B. G.; Mebrahtu, T.; Soriaga, M . ; Zapien, D. C.;
Hubbard, A. T.; Stickney, J . L. Langmuir 1987, 3, 595.
8. Li, T. T.-T.; L i u , H. Y . ; Weaver, M. J . Am. Chem. Soc. 1984,
106, 1233.
9. Li, T. T.-T.; Weaver, M. J . Am. Chem. Soc. 1984, 106, 6107.
10. Daifuku, H . ; Aoki, K . ; Tokuda, K . ; Matsuda, H. J .
11. Enea, O . Electrochim. Acta 1986,31,789.
12. Crouigneau, P.; Enea, O.; Beden, B. J . Electroanal. Chem.
1987, 218, 307.
13. Bruinink, J.; van Zanten, P. J . Electrochem. Soc. 1977, 124,
1232.
14. Bard, A. J.; Faulkner, L. R. Electrochemical Methods:
Fundamentals and Applications, J. Wiley & Sons: New York,
1980: p. 525.
15. M i l l e r , C. J.; Majda, M. J . Am. Chem. Soc. 1986, 108, 3118.
16. Matsuda, H . ; Aoki, K . ; Tokuda, K. J . Electroanal. Chem.
1987, 217, 1 and 15.
RECEIVED May 1 7 , 1988

Chapter 30
Ideal Polarizable Semiconductor—Solution

Interfaces
1 1 2
Carl A. Koval , John B. Olson , and Bruce A. Parkinson
1
Department of Chemistry and Biochemistry, University of Colorado,
Boulder, CO 80309-0215
2
Central Research and Development Department, Experimental Station
E328/216B, E . I. du Pon
Ideal polarizable interfaces are critical for the interpretation of

electrochemical kinetic data. Ideality has been approached for certain metal
electrode-solution interfaces, such as mercury-water, allowing for the
collection of data that can be subjected to rigorous theoretical analysis.
Herein, criteria are developed for ideal polarizable semiconductor
electrode-solution interfaces. A variety of experimental studies involving
metal dichalcogenide-solution interfaces are discussed within the context of
these criteria. These interfaces approach ideality in most respects and are
well suited for fundamental studies involving electron transfer to solution
species or adsorbed dyes.
Interfacial electron transfer is the critical process occurring in all electrochemical cells in
which molecular species are oxidized or reduced. While transfer of an electron
between an electrode and a solvated molecule or ion is conceptually a simple reaction,
rates of heterogeneous electron transfer processes depend on a multitude of factors
and can vary over many orders of magnitude. Since control of interfacial electron
transfer rates is usually essential for successful operation of electrochemical devices,
understanding the kinetics of these reactions has been and remains a challenging and
technologically important goal.
Prior to the 1970's, electrochemical kinetic studies were largely directed
towards faradaic reactions occurring at metal electrodes. While certain questions
remain unanswered, a combination of theoretical and experimental studies has produced
a relatively mature picture of electron transfer at the metal-solution interface (1-4).
Recent interest in photoelectrochemical processes has extended the interest in
electrochemical kinetics to semiconductor electrodes (5 15). Despite the pioneering
work of Gerischer (11-14) and Memming (15), many aspects of electron transfer
kinetics at the semiconductor-solution interface remain controversial or unexplained.
The authors propose that a major difficulty in interpreting kinetic current flow at
the semiconductor-solution interface lies in the inability of experimentalists to prepare
interfaces with ideal and measurable properties. In support of this hypothesis, the
importance of ideal interfacial properties to metal electrode kinetic studies is briefly
reviewed and a set of criteria for ideality of semiconductor-solution interfaces is
developed. Finally, the use of semiconducting metal dichalcogenide electrodes as ideal
interfaces for subsequent kinetic studies is explored.
0097-6156/88/0378-O438$06.00/0

30. K O V A L E T A L . Ideal Polarizable Semiconductor-Solution Interfaces 439
Kinetics of Molecular Processes at Ideal Polarizable Metal-Solution Interfaces
Describing the current in electrochemical cells due to the faradaic processes is the
greatest concern of electrochemical kinetics. There are three general rate processes
controlling this current: mass transfer, electron transfer, and homogeneous chemical
reactions accompanying electron transfer Since mass transfer is often controlled
by hydrodynamics and since diffusion coefficients for different species in solution do
not vary greatly, mass transfer is not usually considered to be a molecular process. In
kinetic studies, the effects of mass transfer must either be controlled or accounted for
mathematically. The processes of electron transfer and associated chemical reactions
are molecular in nature and the major goal of the kineticist is to understand why
different molecules react at widely different rates.
In general, understanding the rates of electrode reactions that involve more
than one electron per molecule is extremely difficult. These processes are usually the
combination of several single electron transfers that proceed through unstable
i n t e r m e d i a t e s ( l £ ) . Furthermore, multi-electron electrode processes can be
accompanied by chemical reactions which can also be rate limiting. Single electron,
outer sphere reactions for many molecules, especially complexed metal ions, are less
complicated because the bondin
Following the theoretical treatmen
rates of single electron transfers are thought to be well understood (17). However,
widespread acceptance of the Marcus model required the acquisition of a considerable
body of experimental data, involving both homogeneous and heterogeneous
(electrochemical) systems (1-4.18.19).
Even in the absence of mass transfer and chemical reactions, relating the
current flowing across an interface to a molecular factor is extremely complicated. In
order for net current to flow, the electrode potential must be different from the
solution potential. The dependence of the current on this overpotential is reasonable
well understood ( ! £ ) • The difficulty lies in describing the spatial distribution of this
potential drop across the interface. At the metal-solution interface, the spatial
distribution of charges that constitutes the potential drop can extend from a few to
several hundred A into the solution. Thus, ionic reactants near the surface develop a
concentration ya. distance profile which can be dramatically different from the bulk
concentration. A description of the spatial distribution of the potential drop combined
with the energetic distribution of electrode and molecular orbitals as a function of
applied electrode potential can be called the interfacial energetics (IE). Since
rates of electron transfer reactions depend exponentially on distance, driving force and
activation energy, knowledge of the interfacial energetics is essential in order to apply
theoretical treatments to experimental kinetic data.
Fortunately, a model describing the metal-solution interface has been
developed together with a methodology for experimentally measuring the necessary
parameters (1-4.16). The basic requirement for application of this model is interfaces
that resist faradaic reactions over a wide range of applied potentials in the absence of
the electroactive species. Such an electrode is referred to as an ideal polarizable
electrode (IPE) (1_£). At an IPE, the interfacial capacitance as a function of applied
potential (which is controlled by the interaction of the metal with the solvent and
electrolyte) can be used to calculate the interfacial energetics. In subsequent
experiments, small amounts of an electroactive species can be added to the solution
and the resulting faradaic current can be analyzed. It should be noted that this model is
most applicable in situations that are dominated by electrostatics. Chemical interactions
between solution species and the electrode which result in specific adsorption greatly
complicate the determination of the interfacial energetics and the kinetic analysis.
Metal-Solution Interfaces that Approach Ideality
By far, most of electrochemical kinetic data that can be subjected to detailed analysis
has been obtained at the mercury-aqueous electrolyte interface or at mercury
electrodes in other solvents (1-4.16). The main advantages of mercury over other

metals are that mercury is a liquid, it is relatively chemically inert, and that a new
interface can be prepared every few seconds. The latter property helps to minimize
complications due to contamination of the surface by organic molecules and other
impurities present in the solvent. Mercury electrodes are very useful for studying
reduction reactions because reduction of protons in protic solvents is very slow (it has
a high overpotential for hydrogen reduction). However, mercury electrodes are not
useful for studying oxidative molecular reactions because mercury itself is easily
oxidized.
Solid metal electrodes such as platinum, gold and carbon are less easily
oxidized than mercury and many faradaic processes can be observed. Unfortunately,
accurate determination of the interfacial energetics at solid metal electrodes interfaces
is rarely possible. Unlike mercury which has a smooth surface, the surfaces of most
polycrystalline solid metal electrodes are microscopically rough with crystal faces of
various orientations exposed. Due to the microscopic roughness, the surface area is
not well defined and molecules reacting at these surfaces can experience a variety of
sites with differing energies. With the exception of gold, metal surfaces react
spontaneously with oxygen to form an oxide layer which can have dramatic and
unpredictable effects on kinetic processes. Preparation of ideal solid metal electrode
surfaces by typical physical and/or chemical treatments cannot be accomplished rapidly
or reproducibly. Within the pas
ultra high vacuum and ultrapurification techniques that allow them to investigate
electrochemical reactions at clean metal electrodes with specific crystallographic
orientations (20-22). While these procedures are elaborate and not generally available,
they do afford the possibility of extending detailed kinetic studies to solid metals.
Criteria for the ideal Polarizable Semiconductor-Solution interface
Based on the discussion above, it seems evident that a detailed understanding of

kinetic processes occurring at semiconductor electrodes requires the determination of
the interfacial energetics. Electrostatic models are available that allow calculation of
the spatial distributions of potential and charged species from interfacial capacitance
y&. applied potential data (23.24). Like metal electrodes, these models can only be
applied at ideal polarizable semiconductor-solution interfaces ( £ 5 ) . In accordance with
the behavior of the mercury-solution interface, a set of criteria for ideal interfaces is:
1. The electrode surface is clean or can be readily renewed within the timescale of
kinetic measurements.
2. The electrode surface is uniform with respect to a known crystal lattice orientation
and the surface area can be accurately measured.
3. The electrode is chemically unreactive with solvents containing electrolytes and
redox couples over a wide range of applied potential.
4. The interfacial capacitance can be determined experimentally as a function of applied
potential.
The potential distribution at the semiconductor-solution interface is quite
different than at the metal-solution interface. Metals do not support internal electric
fields. Excess charge on a metal electrode is localized at the surface and the interfacial
potential drop occurs in the solution. These considerations indicate that energies of
electronic states associated with the metal are continuously variable with respect to
states associated with redox couples in the solution. For semiconductors, excess
charge is contained in the space charge region and determines the concentration of
electrons and holes at the surface. For ideal semiconductors, the energies of
electronic states associated with redox processes are determined by the position of
the conduction and valence band edges. Several processes such as charging of
surface states and adsorption of ions cause the band edges to shift which produces
non-ideal behavior. Thus, for an ideal polarizable semiconductor-solution interface:
5. The band edge postions should be stable over a wide range of applied potential.
6. It should be possible to prepare the material doped both p- and n- type over a wide
range of doping densities.
7. Materials with different band gaps and/or band positions should be available.

Criteria 6 and 7 are important because in order to vary the kinetically relevant
parameters such as the spatial distribution of charge carriers and the thermodynamic
driving force, semiconductor electrodes with different majority carrier types, doping
densities and band gaps must be used.
Metal Dichalcogenides (MDC)
A class of semiconducting solids that has received considerable attention with respect
to photoelectrochemistry is the layered metal dichalcogenides (MDC) (26-33) which
have the formula AB2 where A is a transition metal, formally in the +4 oxidation state,
and B is a chalcogenide ion, S " , S e " or T e " . Many of these materials display a layer
2 2 2
type structure in which the metal is sandwiched between two layers of the chalcogenide
and occupies either an octahedral or trigonal prismatic hole (Figure 1). The sandwiches
themselves are assembled into stacks which are held together by weak van der Waals
forces. Single crystals of many MDC's which have surface areas as large as one c m 2
can be prepared by chemical vapor transport or by Bridgeman techniques.

Semiconductor electrodes often suffer from the same properties that result in
the non-ideality discussed previously for solid metals. MDC crystals have properties
that are especially attractive fo
interfaces. Not surprisingly, the physical properties of these crystals can be highly
anisotropic with respect to the directions parallel and perpendicular to the van der
Waals surfaces. The van der Waals surfaces can be nearly molecularly smooth and fresh
surfaces can be prepared by cleaving the crystal with an adhesive tape. When the
edges of the crystal are masked with epoxy, only the van der Waals surface is exposed
to the solution. Thus, redox couples involved in electron transfer reactions experience
a single set of interfacial energetics. Furthermore, the area of this surface can be
measured to a high degree of accuracy using photographic procedures. An alternative
cell design where the electrochemistry is done on a small drop of electrolyte positioned
on a selected portion of the van der Waals surface allows for both cleavage of the
sample and elimination of dark currents and chemical reactions associated with the
unsaturated chemical bonds at edges and steps (34).
While freshly cleaved surfaces clearly contain some steps and other defects,
the surfaces are remarkably stable to corrosion. Dramatic evidence of the stability of
MoSe2 surfaces was provided by Stickney et al. who obtained L E E D and Auger
spectra of surfaces that had been exposed to the atmosphere and a variety of
oxidizing solutions (25). Except for the presence of a ubiquitous carbon which was
attributed to the epoxy resin or cleaving tape, no evidence for surface reactions was
found. Long term stability tests of a photoelectrochemical cell made with a WSe2
electrode, where over 400,000 coulombs/cm were passed through the cell with no
2
detectable photocorrosion, also attest to the durability of these surfaces (36).

Based on results discussed above and others that have appeared in the
literature, it appears that interfaces derived from MDC's are likely to satisfy the first
three criteria for ideality (at least for certain solvents and redox couples). The
remaining criteria must be examined utilizing data obtained from specific systems.
Tungsten Diselenide-Acetonitrile Interfaces
In order to obtain fundamental kinetic data on outer-sphere electron transfer

processes at the semiconductor-nonaqueous solution interface, Olson investigated the
W S e 2 - C H 3 C N interface (27). Chemical vapor transport was used to prepare WSe2
single crystals. By varying the transporting agent (CI2 or I2), amount of dopant (Re or
Nb) and the transport conditions, n-type and p-type crystals of good to excellent
quality were prepared (25). Crystals from each growth batch were mounted as
electrodes and examined using impedance and photoelectrochemical techniques in
acetonitrile solutions containing 0.5 M supporting electrolyte. The impedance data was
analyzed in the form of Mott-Schottky plots from which the doping densities and
flatband potentials were derived. Doping densities were proportional to the amount of

Chalcogenide
• Metal
Figure 1. Schematic drawing showing the structure of the trigonal prismatic variety
of the metal dichalcogenide structure. Note the structure is not drawn to scale
but to emphasize the layered structure of the materials.

dopant used in the synthesis and ranged from 4 x 1 0 to 3 x 1 0

1 5
c m for the n-
1 9 - 3
type crystals and from 3 x 1 0 to 2 x 1 0

1 6
c m for the p-type crystals (25). Within
1 9 - 3
a given growth batch, the deviations in the doping densities for different crystals was
quite small compared to the range for the different batches, especially for the lower
doped crystals. These two observations taken together with the fact that crystals
were cleaved several times prior to mounting support the conclusion that the dopant
was homogeneously distributed in the crystals.
Flat band potentials and doping densities obtained from Mott-Schottky plots
can be used to calculate the position of the conduction band edge (CBE) for n-type
electrodes and the valence band edge (VBE) for p-type crystals (25). The average
position of the C B E for nine batches of n-type electrodes was -730 ± 90 mV vs E ' 0
for ferricenium/ferrocene (4Q_). The average position of the V B E for seven batches of
p-type electrodes was +670 ± 120 mV. Standard deviations of the band edges for
electrodes from a given growth batch were less than 40 mV. The difference in the
average band edges for the p- and n-type electrodes is 1.4 V which is close to the
direct bandgap of WSe2, 1.35 eV, although the indirect band gap is slightly lower (1.20
eV). These data support the contention that the interfacial energetics for the WSe2-
CH3CN interface is not a function of majority carrier type or concentration, i.e.
controlled by the interaction o
Clearly, the WSe2-CH3C interface satisfies the 6th criterium for ideality. It
would seem that similar synthetic efforts would produce ranges in doping densities for
other MDC's as well. For WSe2-CH3CN, the range of doping densities implies that
for 0.5 V of band bending the width of the space charge layer would range from 7.5 to
240 nm. The impedance data obtained in solutions containing only electrolyte indicate
that criteria 3,4 and 5 are met for this interface in the absence of redox couples.
Electrochemistry of Ferrocenes at the WSe2-CH3CN interface
Although different electrodes within a growth batch yielded similar interfacial

energetics, the quality of these electrodes varies greatly with respect to
photoconversion efficiency. Reduced photoconversion efficiencies have been
attributed to high densities of edge sites and lattice defects which act as recombination
centers (26.28). Parkinson and co-workers used a scanning laser spot system to show
that photocurrents are greatly diminished on regions of MDC surfaces which are
macroscopically flawed and presumably contain a high density of defect sites (41).
Reasoning that surfaces containing many defects would be least likely to display ideal
behavior, Olson measured photocurrent vs. potential curves in order to calculate fill
factors for the WSe2 electrodes (2Z). From approximately 100 candidates, the
electrode from each batch with the highest fill factor and the most ideal impedence
behavior was selected as the "best" electrode. The fill factors for the best electrodes
ranged from 0.37 to 0.65 (35).
The selected electrodes (five n-type and four p-type) were used to obtain
kinetic current vs. potential data in solutions containing poised ferrocene redox couples
(50% oxidized, 50% reduced) (37.39). The electrode potential was varied over a
range of at least 0.5 V to over 1.0 V. Three couples were examined: ferrocene (FER)
itself, decamethylferrocene (DFER) and acetylferrocene (AFER). The reduction
potentials of DFER and AFER with respect to FER (which is assigned a value of 0.0)
are -0.50 and +0.25 V, respectively. The reduction potentials for all three couples are
located between the C B E and V B E of the WSe2-CH3CN interface.
Three concentrations of each redox couple that ranged over two orders of
magnitude were examined as well as a solution containing only electrolyte. The details
of these comprehensive experiments will be published elsewhere (22); however,
several pertinent features are described here. The kinetic currents were measured at
constant potential. In order to eliminate mass transfer limitations to the current, a jet
electrode configuration was utilized ( 4 £ ) . The capacitance of the space charge layer
(C c) was measured at the same potentials simultaneously with the kinetic currents.
S

Repeated visual examination and impedence measurements indicated no degradation of

the electrode over the course of the experiments (3 weeks). During this time, the
selected electrodes were stored in the inert-atmosphere glove box in which the
electrochemical experiments were performed. No electrode pretreatment procedures
were used and the crystals were not recleaved.
The C c vs. potential data was used to calculate band edge positions for each
S
of the nine selected electrodes in each of the ten solutions. These values are
presented in Figure 2. Except for the electrodes with doping densities greater than
10 c m " (which are degenerately doped), the band edge positions were remarkably
1 9 3
stable. These results demonstrate that for outer-sphere redox couples the WSe2-
CH3CN interface satisfies criteria 3 through 5 and therefore approaches ideality in
every respect.
Redox Processes at Non-illuminated MDC-Aqueous Interfaces
An example of the type of kinetic data which can be obtained with a MDC electrode
with a nearly perfect surface can be seen in Figure 3. The currents were all obtained in
1 mM solutions of the oxidized form of the respective redox couple in a 1M
solution which had been exhaustivel
was a n-WSe2 electrode with an area of 0.12 c m , a doping level of about 3 x 1 0
c m ' , a flatband potential of about -0.3 V vs. S C E and a nearly defect free surface as
3
determined from microscopic examination and from the very small (<1 nA) dark
currents in the blocking region of the diode curve (more positive than -0.2 V). Like
mercury, the material has a very high hydrogen overpotential allowing for the study of
reduction reactions in strongly acidic electrolytes. The Tafel lines shown in Figure 3
were remarkably reproducible upon repeated scanning in either anodic or cathodic
directions.
The current-voltage behavior of the various redox couples can be grouped into
four classes. Class one are the very positive redox potential species (Ce + and 4
lrCl62~) which can inject holes directly into the valence band over a wide potential range
but show small (> 500 mV) non-linear Tafel slopes at very negative potentials even
though the driving force for the C e reduction exceeds 2.0 V at these potentials.
4 +
(These redox couples were actually investigated last and some degradation of the
electrode could be observed in the C e solutions undoubtably due to some oxidation
4 +
of the surface by this highly oxidizing couple). It is interesting that the hole injection
current for the two couples is nearly equal despite the large difference in their redox
potentials (0.55 V, Figure 4) suggesting that the hole injection current is not dependent
on the driving force of the reduction reaction.
Class two redox couples have potentials located in the bandgap region ( F e , 3 +
Fe(CN)6 ", Co(phen)3 , phen = o-phenanthroline) and show parallel tafel lines with
3 3+
very low slopes (450 mV/decade) with the more positive redox species showing earlier
onsets of reduction. The currents appear to be due to a tunneling process where holes
can be injected into the valence band of the semiconductor as the bulk valence band
potential passes the redox level of the couple during formation of an accumulation
layer. The tunneling process results in very low currents due to the low number of
surface defects and the large space charge layer width through which the electron must
tunnel in the moderately low doped material.
The third class of redox species are couples located near the conduction band
of WSe2- The only outer-sphere example found, which is suitable for use in aqueous
electrolytes, is Ru(NH3)e3+. Its reduction is characterized by an immediate onset
upon accumulation in the semiconductor and a tafel slope of 130 mV/decade. The
reduction mechanism appears to be direct reduction of the Ru(NH3)63+ by electrons
from the accumulation layer. The only member of the forth class of redox species is
triiodide ion. It is characterized by adsorption onto the semiconductor surface as was
demonstrated by the first application of chronocoulometry to a semiconductor
electrode (another demonstration of the reproducibility and low background currents on

30. KOVALETAL. Ideal Polarizable Semiconductor-Solution Interfaces 445
20
^ 19-
1* LDFER
18
LFER
MFER
HFER
LAFER
MAFER
17" HAFER
-1" BLANK
16
15
•1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
BAND E D G E POTENTIAL (V)

Figure 2. Band edge positions obtained over a period of three weeks for p-and n-
type WSe2 -CH3CN interfaces containing metallocene redox couples (ferrocene,
FER; decamethylferrocene, DFER; and acetylferrocene, AFER) each at three
concentrations (preceding letter refers to high,H; medium.M; and low, L). Two
different electrodes were used to obtain the data for n-WSe2 with doping
densities between 1 0 -10
1 6
cm" .
1 7 3

E (SCE)
Figure 3. Tafel Plots of aqueous redox couples at n-WSe2: open squares -
Co(phen)3 , open triangles - Fe(CN)6 ", closed triangles - F e
3+ 3 3 +
,
closed circles - Ru(NH3)6 ,
3+
closed diamonds - lrCl6 ', open circles - C e
2 4 +
,
closed squares -13".

n-WSe 2
ESCE EABS
--4.0
CB
E F B - —
^-Ru(NH )r/Ru(NH )r
3 3
0-
*-Co(phen)f/Co(phen)f —5.0
Fe(CN)*7Fe(CN)J-
«—Fe* /Fe«
3
•*—ir ci£ /ircig

VB 1.0-
-6.0
Ce«VCe*
Figure 4. Band diagram showing the relative positions of the conduction and
valence bands in WSe2 with respect to the reduction potentials in aqueous
solutions for the redox couples shown in Figure 3.

these surfaces) (2Z). Triiodide reduction is characterized by an early onset of current

due to the positive shift in the band edge as a result of the negative charge on the
surface due to adsorbed triiodide. The Tafel slope is higher (85 mv) than for the other
systems perhaps due to the inner sphere pathway for reduction of the adsorbed
species by electrons in the accumulation layer. Although a quantitative interpretation of
the kinetic currents for reduction of various aqueous redox couples on a WSe2
electrode has not yet been formulated, this section has demonstrated that due to the
low background currents on the nearly perfect surface-state free surfaces, qualitative
information about the different interfacial charge transfer mechanisms can be obtained
even when the kinetic currents are below 1îA/cm . 2
Adsorption of Dyes on Metal Dichalcogenides
An interesting approach to measuring rates of electron transfer reactions at electrodes

is through the study of surface bound molecules (43-45). Molecules can be attached to
electrode surfaces by irreversible adsorption or the formation of chemical bonds (46).
Electron transfer kinetics to and from surface bound species is simplified because
there is no mass transport and because the electron transfer distance is controlled to
some degree.
Photoinduced electro
molecules and semiconductor electrodes are important for practical as well as
fundamental reasons. Absorption of light by the dye can improve the spectral
response of the semiconductor and these systems are models for the photographic
process (47-51). MDC surfaces are excellent substrates for studying electron
injection into the conduction band of the semiconductor.
Understanding of dye and dye aggregate sensitization efficiency, the excited
states involved in injection and the energetic thresholds for electron injection has
mostly resulted from photoelectrochemical and spectroscopic studies of oxide
semiconductors because of their large bandgaps and photocorrosion resistant surfaces.
The quantum yield, defined as electrons per photon absorbed by the dye on oxide
semiconductor single crystal surfaces was consistently limited to less than 0.5%. The
low quantum yield has been attributed to recombination of the photogenerated carriers
via back reaction of the injected electron with the dye radical, perhaps through surface
states located in the bandgap. Surface states are virtually unavoidable on materials
which have a three dimensional structure due to the need to terminate the bonding at
every low index crystal face.
It has recently been shown that van der Waals (001) surfaces of two
dimensional semiconductors such as WS2, MoSe2 and WSe2 are superior substrates
for studying sensitization (52). High quantum yields (>4% per incident photon or >80%
per absorbed photon were measured for the sensitization of the WSe2 surface by an
infrared absorbing pentathiacyanine dye. The high quantum yields were attributed to
the absence of interface states due to the lack of bond termination, characteristic of
van der Waals surfaces.
Metal Dichalcogenides with Band Gaps Greater than 2 eV
Although semiconductors with band gaps ranging from 1 to 1.6 eV are most suited to
solar energy conversion, materials with wider band gaps are useful for fundamental
studies because situations involving larger differences between band edge positions
and reduction potentials for redox species can be examined.
Recently, MDC's and other semiconductors with a layered structure having
large bandgaps have been used in electrochemical studies. The photoanode properties
of n-SnS2 (indirect transition at 2.2 eV) in acidic and basic solutions has been reported
(53) and this material was also shown to have high quantum yields for electron injection
from adsorbed dyes (54) GaS has a band gap of approximately 2.4 eV and has a
double sandwich structure with two metal layers sandwiched between chalcogenide
layers (S-Ga-Ga-S repeat unit along the c axis). Preliminary dye-sensitization studies
indicate that G a S (or Ga2S2) has an extremely negative conduction band edge (-1.3

30. KOVALETAL. Ideal Polarizable Semiconductor-Solution Interfaces 449
volts vs S C E ) . CCIPS3 is an example of another class of layered semiconductors. It is

colorless with a bandgap of about 3.1 eV. Synthetic procedures for controlling the
type and level of doping for these wide bandgap materials have not been developed
and further electrochemical characterization is necessary to determine band edge
positions and the surface stability of these materials. Nevertheless, they represent a
large class (55) of potentially ideal interfaces for use in electrochemical kinetic studies.
Acknowledgment
Research performed by CAK and J B O was supported by the Department of Energy
(Division of Chemical Sciences) Contract No. DE-FG02-84ER13247. The authors
thank Arthur Nozik, Mark Peterson and John Turner (Solar Energy Research Institute,
Golden, CO) for the generous use of their equipment and for valuable discussions.
Literature Cited
1. Albery, W.J. Electrode Kinetics, Clarendon Press, Oxford, 1975.
2. Bockris, J. O'M.; Reddy, A.K.N. Modern Electrochemistry, Plenum Press, New
York, 1970.
3. Vetter, K.J. Electrochemica
4. Delahay, P. Double-Layer and Electrode Kinetics, Interscience Publishers, New
York, 1965.
5. Bard, A.J.; J . Phys. Chem. 1982, 86, 172.
6. Wrighton, M.S.; Acc. Chem. Res. 1979, 9, 303.
7. Rajeshwar, K.; Singh, P.; Dubow, J . ; Electrochim. Act. 1978, 23, 1117.
8. Nozik, A.J.; Ann. Rev. Phys. Chem. 1978, 29, 189.
9. Wilson, R.H.; C R C Crit. Rev. Sol. State Mat. Sci. 1980, 10, 1.
10. S. R. Morrison, Electrochemistry at Semiconductor and Oxidized Metal
Electrodes, Plenum Press, N.Y., 1980.
11. Gerischer, H. Z. Physik. Chem. 1960, 26, 223.
12. Gerischer, H. Z. Physik. Chem. 1961, 27, 48 1961.
13. Gerischer, H. Adv. Electrochem. Electrochem. Engr. 1961, 1, 139;
14. Gerischer, H. Top. Appl. Phys. 1979, 31, 115.
15. Memming, R. Electroanal. Chem. 1979, 11, 1.
16. Bard, A.J.; Faulkner, L.R. Electrochemical Methods, Wiley, New York, 1980,
Chapters. 1, 3,.11, 12.
17. Marcus, R.A.; J . Chem. Phys. 1956, 24, 966; Disc. Far. Soc. 1960, 29, 21; J.
Chem. Phys. 1965, 43, 2654.
18. Marcus, R.A.; Sutin, N. Biochim. Biophys. Act. 1985, 811, 265.
19. J . Phys. Chem. (R.A. Marcus Commemorative Issue), 1986, 90(16), 3453-3862.
20. Baltruschat, H.; Martinez, M.; Lewis, S.K.; Frank, L .; Dian, S.; Stern, D.A.; Datta,
A.; Hubbard, A.T. J . Electroanal. Chem, (1987) 217, 111.
21. Stern, D.A.; Baltruschat, H.; Martinez, M.; Stickney, J.L.; Song, D.; Lewis, S.K.;
Frank, D.G.; Hubbard, A.T. ibid. (1987) 217, 101.
22. Schardt, B.C.; Stickney, J.L.; Stern, D.A.; Wieckowski, A.; Zapien, D.C.;
Hubbard, A.T. Langmuir (1987) 3, 239.
23. Mott, N.F. Proc. R. Soc. London 1939, A171. 27.
24. Schottky, W. Z. Phys.1942, 118, 539.
25. Dutoit, E.C.; Meirhaeghe, R.L.; Cardon, F.; Gomes, W.P.; Ber. Bunsenges.
Physik. Chem.1975, 79, 1206.
26. Tributsch, H. Struct. & Bonding 1982, 49, 127.
27. Turner, J.A. and Parkinson, B.A. J . Electroanal. Chem. 1983, 150, 611.
28. Kline, G . ; Kam, K.; Canfield, D.; Parkinson, B.A. Sol. Ener. Mat. 1981, 4, 301.
29. Parkinson, B.A.; Furtak, T . E . ; Canfield, D.; Kam, K.K.; Kline, G . , Faraday Disc.
1980, 70, 233.

30. White, H.S.; Fan, F.F.; and Bard, A.J.; J . Electrochem. Soc. 1981, 128, 1045;
ibid. 1980, 127, 518; J . Am. Chem. Soc. 1980, 102, 5142.
31. Nagasubramanian, G.; Bard, A . J . J. Electrochem. S o c ., 128, 1055 (1981).
32. Wrighton, M.S.; Schneemeyer, L.F. J . Am. Chem. Soc. 1979, 101. 6496; ibid.
1980, 102, 6946.
33. Lewerenz, H.J.; Heller, A.; DiSalvo, S . J . J. Am. Chem Soc. 1980, 102, 1877.
34. Parkinson, B.A., unpublished results.
35. Stickney, J.L.; Rosasco, S.D.; Schardt, B.C.; Solomun, T.; Hubbard, A.T.;
Parkinson, B.A. Surface Science 1984, 136, 15.
36. Kline, G . ; Kam, K.; Ziegler, R.; Parkinson, B.A. Solar Energy Materials 1982, 6,
337.
37. Olson, J.B. Ph.D. Thesis, University of Colorado, 1987.
38. Koval, C.A.; Olson, J.B. J . Electroanal. Chem. 1987, 234, 133 .
39. Koval, C.A.; Olson, J.B., submitted for publication.
40. The difference in the band edge positions for n - W S e 2 - C H C N discussed in this
3
section and the value stated later for n - W S e - H2O is due to problems
2
associated with relating reference electrode potentials in different solvents. See

Gagne', R.R.; Koval, C.A.
41. Furtak, T.; Canfield, D.;
42. Olson, J.B.; Koval, C.A. Anal. Chem., 1988, 60, 88.
43. Li, T.-T.; Weaver, M.J. J . Am. Chem. Soc. 1984, 106, 6107.
44. Li, T.-T.; Liu, Y.Y.; Weaver, M.J. J. Am. Chem. Soc. 1984, 106, 1233.
45. Guyer, K.L.; Weaver, M.J. Inorg. Chem. 1984, 23, 1664.
46. Murray, R.W. Acc. Chem. Res. 1980, 13, 135.
47. The Theory of the Photographic Process. 4th Edition, T. H. James, Ed.; Macmillan,
New York, 1977.
48. Berriman, R.W.; Gilman, P.B., Jr. Photographic Science and Engineering,
1973, 17, 235.
49. Gerischer, H.; Tributsch, H. Ber. Bunsenges. Phys. Chem., 1968, 72, 437.
50. Memming, R.; Tributsch, H. J . Phys. Chem.,1971. 75, 562.
51. Memming, R. Photochemistry and Photobiology, 1972, 16, 325.
52. Spitler, M.; Parkinson, B.A. Langmuir, 1986, 2, 549.
53. Katty, A.; Fotouhi, B.; Gorochov, O. J . Electrochem. Soc. 1984, 131, 2806.
54. Parkinson B. A. Proceedings of the Electrochemical Society, Honolulu, in press
55. Physics and Chemistry of Layered Materials, Vol. 1-6 , D. Reidel, Dordrecht,
Holland.

Chapter 31
Electrosynthesis and Electrochemistry

of Metalloporphyrins Containing
a Metal—Carbon σ-Bond
Reactions of Rhodium, Cobalt, Germanium,
and Silicon Complexes
1
K. M . Kadish, Q. Y. Xu, and J . E. Anderson
The electrosynthesi
t a i n a metal-carbon σ-bond is reviewed i n t h i s
paper. The electron transfer mechanisms of σ-bonded
rhodium, cobalt, germanium, and silicon porphyrin
complexes were also determined on the basis of
voltammetric measurements and c o n t r o l l e d - p o t e n t i a l
electrooxidation/reduction. The four described
electrochemical systems demonstrate the v e r s a t i l i t y
and s e l e c t i v i t y of electrochemical methods f o r the
synthesis and c h a r a c t e r i z a t i o n of metal-carbon σ-
bonded metalloporphyrins. The reactions between
rhodium and cobalt metalloporphyrins and the com
monly used CH2Cl2 is also discussed.
Metalloporphyrins containing a metal-carbon σ-bond are

currently l i m i t e d to complexes with eight d i f f e r e n t t r a n s i t i o n
metals ( T i , N i , Fe, Ru, Co, Rh, I r and Zn) and seven d i f f e r e n t
non-transition metals ( A l , Ga, I n , T l , S i , Ge, and Sn). These
compounds have been the subject of several recent reviews(l-3)
which have discussed t h e i r synthesis and physicochemical proper
ties.
The synthesis of metalloporphyrins which contain a metal-
carbon σ-bond can be accomplished by a number of d i f f e r e n t
methods(_1^2). One common synthetic method involves reaction of a
Grignard reagent or a l k y l ( a r y l ) l i t h i u m with (P)MX or
(P)M(X) where Ρ i s the dianion of a porphyrin macrocycle and X
2
i s a halide or pseudohalide. Another common synthetic technique

involves reaction of a chemically or electrochemically generated
low valent metalloporphyrin with an a l k y l or a r y l h a l i d e . This
l a t t e r technique i s s i m i l a r to methods described i n t h i s paper
for electrosynthesis of cobalt and rhodium σ-bonded complexes.
However, the p r e v a i l i n g mechanisms and the chemical reactions
1
Current address: Department of Chemistry, Boston College, Chestnut Hill, M A 02167
0097-6156/88/0378-0451$06.00/0
β

following electrogeneration may d i f f e r due to the difference i n

reaction conditions for generation of the reactive species.
Two aspects of porphyrin electrosynthesis w i l l be discussed
i n t h i s paper. The f i r s t i s the use of c o n t r o l l e d p o t e n t i a l
electroreduction to produce metal-carbon σ-bonded porphyrins of
rhodium and cobalt. This e l e c t r o s y n t h e t i c method i s more selec
t i v e than conventional chemical synthetic methods for rhodium and
cobalt metal-carbon complexes and, when coupled with c y c l i c
voltammetry, can be used to determine the various reaction path
ways involved i n the synthesis. The e l e c t r o s y n t h e t i c method can
also lead to a simultaneous or stepwise formation of d i f f e r e n t
products and several examples o f t h i s w i l l be presented.
The second type of porphyrin electrosynthesis discussed i n
t h i s paper i s c o n t r o l l e d p o t e n t i a l electrooxidation of σ-bonded
b i s - a l k y l or b i s - a r y l porphyrins of Ge(IV) and S i ( I V ) . This
electrooxidation r e s u l t s i n formation of σ-bonded mono-alkyl or
mono-aryl complexes which can be i s o l a t e d and characterized i n
s i t u . Again, c y c l i c voltammetr
and w i l l lead to an understandin
ways involved i n the electrosynthesis.
Dozens of electrochemical and spectroelectrochemical papers
on t r a n s i t i o n metal and main group metal-carbon σ-bonded metallo
porphyrins were published between 1984 and 1987 and a summary of
these r e s u l t s are well covered i n three recent reviews(l-3).
Therefore, a characterization of chemically synthesized metal-
carbon porphyrins w i l l not be discussed i n t h i s paper.
Rhodium Porphyrins. Chemical syntheses of [(P)Rh] and (P)Rh(R) 2
complexes are w e l l known(A-ll). Electrochemical techniques have

also been used to synthesize dimeric metal-metal bonded
L(TPP)Rh] as well as monomeric metal-carbon σ-bonded (TPP)Rh(R)
2
and (OEP)Rh(RX12-16). The e l e c t r o s y n t h e t i c and chemical synthe

t i c methods are both based on formation of a highly reactive
monomeric rhodium(II) species, (P)Rh. This chemically or
electrochemically generated monomer r a p i d l y dimerizes i n the
absence of another reagent as shown i n Equation 1.
(P)Rh * 1/2 [(P)Rh] 2 (1)
However i n the presence of hydrogen gas, (P)Rh(H) can be formed

as shown i n Equation 2.
(P)Rh + 1/2 H 2 * (P)Rh(H) (2)
Reactions 1 and 2 involve an equilibrium which i s s h i f t e d to

the r i g h t . The methods generally u t i l i z e d for chemical genera
t i o n of (P)Rh i n i t i a l l y involve a dimeric Rh(II) species or the
Rh(III) hydride, and r e l a t i v e l y high temperatures and/or long
reaction times are required to s y n t h e t i c a l l y generate (P)Rh(4-9).
For t h i s reason, much of the mechanistic information i n v o l v i n g
(P)Rh reactions i s l o s t and a detection of reaction intermediates
i n the synthesis of the σ-bonded (P)Rh(R) complexes i s generally
not possible.

31. KADISH ET AL. Metalloporphyrins Containing Metal-Carbon σ-Bonds 453
The method for electrosynthetic generation of (P)Rh(R)

involves an i n i t i a l formation of (P)Rh and i s accomplished by the
one electron reduction of an i o n i c Rh(III) porphyrin s p e c i e s ( l A ) .
The generated Rh(II) porphyrin can dimerize as shown i n Equation
1 but, i n the presence of an a l k y l halide RX, w i l l react to form
11
(P)Rh(R). The o v e r a l l reaction between RX and ( P ) R h i s given by
Equation 3, where S i s an electron source other than the
electrode.
11 +
(P)Rh + RX + S + (P)Rh(R) + X" + S (3)
The reactions associated with Equation 3 can be monitored by

c y c l i c voltammetry which give current voltage curves of the type
shown i n Figures l a and lb for the case of RX = CH I. The f i r s t 3
reduction i n Figure l b i s the Rh(III) Rh(II) t r a n s i t i o n and the

second i s the r e v e r s i b l e reduction of (TPP)Rh(CH ). An analysis 3
of these c y c l i c voltammogram
spectroelectrochemical
where L i s dimethylamine(14)
Scheme I
+
[(TPP)Rh(L)J + e - (TPP)Rh + 2L (4)
(TPP)Rh + RX + (TPP)Rh(R) + X* (5a)

+
(TPP)Rh + RX + [(TPP)Rh(R)] + X" (5b)
+
X* + S X" + S (6a)
+ +
[(TPP)Rh(R)] + S - (TPP)Rh(R) + S (6b)
After electrogeneration of (TPP)Rh (Equation 4) and the
attack at the R-X bond, either a loss of X* and formation of
ÇTPP)Rh(R) (Equation 5a) or a loss of X- with formation of
+
L(TPP)Rh(R)J (Equation 5b) w i l l occur. Reaction pathways 5a and
6a occur for RX complexes where X = I or Br while reactions 5b
and 6b occur for RX complexes where X = CI or F.
The mechanism shown i n Scheme I was supported by coulometric
determinations, the formation of X- as one of the reaction pro-
ducts, and the absence of any (TPP)RhX as a f i n a l product(14).
Equations 6a and 6b i n Scheme I indicate that a second electron
source other than the electrode i s involved i n the o v e r a l l reac-
t i o n and was postulated on the basis of coulometric data which
indicated that only one electron was electrochemically trans-
ferred. This was true despite the fact that the o v e r a l l reaction
requires a t o t a l of two electrons. A f u l l discussion of these
r e s u l t s are presented i n the o r i g i n a l report(14).
An electrosynthetic method was used to generate the 25 d i f -
ferent (P)Rh(R) complexes l i s t e d i n Table 1(14,16). Many of the
complexes i n t h i s Table had not been previously reported, espe-
c i a l l y (P)Rh(RX). In a l l cases, bulk e l e c t r o l y s i s of

I ι ι ι ι ι ι ι ι I I
0.0 -0.4 -0.6 -1.2 -1.6 -2.0
POTENTIAL, (V vs SCO
4
Figure 1. Cyclic voltammograms obtained at Pt electrode: a, 9.9 χ Ι Ο " M
4
[(TPP)Rh(L)2] Cr; b, 9.9 χ Ι Ο " M [ ( T P P J R h ^ J + C r and 1.0 equivalent of
+
C H I ; c, (TPP)Co; and d, (TPP)Co and 1.5 equivalent of C H I in T H F containing

3 3
0.1 M TBAP. Adapted from refs. 14 and 26.

31. KADISH E T AL. Metalloporphyrins Containing Metal—Carbon σ-Bonds 455
Table I. The Redox Potentials and UV-vis Spectral Data for the Electrogenerated
a
(TPP)Rh(R) Complexes in THF Containing 0.2 M TBAP
c
Complex R Group E ( R e d )
UV-Vis
E
l/2 ( 0 x ) b
l/2
— — -1.45 -1.90 418(22.9) 525(2.3)

U
(R)Rh(R) CH 3
CH 2 5
1.12
— -1.41
-1.42
-1.90
-1.91
411(21.6) 524(1.9)
411(17.7) 524(1.5)
CH 3 7
0.97 1.33
C H
0.97 1.3A -1.42 -1.92 411(21.5) 524(1.7)
49
C H 0.98 1.34 -1.42 -1.91 411(25.2) 524(2.3)
5 11
C H 0.97 1.34 -1.42 -1.91 411(27.9) 524(2.8)
6 13
CH(CH,)CH'2"'3
CH. 0
e
C(CH ) 3 3
(P)Rh(RX) C H C 1
— — -1.41 -1.86 411(27.2) 524(2.5)
3 6
C H C1
A 8
— — -1.41 -1.88 411(27.9) 524(2.7)
C H C1
5 10
— — -1.42 -1.90 411(24.9) 524(2.0)
CjHgBr -1.39 f
-1.81 -1.83 f
411(24.7) 524(2.4)
C H Br
A 8 1.14 9
-1.40 -1.85 -2.01
f f
411(29.2) 524(3.2)
1.149 — -1.40 -1.89 e
411(23.7) 524(1.9)
C
5 10 H Br 0.98 1.35 -1.38 f
411(26.9) 524(2.2)
0.97 1.34 -1.39 -1.78^ -1.99 f
411(30.9) 524(2.6)
W 0.98 1.35 -1.40 -1.8lf -1.88 411(27.7) 524(2.2)
C H,6 A 0.99 1.35 -1.41 -1.82^ -1.88 411(27.2) 524(2.2)
12
— — -1.42 415(20.0) 527(2.0)
CH Br 2 -1.43 413(21.9) 526(2.2)
CH I 2
-- - -1.43 415(18.5) 527(1.8)
(P)Rh(CHX ) 2 CHC1 2
-1.41 418(20.8) 529(2.2)
CHIo - - -1.43 418(15.5) 528(2.0)
(P)Rh(CX ) 3 CC1 3
-1.41 421(21.2) 533(2.1)
CI, -1.43 416(11.8) 526(1.7)
From reference 12, 13, 14.

Measured in PhCN.
nm (e χ 10-4, - l cm-1). M
Measured in PhCN.
Complete formation of (P)Rh(R) is not observed.
E
p measured at 0.1 V/s.
Measured in THF.

+
[(TPP)Rh(L)J C1~ i n the presence of an a l k y l halide leads to a
given (P)Rh(R) or (P)Rh(RX) complex. The y i e l d was nearly quan-
t i t a t i v e (>80%) i n most cases based on the rhodium porphyrin
s t a r t i n g species. However, i t should be noted that excess a l k y l
halide was used i n Equation 3 i n order to suppress the competing
dimerization reaction shown i n Equation 1. The ultimate (P)Rh(R)
products generated by electrosynthesis were also characterized by
H NMR, which demonstrated the formation of only one porphyrin
product(14). No reaction i s observed between (P)Rh and a r y l
halides but this i s expected from chemical reactivity
studies(10,15). Table I also presents e l e c t r o n i c absorption
spectra and the reduction and oxidation potentials of the
electrogenerated (P)Rh(R) complexes.
C y c l i c voltammetry was used to monitor the mechanism for
(TPP)Rh(R) formation according to Equation 3 where RX i s a t e r -
minal a l k y l halide. The current for reduction of electroge-
nerated (P)Rh(R) or (P)Rh(RX) specie i f th
concentration of t h i s produc
a measure of i t s rate o
dized for experimental factors such as scan rate, i n i t i a l con-
+
centration of [(TPP)Rh(L)J cr (or other i n i t i a l Rh(III)
species), electrode area, and concentration of the a l k y l halide
reactant.
The r e s u l t s of k i n e t i c experiments with terminal a l k y l h a l i -
des demonstrate that the o v e r a l l reaction rate between (P)Rh and
RX i s dependent upon the s i z e of the a l k y l h a l i d e , the number of
halide groups (RX or RX ) and on the type of halide. The reac-
2
t i o n rate of RX follows the trend I > Br > F = C1(1A). Also, the

larger the a l k y l group, the slower i s the chemical reaction(14).
Mechanistic studies of homogenous chemical reacTTons
involving formation of (P)Rh(R) from (P)Rh and RX demonstrate a
r a d i c a l pathway(9). These studies were c a r r i e d out under d i f -
ferent experimental conditions from those i n the electrosynthe-
s i s . Thus, the difference between the proposed mechanism using
chemical and electrochemical synthetic methods may be due to d i f -
ferences related to the p a r t i c u l a r investigated a l k y l halides i n
the two d i f f e r e n t studies or a l t e r n a t i v e l y to the d i f f e r e n t reac-
t i o n conditions between the two sets of experiments. However, i t
should be noted that the electrochemical method for generating
the reactive species i s under conditions which allow for a
greater s e l e c t i v i t y and control of the reaction products.
The highly reactive nature of (P)Rh i s perhaps best
demonstrated by the reaction of electrochemically generated
(TPP)Rh with terminal alkenes and alkynes. The o v e r a l l reaction
with alkynes i s given by Equation 7 and the suggested mechanism
(P)Rh + HC"CR ·* (P)Rh(R) + products (7)
i s presented i n Scheme 11(15). A s i m i l a r reaction mechanism was

also found to occur with aïl<ênes.

Scheme I I
+
[(TPP)Rh(L)J Cl- + (TPP)Rh * l/2[(TPP)Rh] 2
fast HC CR5
Η
C slow
(TPP)Rh(R)
C
R
The reactive (TPP)Rh i n Scheme I I i s electrogenerated from

L(TPP)Rh(L)J cl" i n th
formation of an intermediat
not detected by chemical reaction methods and was t e n t a t i v e l y
assigned as a IT complex(15). Similar π complexes have been
reported for ruthenium porphyrin species(17^18).
The reaction of (TPP)Rh with terminal alkenes or alkynes i s
of special i n t e r e s t due to the cleavage of the carbon-carbon bond
adjacent to e i t h e r the alkene or the alkyne f u n c t i o n a l i t y and
r e s u l t s i n the ultimate formation of (TPP)Rh(R). This o v e r a l l
reaction implies a c t i v a t i o n of a r e l a t i v e l y i n e r t carbon-carbon
bond, especially for the case of the terminal alkene. However,
the ultimate formation of (P)Rh(R) i s not surprising i f one con
siders the r e l a t i v e s t a b i l i t y of the rhodium carbon bond i n t h i s
species(17).
Cobalt Porphyrins. The primary synthetic method for generating

cobalt porphyrins with a metal carbon σ-bond i s to react a chemi
c a l l y or electrochemically generated c o b a l t ( I ) anion, [(p)Co]~,
with an a l k y l or an a r y l halide( 19-26). [(P)Co]~ i s stable and
the spectroscopic properties of isolated Na[(TPP)£oJ ·5ΤΗΓ has
been reported(27). The s o l u t i o n spectra of [ ( T P P ) C O L J - i n toluene
and benzene are also known (Kadish, K. M. ; Mu, X. H., submitted
for p u b l i c a t i o n ) .
The generated [(P)CoJ- i s stable i n numerous solvents but
reacts with a l k y l halides as shown i n Equation 8 U ) .
[(P)Co]~ + RX ^ (P)Co(R) + X" (8)
The above r e a c t i v i t y i s d i f f e r e n t from that of rhodium porphyrins

in two respects. The f i r s t difference i s that (P)Rh i s not
1
stable, as i s the case for electrogenerated [(P)Co ]". In addi
t i o n , the Rh(I) state i s not accessible for (P)Rh and at low tem
perature only a porphyrin ring reduction to generate the Rh(II) π
anion r a d i c a l , L(P)Rh]~ w i l l occur(12). Hence, the electroge
nerated cobalt species can be viewecTas a two electron reagent
while the rhodium species i s an one electron reagent.

The electrogeneration of [(TPP)Co]"" from (TPP)Co, and the

reaction of t h i s species with CH I can be followed by c y c l i c 3
voltammetry as shown i n Figures l c and Id. In the absence of any

added reagent, there are two r e v e r s i b l e reduction waves which
occur at E i / = 0.85 and -1.86 V (see Figure l c ) . These are due
2
to the formation of L(TPP)CoJ- and L(TPP)Co] -, where the second 2
reduction has occurred at the porphyrin π ring system. The f i r s t

reduction of (TPP)Co i s not r e v e r s i b l e i n the presence of CH I, 3
and occurs at E = -0.86 V (see Figure Id). A new reversible

p
reduction also appears at E / = -1.39 V. This process i s due to

x 2
(TPP)Co(CH ) which i s formed as shown by Equation 8. The f o r

3
mation of (TPP)Co(CH ) as the f i n a l product of the electrosynthe

3
s i s was confirmed by spectroelectrochemical experiments which

were carried out under the same experimental conditions(26).
Reactions of Low Valent Rh and Co with Methylene Chloride. A

number of porphyrin electrochemica studie carrie
i n CH C1 (3). However
2 2
believed and w i l l reac complexe

to generate (P)Rh(CH ci)(13) and (P)Co(CH Cl)(26), respectively.
2 2
These reactions can be monitored by c y c l i c voTFammetry and give

current-voltage curves verv s i m i l a r to those obtained during the
reaction of (P)Rh or [(P)CoJ- with RX (See Figure 1).
Figure 2 shows c y c l i c voltammograms of (TPP)Co and
+
L(TPP)Rh(L)J i n CH C1 . The formation of both [(TPP)CoJ- and
2 2
(TPP)Rh i s i r r e v e r s i b l e and for the case of the cobalt complex,

the o v e r a l l reaction i s shown i n Scheme 111(26).
Scheme I I I
e e
1 1 2
(P)CoH * [(P)Co ]' * [(P)Co ]"
n
(P)Coni(CH Cl) 2 * [(P)Co (CH Cl)]~ 2
As seen i n Figure 2, s i m i l a r reactions occur between CH C1 2 2
and (P)Rh or [(P)Co]- but the current-voltage curves d i f f e r i n

that the electrosynthesized (P)Rh(CH Cl) i s reversibly reduced at 2
E i / = -1.43 V (see Table I ) .

2
Germanium Porphyrins. The electrosynthesis of σ-bonded mono-alkyl

or mono-aryl germanium porphyrins involves the conversion of
(P)Ge(R) to (P)Ge(R)X where X i s an anionic ligand. A standard
2
Grignard reaction between (P)Ge(Cl) and RMgX leads to the σ- 2
bonded b i s - a l k y l or b i s - a r y l complexes, (P)Gjp(R) . These 2
complexes were initially synthesized as H NMR shift

reagents(28,29). However, almost no r e a c t i v i t y of these species
was reported u n t i l several years l a t e r when i t was shown that the

31. KADISH E T A L . Metalloporphyrins Containing Metal-Carbon σ-Bonds 459
(P)Co(R)/[(P)Co(R)]"
I I I I ι ι • ι 1 1 1
0.0 -0.4 -0.8 -1.2 -1.6 -2.0
POTENTIAL (V vs S C O
Figure 2. Cyclic voltammograms obtained at Pt electrode: a, (TPP)Co; and b, 4.8 χ
1(T M [(TPP)Rh(L)2] Cr in C H C 1 containing 0.1 Μ ΤΓΒΑΡ. Adapted from
4 +
2 2
refs. 13 and 26.

Ge(IV) porphyrins underwent a photochemical i n s e r t i o n of 0 into 2
the germanium-carbon bond to give peroxides(30-34). The σ-bonded

compounds also undergo photohomolytic cleavage of the germanium-
carbon bond i n the absence of oxygen to give a l k y l or a r y l r a d i
cals and porphyrin r a d i c a l anions(Xu, Q. Y.; Guilard, R.;
Kadish, Κ. M., submitted for publication and 35).
The o v e r a l l mechanism for electrochemical conversion of
(P)Ge(R) to (P)Ge(R)X i s presented i n Scheme IV where Ρ =
2
0EP(35).
+
In Scheme IV, a [ ( 0 E P ) G e ( C H ) ] cation r a d i c a l i s i n i t i a l l y
6 5 2
generated upon oxidation of (0EP)Ge(C H ) but one germanium car 6 5 2
bon bond rapidly cleaves to give (0EP)Ge(C H )C10i». The C10 " 6 5 H
counterion i s from the supporting e l e c t r o l y t e . This cleavage of

the germanium-carbon bond r e s u l t s i n an o v e r a l l i r r e v e r s i b l e o x i
dation process which occurs at Ep values between 0.64 and 0.95 V
depending upon the nature of R and the s p e c i f i c porphyrin macro-
cycle. An example of th r e s u l t i n c y c l i voltammogra i show
i n Figure 3.
The electrosynthesize (0EP)Ge(C )C10 6 5
s i t u by thin-layer spectroelectrochemistry. The f i n a l product of

electrosynthesis was s p e c t r a l l y compared with the same compounds
which were synthesized using chemical and photochemical
methods(35). (0EP)Ge(C H )Cl and (0EP)Ge(C H )0H were also
6 5 6 5
electrochemically generated by the use of specific

solvent/supporting e l e c t r o l y t e systems(35).
The electroreduction/oxidation reactions of (OEPteetCeHsJCKU,
(0EP)Ge(C H )Cl and (0EP)Ge(C H )0H were investigated i n PhCN
6 5 6 5
containing 0.1 M TBAP(35). Under these experimental conditions,

the o v e r a l l reaction mechanism shown i n Scheme V i s demonstrated
to occur.
Half-wave potentials for each of the electron transfer steps
shown i n Scheme V are l i s t e d i n Table I I . The f i r s t oxidations of
(0EP)Ge(C H )Cl and (0EP)Ge(C H )0H are i r r e v e r s i b l e and occur at
6 5 6 5
E = 1.00 V for X = OH*.

p The second oxidations of these
complexes are r e v e r s i b l e and both occur at E i / = 1.40 V. These 2
second oxidation processes occur at i d e n t i c a l to the E i / values 2
for oxidation of (0EP)Ge(C H )C10 and t h i s was presented as

6 5 H
strong evidence for an oxidation of CI- on (0EP)Ge(C H )C1 and 6
OH- on (0EP)Ge(C H )0H(35).

6 5
S i l i c o n Porphyrins. The electrosynthesis of σ-bonded mono-alkyl

or mono-aryl s i l i c o n porphyrins p a r a l l e l s that of the germanium
complexes i n that ( P ) S i ( R ) 2 can be converted to (P)Si(R)X after
electrooxidation. However, ( 0 E P ) S i ( C H ) and (0EP)Si(CH ) show 6 5 2 3 2
s l i g h t l y d i f f e r e n t oxidative behavior than the germanium analo

gues with the same R groups. For example, (0EP)Si(R)0H i s
generated immediately following oxidation of (0EP)Si(R) which 2
+
d i f f e r s from [(OEP)Ge(R)J which produces (0EP)Ge(R)C10.» a f t e r
the cleavage of one metal-carbon bond. A l l of the electrosynthe
sized (P)Si(R)X complexes undergo r e v e r s i b l e reductions and h a l f -
wave potentials for these reactions are summarized i n Table I I .
The o v e r a l l oxidation-reduction mechanisms of ( P ) S i ( R ) and 2
(P)Si(R)X are summarized i n Scheme VI(36).

31. KADISH E T A L . Metalloporphyrins Containing Metal-Carbon σ-Bonds 461
Scheme IV
+ - β
C(OEP)Ge(C H ) ]
6 5 2 = (OEP)Ge(C H )
6 5 2
' 1.20 0.80 0.40 0.00 -0.40 -0.80 -1.20 -1.60 -2.00
POTENTIAL, vs SCE
Figure 3. Cyclic voltammograms obtained at Pt electrode: a, ( O E P ) G e ( C H ) ; 6 5 2
3
and b, 10~ M (TPP)Ge(C H ) in PhCN containing 0.1 M TBAP. Adapted from
6 5 2
ref. 35.

Scheme V
+ - β β - β
C(OEP)Ge(C H )CI0 ] =====
6 5 4 (OEPJGeŒeHsJCIO* = = C(OEP)Ge<C H5)CI04]
6 ===== [{OEP)Ge(C H )CI04]
6 5
- H 0 HCIO4
2
- H 0 HCIO4
2
[(OEP)Ge(C H )(OH)]
6 5 ===== (OEP)Ge(C H )(OH) 6 5 ====== C(OEP)Ge(C H )(OH)]6 5
3
Table II. Half-wave and Peak Potentials for Metal-Carbon σ-bonded Germanium and
0
Silicon Porphyrins in PhCN or CH C1 (0.1 M TBAP) 2 2
Oxidation Reduction
Complex Axial Ligand Porphyrin Ring Porphyrin Ring
(0EP)Ge(C H )C10 6 5 4
— — 1.40 -0.82 -1.30
— 1.A0
— -1.38
C d
(OEPDGeCCgHÔH 1.00 '
—
c , e
(OEPjGeCCgH^Cl i.io 1.40 -0.89 -1.30
— —
C
(0EP)Ge(CH C H ) 2 6 5 2 0.64 1.34 C
-1.54
— -1.48
C
(0EP)Ge(CH ) 3 2 0.75 1.37
(0EP)Ge(C H ) 6 5 2
— 0.88° 1.39 -1.40
—
(TPP)Ge(CH C H )
— -1.17 -1.72
C C
2 6 5 2 0.73 1.34
(TPP)Ge(C H )
— -1.10 -1.65
C C
6 5 2 0.95 1.45
(OEPÎSKC^DOH 1.14 ' C d
0.86C
-1.43 ~
-1.42
—
C
(0EP)Si(C H ) 6 5 2 0.80
(0EP)Si(CH ) 3 2 1.12 ' C d
0.72C
-1.46
From reference 35.

From reference 36.
E__ measured at 0.1 V/s.
pa
-
Corresponds to oxidation of OH ligand.
Corresponds to oxidation of CI- ligand.

31. KADISH E T AU Metalloporphyrins Containing Metal-Carbon σ-Bonds 463
Scheme VI
[(OEP)SKC Hs) ] 6 2
[(0EP)SKC H5) ]
6 2
HCK> (aq)
4
•2 -β
C(0EP)Si(C H5)0H]
6 ===== [(OEPJSKCeHsJOH] ===== (0EP)SKC H5)0H
e
> [(0EP)SKC H5)0H]"
e
^y- OH* \
HCK>4(aq) \
•2 • -β ' β \
[(OEPJSKCeHgJCIOj - — - [(OEP)Si(C H )CIOJ
6 5 ====== (OEP)SKC H5)^4=======C(OeP)SJ(C H5)Cl04J
6 6

A comparison of Schemes V and VI show that the electroche

mistry of (0EP)Ge(C H )0H and (0EP)Si(C H )0H are s i m i l a r . The
6 5 6 5
f i r s t oxidation of (0EP)Si(C H )0H occurs at the hydroxyl ligand

6 5
and generates (0EP)Si(C H )ClCU as a f i n a l product.

6 5 This com
pound can be r e v e r s i b l y oxidized by up to two electrons at more
p o s i t i v e p o t e n t i a l s and gives a porphyrin π cation r a d i c a l and
dication(36).
In summary, the four chemical systems described i n t h i s paper
demonstrate the v e r s a t i l i t y and s e l e c t i v i t y of electrochemical
methods f o r synthesis and characterization of metal-carbon σ-
bonded metalloporphyrins. The described rhodium and cobalt
systems demonstrate s i g n i f i c a n t differences with respect to t h e i r
formation, s t a b i l i t y and to some extend, r e a c t i v i t y of the low
valent species. On the other hand, properties of the electroche-
mically generated mono-alkyl or mono-aryl germanium and s i l i c o n
systems are s i m i l a r to each other.
Acknowledgment. The suppor

[Grant CHE-8515411) i
acknowledge numerous discussions with our c o l l a b o r a t o r , Dr. Roger
Guilard, from the University of Dijon i n France.
( 1) Guilard, R.; Lecomte, C.; Kadish, Κ. M. Struct. Bond. 1987,
64, 205-268.
( 2) Brothers, P. J . ; Collman, J . P. Acc. Chem. Res. 1986, 19,
209.
( 3) Kadish, Κ. M. Prog Inorg. Chem. 1986, 34, 435-605.
( 4) Highes, R. P. Comprehensive Organometallic Chemistry;
Wilkinson, G. Ed.; Pergamon Press: Ν. Y., 1982, V o l . 5,
p. 277.
( 5) Wayland, Β. B.; Woods, Β. Α.; C o f f i n , V. L. Organometallics
1986, 5, 1059.
( 6) Del Rossi, K.; Wayland, Β. B. J. Am. Chem. Soc. 1985, 107,
7941.
( 7) Wayland, Β. B.; Woods, Β. Α.; Pierce, R J. Am. Chem. Soc.
1982, 104, 302.
( 8) Setsune, J . ; Yoshida, Z.; Ogoshi, H. J . Chem. Soc. Perkin
Trans. 1982, 983.
( 9) Paonessa, R. S.; Thomas, N. C.; Halpern, J . J. Am. Chem.
Soc. 1985, 107, 4333.
(10) Aoyama, Y.; Yoshida, T.; Sakurui, K.-I.; Ogoshi, H. J.
Chem. Soc. Chem. Comm. 1983, 478.
(11) Aoyama, Y.; Yoshida, T.; Sakurui, K.-I.; Ogoshi, H.
Organometallics 1986, 5, 168.
(12) Kadish, K. M.; Yao, C.-L.; Anderson, J . E.; Cocolios, P.
Inorg. Chem. 1985, 24, 4515.
(13) Anderson, J . E. Yao, C.-L.; Kadish, Κ. M. Inorg. Chem.
;
1986, 25, 718.

(14) Anderson, J . E.; Yao, C.-L.; Kadish, Κ. M. J. Am. Chem.
Soc. 1987, 109, 1106.

(15) Anderson, J . Ε.; Yao, C.-L.; Kadish, Κ. M. Organometallics

1987, 6, 706.
(16) Anderson, J . E.; L i u , Y. H.; Kadish, Κ. M. Inorg. Chem.
1987, 26, 4174.
(17) Collman, J . P.; Barnes, C. E.; Swepston, P. N.; Ibers, J .
J . Am. Chem. Soc. 1984, 106, 3500.
(18) Farnor, M. D.; Woods, Β. Α.; Wayland, Β. B. J . Am. Chem.
Soc. 1986, 108, 3659.
(19) Dolphin, D.; Halko, D. J . ; Johnson, E. Inorg. Chem. 1981,
30, 4348.
(20) Lexa, D.; Saveant, J.-M.; S o u f f l e t , J.P. J. Electroanal.
Chem. I n t e r f a c i a l Electrochem. 1979, 100, 159.
(21) Perree-Fauvet, M.; Gaudemer, Α.; Boucly, P.; Devynck, J. J .
Organomet. Chem. 1976, 120, 439.
(22) Clarke, D. Α.; Grigg, R.; Johnson, A. W.; Pinnock, H. A. J.
Chem. Soc. Chem. Comm. 1967, 305.
(23) Clarke, D. Α.;
Pinnock, H. A. J.
(24) Ogoshi, H.; Wantanabe, E.; Koketsu, N.; Yoshida, Z. B u l l .
Chem. Soc. Jpn. 1976, 49, 2529.
(25) Momenteau, M.; Fournier, M.; Rougee, M. J. Chim Phys. 1970,
67, 926.
(26) Kadish, K. M.; L i n , X. Q.; Han, B. C. Inorg. Chem. 1987,
26, 4161.
(27) Kobayashi, H.; Hara, T.; Kaizu, Y. B u l l . Chem. Soc. Jpn.
1972, 45, 2148.
(28) Maskasky J . E.; Kenney, M. E. J . Am. Chem. Soc. 1971, 93,
2060.
(29) Maskasky, J. E.; Kenney, M. E. J . Am. Chem. Soc. 1973, 95,
1443.
(30) Cloutour, C.; Lafargue, D.; Richards, J . Α.; Pommier, J . C.
J. Organomet. Chem. 1977, 137, 157.
(31) Cloutour, C.; Debaig-Valade, C.; Pommier, J . c.; Dabosi,
G.; Marthineau, J . J . Organomet. Chem. 1981, 220, 21.
(32) Cloutour, C.; Lafargue, D.; Pommier, J . C. J. Organomet.
Chem. 1983, 190, 35.
(33) Cloutour, C.; Debaig-Valade, C.; Gacherieu, C.; Pommier, J .
C. J. Organomet. Chem. 1984, 269, 239.
(34) Cloutour, C.; Lafargue, D.; Pommier, J . C. J . Organomet.
Chem. 1978, 161, 327.
(35) Kadish, K. M.; Xu, Q. Y.; Barbe, J.-M.; Anderson, J . E.;
Wang, E.; Guilard, R. J . Am. Chem. Soc. 1987, 109, 7705.
(36) Kadish, Κ. M.; Xu, Q. Y.; Barbe, J.-M.; Guilard, R. Inorg.
Chem. 1988, 27, 1191.

Chapter 32
Formation of Metal—Oxygen Surface
Compounds on Copper, Silver,
and Gold Electrodes
Reaction with Dioxygen and Electrochemical
Oxidation of ΟΗ¯ in Acetonitrile
Donald T. Sawyer and Pipat Chooto
Department of Chemistry, Texas A & M University, College Station,
The oxidation
trile at copper, s i l v e r , gold, and glassy
-carbon electrodes has been characterized by
c y c l i c voltammetry. In the absence of bases
the metal electrodes are oxidized to t h e i r
+ + +
respective cations (Cu , Ag , and Au ) at po -
t e n t i a l s that range from 0 . 2 V vs. SCE for Cu -
to +1.3 V for Au. At glassy carbon OH i s
-
oxidized to 0 · (+0.35 V vs SCE) and then to
·O· by an ECE mechanism. In contrast, with -
clean metal electrodes the oxidation of OH
-
to O · and ·O· is f a c i l i t a t e d v i a formation
of metal-s/oxygen-p covalent bonds to give a
series of surface compounds (MOH, MOM, MOOM,
-
and MO ). The shift to less positive oxida
tion potentials has been used to obtain an
estimate of the metal-oxygen covalent bond
energies (about 50-70 k c a l ) . Concurrent re
+ +
duction of Cu plus O , and of Ag plus O
2 2
yields a series of surface compounds (MOM,

-
MOOM, and MO) that p a r a l l e l those that re
-
sult from OH oxidation at the metal sur
faces.
A r e c e n t s t u d y (1) h a s d e m o n s t r a t e d t h a t t h e e l e c t r o c h e m -
i c a l o x i d a t i o n o fhydroxide ion y i e l d s hydroxyl r a d i c a l
(•OH) a n d i t s a n i o n ( 0 ~ · ) . These s p e c i e s i n t u r n a r e s t a -
b i l i z e d a t g l a s s y carbon e l e c t r o d e s by t r a n s i t i o n - m e t a l
i o n s v i a t h e f o r m a t i o n o fmetal-oxygen c o v a l e n t bonds
( u n p a i r e d d e l e c t r o n w i t h u n p a i r e d ρ e l e c t r o n o f -OH a n d
0"·). T h e c o i n a g e m e t a l s (Cu, A g , a n d A u ) , w h i c h a r e u s e d
as oxygen a c t i v a t i o n c a t a l y s t s f o r s e v e r a l i n d u s t r i a l
processes (e.g., Ag/02 f o r p r o d u c t i o n o f ethylene oxide)
1 0 1 9 2
(2-10), have an u n p a i r e d e l e c t r o n ( d s o r d s valence-
0097-6156/88/0378-0466$06.00/0

32. SAWYER AND C H O O T O Formation of Metal-Oxygen Surface Compounds 467
s h e l l ) a n d t h e i r mode o f a c t i v a t i o n may i n v o l v e c o v a l e n t
b o n d f o r m a t i o n w i t h d i o x y g e n as a f i r s t s t e p t o w a r d s i t s
atomization. Likewise, the o x i d a t i o n of hydroxide ion at
coinage-metal e l e c t r o d e s i s f a c i l i t a t e d by t h e p r e s e n c e
o f a n u n p a i r e d e l e c t r o n t o c o u p l e w i t h -OH a n d / o r 0"~ · t o
f o r m m e t a l - o x y g e n a d d u c t s , w h i c h a p p e a r t o be s i m i l a r t o
those t h a t r e s u l t from metal-dioxygen surface r e a c t i o n s .
The p r e s e n t p a p e r s u m m a r i z e s t h e r e s u l t s o f a n e l e c t r o -
c h e m i c a l i n v e s t i g a t i o n i n a c e t o n i t r i l e o f (a) t h e o x i d a -
t i o n o f "OH a t Cu, A g , a n d Au e l e c t r o d e s , (b) t h e p o t e n -
+ + +
t i o m e t r i c t i t r a t i o n o f Cu , A g , and Au w i t h "OH, and (c)
+ +
t h e c o n c e r t e d r e d u c t i o n o f O2 a n d C u or Ag at a glassy
carbon electrode.
Experimental Section
Equipment. C y c l i c voltammetr
e l e c t r o l y s i s were a c c o m p l i s h e
t e m s M o d e l CV-27 a n d a H o u s t o n I n s t r u m e n t s M o d e l 2 0 0 0 XY
recorder. The e l e c t r o c h e m i c a l m e a s u r e m e n t s w e r e made
w i t h a 10-mL m i c r o c e l l a s s e m b l y t h a t was a d a p t e d t o u s e a
working electrode, a platinum-wire a u x i l l i a r y electrode
(contained i n a glass tube with a medium-porosity g l a s s
f r i t and f i l l e d w i t h a c o n c e n t r a t e d s o l u t i o n o f support-
i n g e l e c t r o l y t e ) , and a A g / A g C l r e f e r e n c e e l e c t r o d e
( f i l l e d w i t h aqueous tetramethylammonium c h l o r i d e s o l u -
t i o n a n d a d j u s t e d t o 0.000 V v s SCE) (11) w i t h a s o l u t i o n
j u n c t i o n v i a a glass tube closed with a cracked-glass
b e a d t h a t was c o n t a i n e d i n a l u g g i n c a p i l l a r y . Glassy
c a r b o n , g o l d , and s i l v e r w o r k i n g e l e c t r o d e s were o b t a i n e d
f r o m B i o a n a l y t i c a l S y s t e m s , t h e c o p p e r e l e c t r o d e was pre-
p a r e d by e l e c t r o d e p o s i t i o n o f c o p p e r on a glassy-carbon
electrode.
C h e m i c a l s and Reagents. A c e t o n i t r i l e (MeCN), " d i s t i l l e d -

i n - g l a s s " g r a d e ( 0 . 0 0 2 % H2O) from B u r d i c k and J o h n s o n ,
was u s e d w i t h o u t f u r t h e r p u r i f i c a t i o n . Tetraethylammon-
i u m p e r c h l o r a t e (TEAP) was v a c u u m - d r i e d f o r 24 h p r i o r t o
use. Tetrabutylammonium hydroxide (TBAOH) was obtained
f r o m A l d r i c h as a 25% s o l u t i o n i n m e t h a n o l and i t s c o n -
c e n t r a t i o n was d e t e r m i n e d b y a c i d - b a s e t i t r a t i o n . Cu-
(H2O)4(0104) was p r e p a r e d f r o m r e d u c t i o n o f c o p p e r ( I I )
p e r c h l o r a t e (G.F. S m i t h C h e m i c a l s ) o r f r o m t h e d i s s o l u -
t i o n o f CU2O w i t h HCIO4 (12) . The r e s u l t i n g s a l t was r e -
1
c r y s t a l l e d f r o m d r y MeCN f o u r t i m e s t o g i v e C u ( M e C N ) 4 "
(CIO4). G o l d ( I ) s o l u t i o n s were p r e p a r e d by a n o d i c e l e c -
t r o l y s i s o f a g o l d f o i l i n a c e t o n i t r i l e (0.1M T E A P ) ( 1 3 ) .
A g C 1 0 4 was o b t a i n e d f r o m G.F. Smith Chemicals.
Results
O x i d a t i o n o f ~~QH. The v o l t a m m e t r i c o x i d a t i o n o f h y d r o x -
ide i o n at g l a s s y c a r b o n (GC), c o p p e r , s i l v e r , and g o l d

e l e c t r o d e s i s i l l u s t r a t e d b y F i g u r e s 1, 2, a n d 3. F o r
e a c h m e t a l t h e p r e s e n c e o f e x c e s s ~0H r e s u l t s i n a n i n i -
t i a l oxidation a t a p o t e n t i a l that i s less p o s i t i v e than
t h a t ( a ) f o r "OH a t a g l a s s y c a r b o n e l e c t r o d e a n d (b) f o r
the o x i d a t i o n o f t h e metal e l e c t r o d e . A f t e r a negative
s c a n t o - 1 . 5 V v s . SCE e a c h o f t h e m e t a l e l e c t r o d e s e x h i b -
its ( a f t e r t h e scan d i r e c t i o n i s reversed) an o x i d a t i o n
peak (Ep, : a C u , - 0 . 8 0 V v s S C E ; A g , - 0 . 2 7 V; A u - 0 . 3 5 V )
t h a t i s d u e t o t h e p r e s e n c e o f 3 mM "OH. I n each case t h e
p r o d u c t o f t h e a n o d i c peak i s r e d u c e d upon r e v e r s a l o f
the scan d i r e c t i o n . Each e l e c t r o d e e x h i b i t s a second ox-
i d a t i o n p e a k ( E , : C u , - 0 . 4 7 V v s S C E ; A g , 0.00 V; A u ,
p a
+0.20 V ) , w h i c h p r o d u c e s a p r o d u c t s p e c i e s t h a t i s r e -
duced as an a d s o r b e d f i l m upon s c a n r e v e r s a l ( E p : f C Cu,
- 0 . 9 0 V v s S C E ; A g , - 0 . 7 5 V; A u , - 0 . 6 0 V ) .
1
The p o t e n t i o m e t r i c t i t r a t i o n s o f [Cu (MeCN)4](CIO4),
I I
Ag C104, and Au C10
t e d i n F i g u r e 4, a n
one-to-one s t o i c h i o m e t r y . The t h r e e s y s t e m s f o r m p r e c i p -
i t a t e s such t h a t a l l o f t h e m e t a l i s removed from s o l u -
t i o n at the equivalence point. A d d i t i o n o f e x c e s s ""OH
c a u s e s some d i s s o l u t i o n o f t h e CuOH a n d AgOH p r e c i p i -
t a t e s , and appears as a second step f o r t h e t i t r a t i o n
curve of Ag(I) (Figure 4b).
C o n c e r t e d R e d u c t i o n o f Q a n d Cu+ o r Aa+. F i g u r e 5 i l l u s -
2
t r a t e s t h e c y c l i c v o l t a m m o g r a m s f o r O2 i n M e C N ( 0 . 1 M T E A P )
a t g l a s s y c a r b o n , Cu, Ag, a n d Au e l e c t r o d e s (each p o l i s h -
e d i m m e d i a t e l y p r i o r t o e x p o s u r e t o O2). T h e d r a w n o u t
r e d u c t i o n waves a n d t h e absence o f s i g n i f i c a n t a n o d i c
peaks upon s c a n r e v e r s a l f o rt h e t h r e e m e t a l e l e c t r o d e s
i n d i c a t e t h a t 02 r e a c t s w i t h t h e s u r f a c e p r i o r t o e l e c -
tron transfer.
The c y c l i c v o l t a m m o g r a m s a t a g l a s s y c a r b o n e l e c -
1
t r o d e f o r [Cu (MeCN)4]CIO4 a n d AgC104, r e s p e c t i v e l y , i n
t h e a b s e n c e a n d p r e s e n c e o f O2 a r e c o n s i s t e n t w i t h t h e
i n i t i a l d e p o s i t i o n o f m e t a l atoms ( F i g u r e s 6 a n d 7 ) . I n
t h e a b s e n c e o f O2 , b o t h m e t a l i o n s a r e r e d u c e d t o m e t a l
+
f i l m s on t h e g l a s s y c a r b o n e l e c t r o d e ( E P f C : C u , -0.45 V
+
v s S C E ; A g , - 0 . 1 0 V) a n d e x h i b i t t y p i c a l s t r i p p i n g - d i s s o -
l u t i o n peaks upon r e v e r s a l o f t h e v o l t a g e s c a n . However,
t h e p r e s e n c e o f O2 c a u s e s t h e r e d u c t i o n p e a k s f o r a n i n i -
t i a l n e g a t i v e v o l t a g e s c a n t o be somewhat l e s s i n t e n s e
+
and a t -0.6 V f o r C u ; s c a n r e v e r s a l does n o t y i e l d a
s t r i p p i n g peak f o rcopper and a s m a l l e r s t r i p p i n g peak
for s i l v e r . Continuation o f t h e i n i t i a l negative scan
y i e l d s two a d d i t i o n a l o n e - e l e c t r o n r e d u c t i o n peaks (E :P f C
C u , - 1 . 0 2 V a n d - 1 . 8 0 V; A g , - 0 . 9 5 V a n d - 1 . 6 V ) , a n d
with c y c l i n g o f t h e scan d i r e c t i o n , r e s u l t s i n t h e ap-
pearance o f a c h e m i c a l l y - r e v e r s i b l e c o u p l e (Cu: E p a j f
+0.20 V a n d E P f C , - 0 . 4 0 V; A g : E , , - 0 . 1 8 V a n d E
p a ,
P f C

32. SAWYER AND C H O O T O Formation ofMetal-Oxygen Surface Compounds 469
1 1 1 1 1 1 1 1
(a) Cu(GC)
10/iAj
(b) ZmWOH (Λ^^^^^^
J,
•» J
(c) 0.5 mM'OH Cu(GC)
(d) 3mM"OH Cu(GC)
1 1 1 1
+1.5 +1.0 +0.5 0.0 -0.5 -1.0 1.5 -2.0

Ε, V vs. SCE
F i g u r e 1. C y c l i c v o l t a m m o g r a m s i n MeCN(0.1M t e t r a -
e t h y l a m m o n i u m p e r c h l o r a t e ) f o r t h e o x i d a t i o n o f (a) a
c o p p e r e l e c t r o d e , (b) 3 mM ~OH a t a g l a s s y c a r b o n
e l e c t r o d e , ( c ) 0.5 mM "OH a t a c o p p e r e l e c t r o d e , a n d (d)
1
3 mM ""OH a t a c o p p e r e l e c t r o d e . S c a n r a t e , 0. I V s " ;
2
e l e c t r o d e a r e a , 0.08 c m ; c o p p e r e l e c t r o d e p r e p a r e d b y
e l e c t r o p l a t i n g Cu(C104) o n t o a g l a s s y c a r b o n e l e c t r o d e
(GCE).

τ 1 1 1 1 1 Γ
I I I I I I I I I
+1.0 +0.5 0.0 -0.5 -1.0 -1.5 -2.0
Ε, V VS. SCE
F i g u r e 2. C y c l i c v o l t a m m o g r a m s i n MeCN(0.1M TEAP) f o r
t h e o x i d a t i o n o f (a) a s i l v e r e l e c t r o d e , (b) 3 mM "OH
a t a GCE, ( c ) 0.5 mM "OH a t a s i l v e r e l e c t r o d e , a n d
(d) 3 mM "OH a t a s i l v e r e l e c t r o d e . S c a n r a t e , 0.1 V
1 2 2
s " ; GCE a r e a , 0.08 c m ; A g e l e c t r o d e a r e a , 0.03 c m .

+2.0 +1.5 +1.0 +0.5 0.0 -0.5 -1.0 -1.5 -2.0

Ε, V vs. SCE
F i g u r e 3. C y c l i c v o l t a m m o g r a m s i n MeCN(0.1M TEAP) f o r
t h e o x i d a t i o n o f (a) a g o l d e l e c t r o d e , (b) 3 mM "OH a t
a GCE, ( c ) 0.5 mM "OH a t a g o l d e l e c t r o d e , a n d (d)
1
3 mM "OH a t a g o l d e l e c t r o d e . S c a n r a t e , 0 . I V s " ; GCE
2 2
a r e a , 0.08 c m ; A u e l e c t r o d e a r e a , 0.03 c m .

H
(a) 0.01 M C u
-0.2
> -0.6
-1.0
100 200 300
V
TBAOH(MO
+ 0.5
200 400
V
TBAOH(MO
+ 2.0
. (c) 0.007 M Au +
+1.0 l -
0.0
-1.0
0 200 400 600
V
TBA0H(pL)
F i g u r e 4. Potentiometric t i t r a t i o n s i n MeCN (0.1M
1
T E A P ) o f (a) 0.012 M C u ( M e C N ) 4 C I O 4 w i t h 1.1M "OH ( C u
indicator electrode), (b) 0.020M AgC10 w i t h 1.2 M "OH
4
+
(Ag i n d i c a t o r e l e c t r o d e ) , a n d ( c ) 0 . 0 0 7 2 M A u with
0.11 M "OH ( A u i n d i c a t o r e l e c t r o d e ) .

1 1
1 1 Τ I 1
1.7mM0 2
J50/iA
(a) G C E
(b) Cu + · —
(c) Ag 'S !
(d) Au
ι I ι ι I 1 1 .
+1.0 +0.5 0.0 -0.5 -1.0 -1.5 -2.0
E,V VS S C E
F i g u r e 5. C y c l i c v o l t a m m o g r a m s i n MeCN(0.1M T E A P ) o f
1.7 mM O2 (0.21 atm) a t (a) g l a s s y c a r b o n , (b) c o p p e r ,
(c) s i l v e r , a n d (d) g o l d e l e c t r o d e s . S c a n r a t e , 0.1 V
1 2 2
s" ; e l e c t r o d e areas: GCE, 0.08 c m ; C u , 0.08 c m ; A g ,
2 2
0.03 c m ; A u , 0.03 c m .

E.VvsSCE
F i g u r e 6. C y c l i c v o l t a m m o g r a m s i n MeCN(0.1M TEAP) a t
2
a g l a s s y c a r b o n e l e c t r o d e ( a r e a , 0.08 c m ) o f (a) 1.7
1
mM 02/ (b) 6.6 mM C u (MeCN) 4CIO4, a n d ( c ) 1.7 mM 0 +2
1 1
6.6 mM C u ( M e C N ) 4 C I O 4 . S c a n r a t e , 0.1 V s " .

SAWYER AND C H O O T O Formation of Metal-Oxygen Surface Compounds 475
τ 1 1 1 1 1 1 1 Γ
150//A
L : : J
+2!ô +Û +U) +05 ÔO ÔÎ5 î!ô Ï 5 '
E,V vs SCE
F i g u r e 7. C y c l i c v o l t a m m o g r a m s i n MeCN(0.1M TEAP) a t
2
a g l a s s y c a r b o n e l e c t r o d e ( a r e a , 0.08 c m ) o f (a) 1.7
mM 02, (b) 8.2 mM A g C 1 0 4 , a n d ( c ) O2 + 1.7 mM 8.2
1
AgC104. Scan r a t e , 0.IV s " .

-0.31 V ) . A t t e m p t s t o o b s e r v e s i m i l a r e f f e c t s f r o m t h e
+
p r e s e n c e o f O2 f o r t h e r e d u c t i o n o f A u h a v e b e e n u n s u c -
cessful .
Discussion and Conclusions
T h e o x i d a t i o n o f "OH i n a c e t o n i t r i l e a t g l a s s y c a r b o n
e l e c - t r o d e s y i e l d s a h y d r o x y l r a d i c a l (-OH) i n t h e p r i -
m a r y s t e p (1)
"OH -> -OH + e" E ° ' , + 0.68V v s SCE (1)
W i t h e x c e s s "OH t h e p r o c e s s is facilitated via formation

of the anion r a d i c a l .
2 "OH 0"· + H 0 " E°' 0.56V (2)
T h e o x i d a t i o n o f e x c e s s "OH i n t h e p r e s e n c e o f Z n ( T P P )
(TPP = t e t r a p h e n y l p o r p h y r i n ) i s somewhat i m p e d e d
2 "OH + Z n ( T P P ) -> Z n ( T P P ) ( 0 ~ · ) ~ + H 0 2 + e"

E°\ + 0.49V (3)
but i t i s facilitated i n the presence of Co(TPP)
2 "OH + C o ( T P P ) -> (0~·)Co(TPP)" + H 0 2 + e"

E°', - 0 . 2 2 V (4)
The l a t t e r i s a t t r i b u t e d t o t h e f o r m a t i o n o f a c o v a l e n t
b o n d b y t h e u n p a i r e d e l e c t r o n o f 0"· w i t h o n e o f t h e u n -
paired d electrons of cobalt (1).
T h e o x i d a t i o n o f "OH a t c o p p e r , s i l v e r , a n d g o l d
e l e c t r o d e s ( F i g u r e s 1-3) a l s o o c c u r s a t s u b s t a n t i a l l y
less p o s i t i v e p o t e n t i a l s than that at a glassy carbon
electrode. T h i s a p p e a r s t o be t h e r e s u l t o f c o u p l i n g t h e
u n p a i r e d e l e c t r o n o f t h e -OH p r o d u c t w i t h t h e s e l e c t r o n
1 0
of m e t a l l i c (atomic) copper, s i l v e r , o r g o l d ( d s valence
shell).
M + "OH -> M-OH + e" E ,

p a (5)
The t i t r a t i o n c u r v e s o f F i g u r e 4 a l s o a r e c o n s i s t e n t w i t h
+ + +
the p r o p o s i t i o n t h a t Cu , Ag , and A u i o n s r e a c t w i t h "OH
v i a e l e c t r o n t r a n s f e r t o g i v e a c o v a l e n t M-OH p r o d u c t v i a
t h e c o u p l i n g o f t h e u n p a i r e d e l e c t r o n o f -OH w i t h t h e s
e l e c t r o n o f t h e m e t a l atom.
+
M + "OH -» [M- + -OH] -> M-OH (6)

32. SAWYER AND CHOOTO Formation ofMetal-Oxygen Surface Compounds 411
The m e t a l i n d i c a t o r e l e c t r o d e s f o r t h e p o t e n t i o m e t r i c
+
t i t r a t i o n s r e s p o n d t o t h e M /M couple p r i o r to the equiv
a l e n c e p o i n t , a n d t o t h e MOH/M, "OH c o u p l e a f t e r t h e e q u i
valence point
M +
+ e~ —> M E 0 ,
M +
/ M Π)
M-OH + e" -> M + "OH E 0 ,

M O H / M , ~ O H (8)
The l a t t e r i s t h e r e v e r s e o f t h e h a l f r e a c t i o n f o r t h e
o x i d a t i o n o f "OH a t t h e m e t a l e l e c t r o d e s ( e q . 5 ) .
The d a t a o f F i g u r e s 1-4 h a v e b e e n u s e d t o c a l c u l a t e
f o r m a l p o t e n t i a l s f o r R e a c t i o n s 7 and 8 f o r c o p p e r , s i l
v e r , and g o l d ; t h e s e a r e summarized i n T a b l e I . Analo
gous redox p a r a m e t e r s f o r aqueous s o l u t i o n s a l s o a r e i n
c l u d e d (14) .
Whereas the r e d u c t i o
i o n s r a n g e f r o m +0.19
t i a l s f o r o x i d a t i o n o f "OH i n t h e i r p r e s e n c e a r e -0.7 9V v s
NHE(Cu), -0.30V(Ag), and -0.19V(Au). This i s compatible
with the p r o p o s i t i o n that o x i d a t i o n occurs v i a the f a c i l i
t a t e d r e m o v a l o f a n e l e c t r o n f r o m "OH a n d f o r m a t i o n o f a n
M-OH c o v a l e n t bond. The o n l y e x c e p t i o n t o t h e c l o s e a g r e e
m e n t b e t w e e n g a s - p h a s e a n d r e d o x - d e r i v e d M-OH bond energies
i s t h e Cu-OH b o n d e n e r g y f r o m a q u e o u s r e d o x d a t a . This may
b e due t o a n i n a c c u r a t e f o r m a l p o t e n t i a l f o r t h e CuOH/Cu,
"OH c o u p l e (a v a l u e o f 0.0V v s NHE r a t h e r t h a n - 0 . 3 6 V w o u l d
r e s u l t i n a more c o n s i s t e n t b o n d - e n e r g y e s t i m a t e ) .
Consideration of these primary processes together
_
w i t h t h e v o l t a m m e t r i c r e s u l t s f o r t h e M/ OH systems ( F i g
u r e s 1-3), t h e p o t e n t i o m e t r i c t i t r a t i o n d a t a ( F i g u r e 4 ) ,
and t h e v o l t a m m e t r i c d a t a f o r 0 reduction at metal e l e c
2
t r o d e s ( F i g u r e 5) a n d i n t h e p r e s e n c e o f m e t a l i o n s a t a
g l a s s y c a r b o n e l e c t r o d e ( F i g u r e s 6 and 7 ) , p r o m p t s t h e
f o r m u l a t i o n o f s e l f - c o n s i s t e n t r e a c t i o n Schemes f o r t h e
t h r e e m e t a l s i n c o m b i n a t i o n w i t h "OH a n d 0 (Schemes I , 2
I I , and I I I ) .
The s h i f t i n t h e f o r m a l o x i d a t i o n p o t e n t i a l f o r t h e
•OH/'OH c o u p l e f r o m i t s v a l u e a t g l a s s y c a r b o n t o t h a t a t
c o p p e r , s i l v e r , and g o l d i s a measure o f t h e s t a b i l i z a
θ1
t i o n o f -OH v i a c o v a l e n t b o n d f o r m a t i o n (ΔΕ χ 23.1
kcal/eV). H o w e v e r , t h e a t o m s o f t h e Cu, A g , a n d Au e l e c
t r o d e s e x i s t as d i m e r m o l e c u l e s t h a t a r e h e l d t o g e t h e r
1 0 1 0
via a d s-sd c o v a l e n t bond (the bond e n e r g i e s f o r t h e s e
d i m e r s a r e l i s t e d i n T a b l e I) (15). Evidence for t h i s
d i m e r i c bond i s p r o v i d e d from the voltammetric data f o r
+
Ag at a glassy carbon electrode (Figure 7). Reversal of
an i n i t i a l p o s i t i v e s c a n g i v e s a r e d u c t i o n p e a k a t -0.10
+
V v s SCE ( A g / A g - ) f b u t an i n i t i a l n e g a t i v e s c a n g i v e s a
r e d u c t i o n p e a k a t +0.20 V t h a t i s a n a l o g o u s t o r e d u c t i o n

+
Table I . R e d o x P o t e n t i a l s f o r t h e M / M a n d M O H / M , ""OH C o u p l e s o f C o p p e r , Silver,
and G o l d i n A c e t o n i t r i l e and i n Water, a n d Bond-
E n e r g i e s f o r T h e i r M-M a n d M - O H B o n d s
0 f a
E , V v s . NHE 1 — B.E., k c a l mol ^ —
b b c d c
M M+/M MOH/M,"OH M-M M-OH M-O
Acetonitrile
Cu +0.19(CV) -0.79(CV) 46.6 70.6 64.7
+0.05 (Pot.) -0.78 (Pot.) 70.4
Ag +0.54(CV) -0.30(CV) 39.0 55.5 52.6
+0.64 (Pot.) - 0 . 1 2 (Pot.) 51.3
E
Au + 1 . 5 8 (CV) -0.19(CV) 53.8 60.3(>62.5) 53.0
+1.57 (Pot.) -0.43(Pot.) 54.8
•OH/"OH +0.92(CV)
f
Water
Cu +0.52 -0.36 59.8 64.3
Ag +0.80 +0.34 43.6 52.6
Au +1.7 53.0
•OH/"OH +1.89
A
SCE = +0.24V vs NHE
b 0 | + +
For voltammetric data from Figure 1: E M /M = E i / 2 +0.059 l o g ([M ]bulk/2) and

0 |
E MOH/M = E i / 2 " 0.059 l o g (["OH]/2). For potentiometric data from F i g u r e 2 :
0 , + + 1 +
E M /M = (E bs)initial
0 +0.059 log [ M ] i n i t i a l and Ε MOH/M = ( E b s ) (2 "OH/M )
0 - 0.059
l o g ["OH]
c Ref. 1 5

D Ο , Ο Ι
B.E. = (-AGBF) + TASDBE + B.E.M-M/2 = [ Ε Ό Η / " 0 Η " Ε Μ0Η/Μ] Χ 23.1 + 7.8 +
B.E.M-M/2
e f
Gas phase v a l u e , R e f . 1 6 ; Ref.1 4 .
32. SAWYER AND C H O O T O Formation of Metal-Oxygen Surf ace Compounds 479
Scheme I.
A. Cu/~OH ELECTROCHEMISTRY IN MeCN

Cu + ~0H-» CuOH + e" -0.80V vs SCE
•1/2 CuOOCu
OH
CuO' + H 0 + e" E , , -0.47V
2 p a
Cu
CuOCu
CuOCu + 2e~ + H 0-» 2 Cu + 2 "OH

2
E p # c , -0.90V
CuOOCu + 2e"-» 2 CuO" -•p, c/ -1.45V
CuOOCu + 2H 0 + 2e 2
CuO" CuO" + e~
1/2 CuOOCu
B. Cu(I)/0 2 ELECTROCHEMISTREY IN MeCN AT GC ELECTRODE

+
2 Cu + 2e"-> Cu 2 E P r C / -0.45V vs SCE
+
2 Cu + 0 2 + 2e"-> CuOOCu E
P . c / "0.60V vs SCE
2e~ E , , -1.02V
p c
2 CuO'
CuO" + H 0 + e"-> Cu + 2"OH

2 E P r C , - 1.80V
-e" Ep, , -0.80V

a
CuO" + H 0 2
-e" E p , , -0.85V
a
CuO"
I 1/2 CuOOCu
+
CuOOCu -> CuOO" + Cu + e" E , , + 0.20V
p a
E , , - 0.40V
p c
CuOOCu
2+
CuOO" -> Cu + 0 2 + 2 e~ E p # a / + 1.68V

Scheme I I
A. Ag/"OH E L E C T R O C H E M I S T R Y I N MeCN
A g + "OH—> AgOH + e" E p / S , - 0 . 2 7 V v s SCE
θ
* A g + "OH E , -0.50V P f C
ι • 1/2AgOOAg
1
OH
' •AgO* + H 0 + e E , , 0.00V 2 p a
Ag
1
— » AgOAg
A g O A g + e"-> A g + AgO" E p ^ , c -0.7 5V
AgOOAg + 2 e " -> 2AgO
AgO" + H 0 + e"- 2
Ag(I)/0 2 E L E C T R O C H E M I S T R Y I N MeCN AT GC ELECTRODE
+
(1) 4 Ag + 0 2 + 4e"-> 2 A g O A g E P f C , - 0 . 1 0 V v s SCE
|2e" E , , -0.65V
p c
2 AgO" + A g 2
AgO" + H 0 + e"-> A g + 2 "OH 2 E -1.55V

P r cr
+
(2) Ag + e --£2_^ g A 2 E +0.20V
P t or
+
Ag + e^>Ag- _> 1/2 A g 2 E
P, cr -0.10V
I 02f e"
AgOO" -0.95V
E
P. c r
AgOO -> AgOO' + e E

P, ar -0.18V
e~
* AgOO E
P, cr -0.31V
Ag
AgOOAg
+ E
(3) 2 Ag + 0 2 + 2e~—» AgOOAg p,cr -0.10V
AgOOAg + 2e"-> 2 AgO" E P f C , - 1.04V

+
AgOOAg -> 0 2 + 2 Ag + 2e" E , , +0. 90V
p a
+
Ag 2 -> 2 A g + 2e~ E , , + 0.40V
p a

Scheme I I I
A u / OH E L E C T R O C H E M I S T R Y I N MeCN
Au + OH —> AuOH + e , - 0 . 3 5 V v s SCE
1/2 AuOOAu
OH
AuO" + H 0 2 + e Ep, ,a +0.20V
— • AuOAu
AuOH
AuOAu + H 0 2 + e E p , , +0.50V
a
AuOAu + e -» A u + AuO Ep, f

C -0.60V
AuOOAu + 2 e " -» 2 AuO" Ep, , -0.76V

c

+
a t a A g e l e c t r o d e ( A g + A g + e " —» A g ) . T h i s b o n d e n e r 2
gy must b e overcome t o p r o v i d e a n u n p a i r e d s - e l e c t r o n f o r
b o n d i n g w i t h t h e -OH f r o m t h e o x i d a t i o n o f "OH.
M-M + 2 "OH -» 2 M-OH + 2e" E O l

M 0H/M,"0H (9)
( B . E . ) M _ O H = [ E ° " -OH/-OH " E°'MOH/M,-OH]23.1 +

1/2 ( B . E . ) M - M (10)
T a b l e I s u m m a r i z e s t h e b o n d e n e r g i e s f o r t h e M-OH b o n d
t h a t r e s u l t from t h e e l e c t r o c h e m i c a l data a n d t h i s c a l c u
lation. The v a l u e s compare c l o s e l y w i t h t h o s e f o r g a s -
p h a s e M-0 b o n d e n e r g i e s ( 1 5 ) . A recent gas-phase study
e s t i m a t e s t h a t t h e Au-OH b o n d e n e r g y i s g r e a t e r t h a n 6 2 . 5
k c a l (16).
A l t h o u g h t h e i n i t i a l s t e p s o f Schemes I A I I A a n d
IIIA a r e s t r o n g l y supporte
subsequent r e a c t i o n
based s o l e l y on t h e e l e c t r o c h e m i c a l measurements o f F i g
u r e s 1 - 3 , 6 a n d 7. I n t e r m e d i a t e s h a v e n o t b e e n d e t e c t e d
or i s o l a t e d , b u tthere i s s e l f c o n s i s t e n c y i n t h e redox
t h e r m o d y n a m i c s b e t w e e n t h e M/"OH s y s t e m s a n d t h e M+/02
systems. The c y c l i c voltammograms a l s o i n d i c a t e t h e p r e
s e n c e o f common i n t e r m e d i a t e s b e t w e e n t h e t w o s y s t e m s .
One o f t h e s e , MOOM, i s e s p e c i a l l y i n t r i g u i n g a n d i s t h e
focus o f current e f f o r t s t o detect and c h a r a c t e r i z e i t
via surface-analysis techniques.
Although each o f t h e metal e l e c t r o d e s h a sbeen p o l
i s h e d immediately p r i o r t o t h e measurements t h a t a r e i l l
u s t r a t e d i n F i g u r e s 1-3, t h e i n i t i a l n e g a t i v e s c a n s o f t e n
e x h i b i t s i g n i f i c a n t r e d u c t i o n peaks due t o a u t o x i d a t i o n
b y O 2 . T h e p o l i s h i n g p r o c e s s u n d o u b t e d l y a t o m i z e s some o f
t h e M-M s u r f a c e m o l e c u l e s , w h i c h p r o b a b l y i n i t i a t e s t h e
p r o c e s s v i a a mechanism s i m i l a r t o t h a t f o r t h e a u t o x i
d a t i o n o f r e d u c e d i r o n p o r p h y r i n s (17)
M.
Μ· + ·02" -> Μ-00· -» MOOM

2Μ·
• » 2 MOM (11)
T h e f i n a l s t e p may b e s l o w a n d r e p r e s e n t t h e p a t h f o r
p a s s i v a t i o n o f t h e surfaces o f t h e coinage metals.
Acknowledgment
This work was s u p p o r t e d b y t h e N a t i o n a l S c i e n c e Founda

tion u n d e r G r a n t No. CHE-8516247.

32. SAWYER AND CHOOTO Formation ofMetal-Oxygen Surface Compounds 483
Literature Cited
1. Tsang, P . K . S . ; Cofré, P . ; Sawyer, D.T. Inorg. Chem.
1987, 26, 3604.
2. K a r l i n , K . S . , Zubieta, J., Eds. Biological and
Inorganic Copper Chemistry, Adenine: Guilderland,
New York, 1986; V o l . 1 and 2.
3. Verykios, K . E . ; Stein, F . P . ; Coughlin, R.W. Catal.
Rev. S c i . Eng. 1980, 22, 197.
4. Schwank, J . Gold Bull. 1983, 16, 4.
5. Cu: Spitzer, Α.; Luth, H. Surf. S c i . 1982, 118, 121.
6. Campbell, C.T. Surf. Sci., 1986, 173, L641.
7. Gutka, D . A . ; Madix, R . J . J. Am. Chem. Soc. 1987,
109, 1708.
8. C. Pyun, C . - H . ; Park, S.M. J. Electrochem. Soc.
1986, 133, 2024
9. Stonehart, P. Electrochim
10. Herman, G . E . ; Alonso, ; ,
J. Electroanal. Chem., 1987, 223, 277.
11. Sawyer, D.T., Robert, J.L., J r . Experimental
Electro-chemistry For Chemists, Wiley-Interscience,
New York, 1974, pp. 44-46, 144-145, 336-339.
12. Simmons, M.G.; Merrill, C . L . ; Wilson, L.J.;
Bottomley, L . A . ; Kadish, K.M. J. Chem. Soc. Dalton
Trans. 1980, 10, 1827.
13. Goolsby, A . D . ; Sawyer, D.T. Anal. Chem. 1968, 40,
1979.
14. Parsons, R. Handbook of Electrochemical Data,
Butters-worth, London, 1952.
15. CRC Handbook of Chemistry and Physics, 68th E d . ;
CRC: Boca Raton, FL; pp. F-168 - F-177.
16. Weil, D.A.; Wilkins, C.L. J. Am. Chem. Soc. 1985,
107, 7316.
17. Chin, D . - H . ; LaMar, G.N.; Balch, A . L . J. Am. Chem.
Soc. 1980, 102, 4344.

Chapter 33
Effect of Surface Crystallography

on Electrocatalytic Oxidation of Carbon
Monoxide on Platinum Electrodes
B. Love and J. Lipkowski
Guelph-Waterloo Centre for Graduate Work in Chemistry, University

of Guelph,
The kinetics of CO oxidation from HClO solutions on 4
the (100), (111) and (311) single crystal planes of

platinum has been investigated. Electrochemical
oxidation of CO involves a surface reaction between
adsorbed CO molecules and a surface oxide of Pt. To
determine the rate of this reaction the electrode was
first covered by a monolayer of CO and subsequently
exposed to anodic potentials at which Pt oxide is
formed. Under these conditions the rate of CO
oxidation is controlled by the rate of nucleation and
growth of the oxide islands in the CO monolayer. By
combination of the single and double potential step
techniques the rates of the nucleation and the island
growth have been determined independently. The
results show that the rate of the two processes
significantly depend on the crystallography of the Pt
surfaces.
Carbon monoxide adsorbs strongly on platinum surfaces thereby acting
as a poison of platinum catalysts. The adsorption of CO has a
particularly adverse affect on the performance of low temperature
hydrogen/oxygen and methanol/oxygen fuel cells. In the first case
CO is frequently present as an impurity in the hydrogen fuel, in the
second case i t is produced as an intermediate in the methanol
oxidation reaction. In both cases the presence of CO is responsible
for an increase of the overvoltage for the anodic reactions.
Therefore, the electrosorption and electrooxidation of CO on Pt have
been investigated extensively. The bulk of the previous research
was carried out on polycrystalline platinum, see [1-3] for recent
reviews of the literature, and only a few papers have been published
on CO adsorption/oxidation on well defined single crystal surfaces
[3-6].
It is known that CO oxidation involves a surface reaction between
adsorbed CO molecules and an adsorbed oxygen species, which we shall
refer to as a surface oxide, but which may be an adsorbed oxygen
0097-6156/88/0378-0484S06.00/0
β

33. L O V E AND LIPKOWSKI CO Oxidation and Platinum Electrodes 485
atom, OH r a d i c a l or even a water m o l e c u l e . At Pt s u r f a c e s p a r t i a l l y

covered by CO the oxygen s p e c i e s forms i s l a n d s , the r e a c t i o n between
the adsorbed CO m o l e c u l e s and the s u r f a c e o x i d e proceeds at the
p e r i m e t e r of the i s l a n d s [ 7 ] . I f the e l e c t r o d e s u r f a c e i s i n i t i a l l y
c o v e r e d by a m o n o l a y e r o f CO and s u b s e q u e n t l y exposed t o the
c o n d i t i o n s at w h i c h the o x i d a t i o n o f CO o c c u r s , the r a t e of r e a c t i o n
i s c o n t r o l l e d by the r a t e of n u c l e a t i o n and growth of the o x i d e
islands. I t has been shown by P l e t c h e r and McCallum t h a t p o t e n t i a l
s t e p e x p e r i m e n t s p r o v i d e the best way t o s t u d y t h i s r e a c t i o n [ 8 ] .
The o b j e c t i v e of the present work was t o a s s e s s the i n f l u e n c e of
s u r f a c e c y r s t a l l o g r a p h y on t h e m e c h a n i s m and k i n e t i c s o f CO
o x i d a t i o n a t Pt s u r f a c e s . Three c r y s t a l l o g r a p h i c o r i e n t a t i o n s ;
(111), (100) and ( 3 1 1 ) , were s e l e c t e d f o r t h i s i n v e s t i g a t i o n . The
(111) and (100) p l a n e s have smooth s u r f a c e s b u i l d up from t h r e e and
f o u r f o l d c o o r d i n a t i o n c e n t e r s , r e s p e c t i v e l y . The (311) p l a n e i s a
s t e p p e d s u r f a c e p o s s e s s i n g an e q u a l number of the t h r e e f o l d and
four f o l d c o o r d i n a t i o n centers I previou investigation f CO
o x i d a t i o n a t Pt s i n g l e c r y s t a
f o l l o w e d by c y c l i c voltammetr
c u r r e n t s are a complex f u n c t i o n of the r a t e s of n u c l e a t i o n and
growth. Thus, the r e s u l t s p r o v i d e o n l y q u a l i t a t i v e i n f o r m a t i o n . In
the present work p o t e n t i a l s t e p t e c h n i q u e s were a p p l i e d such t h a t
the n u c l e a t i o n and growth r a t e s were measured i n d e p e n d e n t l y . In
t h i s way the e f f e c t o f s u r f a c e m o r p h o l o g y on t h e r a t e o f CO
o x i d a t i o n has been q u a n t i t a t i v e l y a s s e s s e d .
Experimental
The s i n g l e c r y s t a l e l e c t r o d e s were p r e p a r e d a c c o r d i n g t o the

procedure d e s c r i b e d elsewhere [ 9 ] . The e l e c t r o d e s u r f a c e s were
cleaned u s i n g C l a v i l i e ^ s f l a m i n g and quenching t e c h n i q u e [10].
C o n t a c t between the i n v e s t i g a t e d s u r f a c e and the e l e c t r o l y t e was
made u s i n g the hanging e l e c t r o l y t e method [ 1 1 ] . A conventional,
t h r e e e l e c t r o d e c e l l was used i n the e l e c t r o c h e m i c a l i n v e s t i g a t i o n s .
An e x t e r n a l r e v e r s i b l e hydrogen e l e c t r o d e (RHE) was used as the
reference electrode. The 0.1 M HC10,, s o l u t i o n s used i n both the
c e l l and the e x t e r n a l RHE compartment were prepared from s u p r a p u r e
65% HC10 ( S e a s t a r C h e m i c a l s ) and M i l l - Q water (17 ΜΩ cm).
H Argon
was used f o r d e g a s s i n g the s o l u t i o n s . A l l e x p e r i m e n t s were c a r r i e d
out at room temperature (21 ± 1 °C).
C y c l i c voltammetry (CV) c u r v e s were r e c o r d e d on a K i p p and Zonen
BD91 X-Y r e c o r d e r and the c u r r e n t - t i m e t r a n s i e n t s r e s u l t i n g from the
p o t e n t i a l s t e p e x p e r i m e n t s were r e c o r d e d d i g i t a l l y . The a p p a r a t u s
used i n c l u d e d a PAR Model 173 p o t e n t i o s t a t and an IBM XT computer
equipped w i t h a IS-16 A-D i n t e r f a c e (RC E l e c t r o n i c s , C a l i f o r n i a ) .
The i n t e r f a c e had i t s own memory b u f f e r and a l l o w e d f o r the
a c q u i s i t i o n of 2048 p o i n t s at a v a r i a b l e A/D c o n v e r s i o n f r e q u e n c y
which can be as h i g h as 1 MHz w i t h a r e s o l u t i o n 12 b i t s over an
i n p u t range of ±2.5 v o l t s .
Results
C y c l i c Voltammetry. Figure 1 shows the c y c l i c voltammograms (CV's)

d e t e r m i n e d f o r the t h r e e c r y s t a l p l a n e s i n a c l e a n (CO free)

F i g u r e 1. S o l i d l i n e s - c y c l i c v o l t a m m e t r i c curves f o r hydrogen and

oxygen a d s o r p t i o n a t t h e t h r e e P t s i n g l e c r y s t a l p l a n e s i n v e s t i g a t e d
determined from the pure (CO f r e e ) 0.1 M HC10„ s o l u t i o n . Dotted
l i n e s - c y c l i c v o l t a m m e t r i c c u r v e s o f adsorbed CO o x i d a t i o n ( n o t e :
t h e s e n s i t i v i t y f o r t h e CO o x i d a t i o n curves has been t e n f o l d
a t t e n u a t e d . Sweep r a t e 50 mv/s.

electrolyte solution. The shape of the CV's i s v i r t u a l l y i d e n t i c a l

to the curves which have been o b t a i n e d f o r s i m i l a r l y o r i e n t e d f a c e s
of p l a t i n u m s i n g l e c r y s t a l s , c l e a n e d and c h a r a c t e r i z e d by low-energy
e l e c t r o n d i f f r a c t i o n (LEED) and A u g e r - e l e c t r o n s p e c t r o s c o p y (AES) i n
a combined U H V - e l e c t r o c h e m i s t r y experiment [12-14],
f
The d o t t e d curves are CV s determined f o r Pt e l e c t r o d e s covered
by a monolayer of CO i n an e l e c t r o l y t e f r e e from b u l k CO. This
c o n d i t i o n was a c h i e v e d by imposing a p o t e n t i a l of 0.40 V on the
e l e c t r o d e immersed i n a s o l u t i o n s a t u r a t e d w i t h CO f o r 2 min and
s u b s e q u e n t l y removing the CO from the b u l k of the e l e c t r o l y t e by
p u r g i n g the s o l u t i o n w i t h argon f o r a f u r t h e r 2 min. The main
f e a t u r e of these c u r v e s i s the sharp peak c o r r e s p o n d i n g t o CO
oxidation. F o l l o w i n g o x i d a t i o n o f the adsorbed CO at p o t e n t i a l s
T
l e s s than 1.10 V the shape o f CV s r e t u r n e d t o t h a t d e s c r i b e d by a
s o l i d l i n e and c h a r a c t e r i s t i c f o r the CO f r e e e l e c t r o l y t e . This
i n d i c a t e s t h a t the a d s o r p t i o n and the o x i d a t i o n o f CO do not p e r t u r b
the c r y s t a l l o g r a p h i c s t r u c t u r f th surface Th figur als
shows a s m a l l a f f e c t of
CO o x i d a t i o n r e v e a l e d b
CO o x i d a t i o n peak i n the p o s i t i v e d i r e c t i o n from the (100) s u r f a c e
to the (111) s u r f a c e .
P o t e n t i a l Step Experiments
A. S i n g l e S t e p E x p e r i m e n t s . P o t e n t i a l s t e p e x p e r i m e n t s were
p e r f o r m e d i n o r d e r t o determine the r e a c t i o n mechanism and the
reaction rate. As d e s c r i b e d a b o v e , t h e p l a t i n u m s u r f a c e was
i n i t i a l l y covered by a monolayer of CO at a c o n t r o l l e d p o t e n t i a l , E^
= 0.40 V ( r e f e r r e d t o as the i n i t i a l p o t e n t i a l ) and then CO was
removed f r o m t h e b u l k o f t h e s o l u t i o n . Next, the electrode
p o t e n t i a l was s u d d e n l y c h a n g e d t o a more p o s i t i v e v a l u e , E f ,
( r e f e r r e d t o as the f i n a l p o t e n t i a l ) where the adsorbed CO was
o x i d i z e d and the r a t e of o x i d a t i o n was f o l l o w e d by r e c o r d i n g the
r e s u l t i n g current t r a n s i e n t s .
R e p r e s e n t a t i v e c u r r e n t - t i m e t r a n s i e n t s o b t a i n e d f o r a Pt(100)
s u r f a c e are p r e s e n t e d as a t h r e e - d i m e n s i o n a l i - t - E p l o t i n F i g u r e 2.
The graph i s c o n s t r u c t e d i n such a way t h a t the time and c u r r e n t
a x i s are i n the plane o f the f i g u r e w h i l e the Ef a x i s i s normal to
t h i s plane. A l l t r a n s i e n t s d i s p l a y the c h a r a c t e r i s t i c maximum, the
t A s t h e f i n a l
c o o r d i n a t e of which w i l l be denoted as (i ax» max^* m
p o t e n t i a l becomes p r o g r e s s i v e l y more p o s i t i v e i a x i n c r e a s e s and

m
t m adecreases.
x The area under the t r a n s i e n t s g i v e s the charge o f
adsorbed CO (σςο)· A f t e r c o r r e c t i o n f o r c h a r g i n g o f the double
w a s
l a y e r and the charge of the o x i d e f o r m a t i o n , the value o f σςο
2
found t o be equal to 350 yCcm" and t o be w i t h i n an e r r o r of ±10%,
t 0
independent of the e l e c t r o d e p r o t e n t i a l . Thus, the r a t i o of σςο
the doubled charge of adsorbed hydrogen i s a p p r o x i m a t e l y e q u a l t o
0.7. Assuming t h a t the r a t i o of adsorbed hydrogen atoms to p l a t i n u m
atoms at the s u r f a c e i s e q u a l t o one, the above r e s u l t i s e q u a l t o
t h e d e g r e e o f c o v e r a g e o f t h e P t s u r f a c e by CO molecules.
I n c i d e n t a l l y , the same v a l u e of the s a t u r a t i o n coverage was found
for CO a d s o r p t i o n on Pt from the gas phase [ 1 5 ] . The shape o f the
t r a n s i e n t s changes w i t h p o t e n t i a l . F i g u r e 3a shows t h r e e c u r r e n t
t r a n s i e n t s r e c o r d e d at low p o t e n t i a l s and F i g u r e 3b shows t h r e e

2 0 0
o.o T I M E (ms)
Figure 2. T h r e e - d i m e n s i o n a l p l o t s of the CO o x i d a t i o n t r a n s i e n t s
determined i n t h e s i n g l e p o t e n t i a l s t e p experiments on t h e P t ( 1 0 0 )
e l e c t r o d e i n 0.10 M HC10 s o l u t i o n .
U The p o t e n t i a l s t e p was a p p l i e d
from Ej_ = +0.40 V t o E f d i s p l a y e d on the t h i r d a x i s o f the f i g u r e .

33. L O V E AND LIPKOWSKI CO Oxidation and Pfotinum Electrodes 489
< b
Ε
in 10£0
d
980^
TIME 8.0 ms/div

F i g u r e 3 a. Three c u r r e n t t r a n s i e n t s e l e c t e d from F i g u r e 2 f o r t h e
low v a l u e s of the f i n a l p o t e n t i a l . The v a l u e s o f E f i n mV a r e
i n d i c a t e d above t h e c o r r e s p o n d i n g c u r v e s . b. T h r e e c u r r e n t
t r a n s i e n t s s e l e c t e d f r o m F i g u r e 2 f o r the h i g h v a l u e s o f the
potential. The v a l u e s o f E f a r e i n d i c a t e d above the c o r r e s p o n d i n g
curves.

t r a n s i e n t s observed a t h i g h p o t e n t i a l s . The curves presented i n

F i g u r e 3a have a symmetric b e l l shape. I n t e g r a t i o n o f these curves
g i v e s a charge which i s a p p r o x i m a t e l y e q u a l t o t h e product o f i m a x
and t m a .x The curves have a form c o n s i s t e n t w i t h t h a t produced by a

r e a c t i o n c o n t r o l l e d by p r o g r e s s i v e n u c l e a t i o n and growth o f o x i d e
i s l a n d s i n the CO monolayer, and can be d e s c r i b e d by t h e e x p r e s s i o n
[16, 1 7 ] :
2 2 2 3
i = o ïïk k t exp(~rrk k t / 3 )
T 1
where σ? i s the charge c o r r e s p o n d i n g t o t h e a r e a c o n t a i n e d under the
t r a n s i e n t , k^ i s the r a t e o f n u c l e a t i o n , and kQ i s the r a t e o f
n u c l e i growth.
The t r a n s i e n t s g i v e n i n F i g u r e 3b a r e asymmetric. The area under
the curves i s almost two times h i g h e r than the product o f i and m a x
I n
tmax* t h e i n i t i a l segment o f the c u r v e s , t h e c u r r e n t v a r i e s
l i n e a r l y w i t h time. These f e a t u r e s a r e c o n s i s t e n t w i t h t h e process
c o n t r o l l e d by t h e i n s t a n t a n e o u
number o f o x i d e i s l a n d
w e l l d e s c r i b e d by t h e e x p r e s s i o n [16, 1 7 ] :
2 2 2
i = 1(0) + o 2ïïN k texp(-ïïN k t )
T N N Q 2
where c u r r e n t i ( 0 ) c o r r e s p o n d s t o the r e a c t i o n p r o c e e d i n g a t the
perimeter of the oxide i s l a n d s formed d u r i n g t h e time o f t h e
c h a r g i n g o f the double l a y e r . I f the time c o n s t a n t o f the c e l l can
be s u b s t a n t i a l l y reduced i ( 0 ) c o u l d r e a c h v a l u e s c l o s e t o z e r o .
The c h a n g e s i n t h e t r a n s i e n t shapes r e f l e c t changes i n t h e
r e a c t i o n mechanism. At low p o t e n t i a l s , t h e r e a c t i o n i s c o n t r o l l e d
s i m u l t a n e o u s l y by t h e r a t e o f n u c l e a t i o n and t h e growth o f the o x i d e
i s l a n d s , a t h i g h p o t e n t i a l s t h e r e a c t i o n i s c o n t r o l l e d by t h e r a t e
of the i s l a n d growth.
The i n v e r s e o f the time c o r r e s p o n d i n g t o the c u r r e n t maximum can
be taken as a measure o f t h e r e a c t i o n r a t e [16-18]. For a r e a c t i o n
c o n t r o l l e d by p r o g r e s s i v e n u c l e a t i o n and growth t i s g i v e n by the
r n a x
expression:
tmax = (2/irk kG>* N 3
and i f t h e r a t e i s c o n t r o l l e d by i s l a n d growth, t m a x i s equal t o :
1 i
tmax =
( 2 ^
27T%k G
F i g u r e 4 shows a p l o t o f the l o g a r i t h m o f t a g a i n s t the f i n a l

m a x
p o t e n t i a l E f determined f o r t h e t h r e e c r y s t a l l o g r a p h i c o r i e n t a t i o n s
investigated. The p l o t s a r e n o n l i n e a r w h i c h i s c o n s i s t e n t w i t h a
change i n t h e r e a c t i o n mechanism d i s c u s s e d above as the value o f E f
i s increased. They a l s o d i s p l a y an apparent a f f e c t due t o s u r f a c e
c r y s t a l l o g r a p h y on the r a t e o f the o x i d a t i o n r e a c t i o n . T h i s a f f e c t
i s p a r t i c u l a r l y s i g n i f i c a n t i n t h e range o f low p o t e n t i a l s where t h e
r e a c t i o n r a t e i s c o n t r o l l e d s i m u l t a n e o u s l y by the r a t e o f n u c l e a t i o n
and t h e r a t e o f growth o f t h e o x i d e i s l a n d s . To get f u r t h e r i n s i g h t
i n t o t h e mechanism o f the i n v e s t i g a t e d r e a c t i o n an attempt has been

-2.5
0.800 0.900 1.000 E/volts
F i g u r e 4. A p l o t of the l o g a r i t h m o f the time c o r r e s p o n d i n g t o the

maximum on t h e c u r r e n t t r a n s i e n t s p l o t t e d a g a i n s t t h e f i n a l
p o t e n t i a l f o r the three s i n g l e c r y s t a l surfaces i n v e s t i g a t e d .

made t o determine the r a t e o f n u c l e a t i o n and the r a t e o f the growth

independently. T h i s r e q u i r e d double p o t e n t i a l s t e p experiments [ 7 ,
16].
B. Double Step Experiments To determine the r a t e s of o x i d e i s l a n d

growth over the broad range o f e l e c t r o d e p o t e n t i a l s , the f o l l o w i n g
double s t e p experiments were performed. A f t e r the s u r f a c e was
covered by a monolayer of CO u s i n g the procedure d e s c r i b e d i n the
p r e c e d i n g paragraphs a s h o r t d u r a t i o n p u l s e (2 ms) t o Ε = 1.10 V was
a p p l i e d t o the e l e c t r o d e . Next the p o t e n t i a l was stepped back t o a
lower value Ef and the chronoamperometric t r a n s i e n t was recorded.
D u r i n g t h e s h o r t p u l s e t o 1.10 V a l a r g e number of n u c l e i were
generated so t h a t the number of n u c l e i formed d u r i n g the subsequent
p e r i o d at p o t e n t i a l Ef c o n t r i b u t e d n e g l i g i b l y t o the t o t a l number of
n u c l e i present on the s u r f a c e . T h e r e f o r e the o x i d a t i o n o f CO a t
p o t e n t i a l Ef was assumed t o be p r o c e e d i n g from a f i x e d number of
n u c l e i and was expected t o be c o n t r o l l e d o n l y by the r a t e of the
i s l a n d growth. I t shoul
f o r m a t i o n of a n u c l e i i
the CO monolayer o f s u f f i c i e n t s i z e t o i n i t i a l i z e the i s l a n d growth.
The number of the h o l e s made a t Ε = 1.10 V d e f i n i t e l y depends on the
type o f the s u r f a c e o x i d e formed at t h i s p o t e n t i a l . However, the
subsequent expansion of the h o l e s at p o t e n t i a l Ef i s c o n t r o l l e d by
the s t r u c t u r e of the o x i d e o v e r l a y e r w h i c h e x i s t s at the p a r t i c u l a r
value o f E f .
The s h a p e o f t h e t r a n s i e n t s d e t e r m i n e d i n the double s t e p
e x p e r i m e n t s i s compared w i t h the shape of the t r a n s i e n t s o b t a i n e d
from the s i n g l e s t e p e x p e r i m e n t s , f o r t h r e e s e l e c t e d v a l u e s of E f ,
i n F i g u r e 5. As e x p e c t e d , the shape of the t r a n s i e n t determined i n
the double s t e p experiments changes from t h a t c h a r a c t e r i s t i c f o r the
p r o g r e s s i v e n u c l e a t i o n and growth t o t h a t c h a r a c t e r i s t i c f o r the
i n s t a n t a n e o u s n u c l e a t i o n and growth. The i n i t i a l segments of the
t r a n s i e n t s determined i n the double s t e p experiments depend l i n e a r l y
on t i m e . The s l o p e of t h i s s e c t i o n o f the c u r v e s , a c c o r d i n g t o
e q u a t i o n 2, i s p r o p o r t i o n a l to the square o f the growth c o n s t a n t k
and the number o f n u c l e i formed at the s u r f a c e d u r i n g the s h o r t
p u l s e t o Ε = 1.10 V. The l o g a r i t h m of the square r o o t of these
s l o p e s i s p l o t t e d as a f u n c t i o n o f the f i n a l p o t e n t i a l E f , i n F i g u r e
6, f o r the t h r e e c r y s t a l l o g r a p h i c o r i e n t a t i o n s i n v e s t i g a t e d . The
p l o t s are n o n l i n e a r and t h e i r s l o p e changes from about 80 mV/decade
at Ef < 850 mV t o 240 mV/decade at E f > 850 mV. A c t u a l l y the
p o t e n t i a l r a n g e 750 mV < E f < 1000 mV, f o r which the growth
c o n s t a n t s were determined, corresponds t o the i n i t i a l s t a g e of the
o x i d a t i o n o f the p l a t i n u m s u r f a c e , see F i g u r e 1. In t h i s range, the
coverage of t h e e l e c t r o d e s u r f a c e by the water o x i d a t i o n p r o d u c t ,
p r o b a b l y a b s o r b e d OH s p e c i e s i s s m a l l e r than 30% and changes
s t r o n g l y w i t h p o t e n t i a l . T h e r e f o r e , the i s l a n d s w h i c h are formed i n
the monolayer of CO on the s u r f a c e must be composed of adsorbed
water and the OH s p e c i e s . O b v i o u s l y , the c o n c e n t r a t i o n o f OH w i t h i n
the i s l a n d , and at the same time at the p e r i m e t e r of the i s l a n d ,
v a r y w i t h the e l e c t r o d e p o t e n t i a l . Assuming t h a t the i s l a n d growth
i s c o n t r o l l e d by the r e a c t i o n between CO and the OH s p e c i e s present
at the p e r i m e t e r l i n e , t h e v a r i a t i o n o f t h e g r o w t h r a t e w i t h
p o t e n t i a l can be e x p l a i n e d , a t l e a s t q u a l i t a t i v e l y , by t h e
v a r i a t i o n of the OH coverage.

\840
>
5
Ε
δ
d
800
a:
ZD
Ο
84θ;
A \ \ b
< M \ \
m
E
CN
ο
/ \ \
d
ë
LiJ
a:
0d
Ο
><:
TIME 100 ms/div
F i g u r e 5. Comparison o f t h e c u r r e n t t r a n s i e n t s o b t a i n e d i n t h e
s i n g l e s t e p and t h e d o u b l e s t e p e x p e r i m e n t s . a. t h e c u r r e n t
t r a n s i e n t determined i n a s i n g l e s t e p e x p e r i m e n t s , t h e same p l o t as
i n F i g u r e 3a. b. t h e c u r r e n t t r a n s i e n t s r e c o r d e d i n t h e double s t e p
experiments when t h e p o t e n t i a l was f i r s t stepped t o Ε = 1.10 V f o r a
p e r i o d o f 2 ms and t h e n s t e p p e d b a c k t o E f which v a l u e s a r e
indicated at corresponding curves.

1.700 +
E
υ
w 1.200
<
Ε
0.700
Q.
Ο
» 0.200 +
o
ο
-0.300
740 790 840 890 940 990
POTENTIAL E(RHE) (mV)
Figure 6. A p l o t o f the l o g a r i t h m o f the square r o o t o f the i n i t i a l
s l o p e o f t h e c u r r e n t time t r a n s i e n t s determined i n t h e double s t e p
experiments a g a i n s t the f i n a l p o t e n t i a l f o r the t h r e e s i n g l e c r y s t a l
surfaces investigated.
Ο
Q
-1.000
770 780 790 800 810 820 830 840 850 860
POTENTIAL E/RHE (mV)
F i g u r e 7. A p l o t o f the l o g a r i t h m o f the r a t i o k^/N^ a g a i n s t t h e
e l e c t r o d e p o t e n t i a l determined f o r t h e (311) surface".

The v e r t i c a l d i s t a n c e between the p l o t s i n F i g u r e 6 i s a measure

k / N
o f the i n f l u e n c e of s u r f a c e c r y s t a l l o g r a p h y on the product G - N
P r o v i d e d the same number of n u c l e i were generated at each s u r f a c e

d u r i n g the p r e p u l s e to Ε = 1.10 V, the magnitude of the v e r t i c a l
s e p a r a t i o n between the p l o t s i l l u s t r a t e s the v a r i a t i o n of the r a t e
of growth. The maximum d i s t a n c e between the p l o t s i n F i g u r e 6
amounts t o h a l f an order of magnitude and t h i s s u g g e s t s t h a t the
i n f l u e n c e of the s u r f a c e c r y s t a l l o g r a p h y on the r a t e of growth i s
significant.
The s i n g l e s t e p and the double s t e p experiments were f i n a l l y
combined to determine the r a t e c o n s t a n t s f o r n u c l e a t i o n k . By
f i t t i n g e q u a t i o n 1 t o the s i n g l e s t e p t r a n s i e n t s or by u s i n g the ΒFT
2
a n a l y s i s [19] on the t r a n s i e n t s the product k k was o b t a i n e d . The
double s t e p e x p e r i m e n t s a l l o w e d f o r the d e t e r m i n a t i o n of the product
2
N^k . From the r a t i o of the two r e s u l t s , the q u o t i e n t ^ / N ^ was
c a l c u l a t e d . F i g u r e 7 shows a p l o t of the l o g a r i t h m of k / % against
the e l e c t r o d e p o t e n t i a l determined f o Pt (311) electrode Th
relationship i s linear wit
s u g g e s t s t h a t the f o r m a t i o
the CO monolayer i n v o l v e s a charge t r a n s f e r as the r a t e d e t e r m i n i n g
step. The c a l c u l a t i o n s of the n u c l e a t i o n r a t e c o n s t a n t f o r the two
o t h e r s u r f a c e s are i n p r o g r e s s and w i l l be r e p o r t e d s h o r t l y , the
r e s u l t s o b t a i n e d so f a r i n d i c a t e t h a t s u r f a c e c y r s t a l l o g r a p h y has a
s i g n i f i c a n t i n f l u e n c e on r a t e o f n u c l e a t i o n as w e l l .
Surnmar y
O x i d a t i o n o f CO at the i n t e r f a c e between ( 1 1 1 ) , (100) and (311) Pt

s i n g l e c r y s t a l s u r f a c e s and a s o l u t i o n of an aqueous e l e c t r o l y t e has
been i n v e s t i g a t e d . A monolayer of CO has been adsorbed onto the Pt
e l e c t r o d e s u r f a c e and t h e n o x i d i z e d by a p p l y i n g an a n o d i c p o t e n t i a l
pulse. The onset of CO o x i d a t i o n c o i n c i d e s w i t h the b e g i n n i n g o f
oxygen a d s o r p t i o n (OH r a d i c a l s or 0 atoms) at the f r e e platinum
surfaces. The p l o t s of the o x i d a t i o n r a t e v e r s u s time d i s p l a y
maximum and t h e i r shape i s c h a r a c t e r i s t i c f o r a r e a c t i o n c o n t r o l l e d
by n u c l e a t i o n and growth phenomena. T h e r e f o r e , the o v e r a l l r a t e o f
the r e a c t i o n can be e x p r e s s e d i n terms of the r a t e of n u c l e a t i o n
(formation of oxide i s l a n d s ) and t h e r a t e o f n u c l e i g r o w t h
( e x p a n s i o n of the o x i d e i s l a n d ) . By a c o m b i n a t i o n of the s i n g l e
p o t e n t i a l s t e p and t h e d o u b l e p o t e n t i a l s t e p e x p e r i m e n t s the
n u c l e a t i o n and t h e n u c l e i g r o w t h r a t e s have been d e t e r m i n e d
independently. The r e s u l t s have shown t h a t the r a t e of the n u c l e i
growth (island expansion) s i g n i f i c a n t l y depends on the
c r y s t a l l o g r a p h y of the Pt s u r f a c e . P r e l i m i n a r y c a l c u l a t i o n s have
shown t h a t the r a t e of t h e n u c l e a t i o n depends on t h e surface
s t r u c t u r e as w e l l .
Acknowledgments
T h i s work was s u p p o r t e d by a g r a n t from N a t u r a l S c i e n c e s and

E n g i n e e r i n g Research C o u n c i l o f Canada. We thank J . R i c h e r f o r h i s
h e l p i n w r i t i n g s o f t w a r e f o r the data a c q u i s i t i o n and p r o c e s s i n g .

Literature Cited
1a) Kunimatsu, K.; Golden, W.G.; Seki, H.; Philpott, M.R. Langmuir,
1985, 1, 245.
b) Kunimatsu, K.; Seki, H.; Golden, W.G.; Gordon, J.D.; Philpott,
M.R. Langmuir, 1986, 2, 464.
2. Sobkowski, J.; Czerwinski, A. J. Phys. Chem. 1985, 89, 365.
3. Wagner, F.T.; Moylan, T.E.; Schnieg, J.S. Surface Science, in
press.
4a) Beden, B.; Bilmes, S.; Lamy, C.; Leger, J.M.; J. Electroanal.
Chem. 1983, 149, 295.
b) Lamy, C . ; Leger, J . M . ; Clavilier, J . ; Parsons, R. J.
Electrochem. Chem. 1983, 150, 71.
c) Leger, J.M.; Beden, B.; Lamy, C.; Bilmes, S. J. Electroanal.
Chem. 1984, 170, 305.
5. Wagner, F.T.; Ross, Jr., Ph.N.; J. Electroanal. Chem., 1983,
50, 141.
6a) Palaikis, L.; Zurawski
Science, in press.
b) Santo, E . ; Leiva, E.P.M.; Vielstich, W.; Linke, V. J.
7a) Gilman, S. J. Phys. Chem. 1963, 67, 78.
b) Gilman, S. J. Phys. Chem. 1964, 68, 70.
8. McCallum, C.; Pletcher, D. J. Electroanal. Chem. 1976, 70, 277.
9. Seto, K.; Iannelli, Α.; Love, B.; Lipkowski, J. J. Electroanal.
Chem. 1987, 226, 351.
10. C l a v i l i e r , J.; Faure, R.; Guinet, G.; Durand, R. J.
11. Dickertmann, D.; Koppitz, F.D.; Schultze, J.W. Electrochim.
Acta. 1976, 21 967.
12. Ross, P.N.; Wagner, F.T. In Advances in Electrochemistry and
Electrochemical Engineering; Gerischer, H.; Tobias, C.W., Eds.;
Wiley; New York, 1984; Vol. 13, p. 69.
13. Aberdam, D.; Durand, R.; Faure, R.; El-Omar, F. Surf. Sci.
1986, 171, 303.
14. Markovic, N.; Hanson, M.; McDougall, G.; Yeager, E.; J.
15. Norton, P.R.; Davis, J.Α.; Jackman, T.E. Surf. Sci., 1982, 122,
L593.
16. Fleischmann, M.; Thirsk, H.R. In Advances in Electrochemistry
and Electrochemical Engineering; Delahay, P., Ed.;
Interscience; New York, 1963; Vol. 3.
17. Deutscher, R.E.; Fletcher, S. J. Electroanal. Chem. 1983, 153,
67.
18. Quarin, G.; Buess-Herman, U.; Gierst, L. J. Electroanal. Chem.
1981, 123, 35.
19. Bewick, Α.; Fleischmann, M.; Thirsh, H.R. Trans. Faraday. Soc.
1962, 58, 2200.

Chapter 34
Hydrogen Electrosorption and Oxidation

of Formic Acid on Platinum
Single-Crystal Stepped Surfaces
N. M . Marković, Α. V. Tripković, N. S. Marinković,

and R. R. Adžić
Institute of Electrochemistry
Metallurgy, and Center for Multidisciplinary Studies, University of
Belgrade, P.O. Box 815, Belgrade, Yugoslavia
Hydrogen adsorption and oxidation of formic a c i d

show a pronounced dependence on the structure of
single c r y s t a l surfaces. The influence o f the
terrace and step orientation and step density is
r e f l e c t e d i n both reactions on step surfaces. The
multiple states of hydrogen adsorption can be
correlated with the nature of adsorption s i t e s .
There i s a n e g l i g i b l e e f f e c t o f adsorbate-
-adsorbate i n t e r a c t i o n on step surfaces. Some
l a t e r a l repulsion of hydrogen adsorbed on Pt(111)
could be i n f e r r e d . A strong adsorption o f
bisulphate and sulphate anions on the (111)
oriented terraces and step s i t e s considerably
affects both reactions. These data show that each
crystallographic o r i e n t a t i o n of the electrode
surfaces gives a different electrochemical
entity.
A remarkable progress has been made i n the l a s t several

years i n e l e c t r o c a t a l y s i s on single c r y s t a l surfaces. This
p a r a l l e l s the progress i n surface science and i t has been p a r t l y
stimulated by developments i n that f i e l d , mostly regarding the
preparation and characterization o f surfaces. New advances i n
preparation of surfaces outside o f high vacuum, achieved i n
e l e c t r o c a t a l y t i c studies, also helped t h i s trend.
E l e c t r o c a t a l y s i s i s a complex area which has lacked so far a
molecular-level understanding of elementary steps in
e l e c t r o c a t a l y t i c reactions. This lack has been due to unsuitable
techniques f o r i n s i t u i d e n t i f i c a t i o n of reaction intermediates
and products and to poor characterization of surfaces, despite
the high s e n s i t i v i t y of electrochemical techniques. A l l e x i s t i n g
0097-6156/88A)378-0497$06.25/0
c

concepts, however, are based on the data obtained with

p o l y c r y s t a l l i n e electrodes. I t already appears that the concepts
r e s u l t i n g from studies with single c r y s t a l surfaces w i l l cast
doubts on e a r l i e r established ideas. Many i n t e r e s t i n g features,
not recognizable with p o l y c r y s t a l l i n e surface, have been
observed. These studies, with in situ spectroscopic
investigations, could provide a rapid development of this
e x c i t i n g area. Since the f i r s t observation of the s t r u c t u r a l
dependence of hydrogen adsorption on Pt single c r y s t a l electrodes
(1), many experiments have been reported on t h i s topic including
the transfer of the samples from the UHV chambers into the
electrochemical c e l l (2-5). Another important development i n
surface preparation i s the flame annealing technique (6) with i t s
modifications (7). Only recently have data from various
laboratories started to agree.
Oxidation of formic acid shows a pronounced s t r u c t u r a l
dependence which i s well i l l u s t r a t e d by data on the low index
planes (8-10) and preliminar
surfaces (11). In t h i
adsorption and oxidation of formic acid on single c r y s t a l Pt
surfaces with 15 orientations are reported.
Experimental
Single c r y s t a l electrodes were obtained from Metal C r y s t a l

Ltd. (Cambridge, England) oriented and cut to better than l o . The
H l a m e
surfaces have been prepared by / ° 2 ^ 2 annealing at 1200K,
followed by cooling i n down to 400K, and were protected by a
drop of water while being transferred into the c e l l . The surface
structures of several electrodes have been checked by LEED.
However, no direct transfer from the UHV chamber into the c e l l
has been achieved. The solutions have been prepared from the
organic-free water obtained from 18 MftMillipore water i r r a d i a t e d
by a UV-radiation f o r 24 h or distilled from a l k a l i n e
permanganate to remove traces of organics. The e l e c t r o l y t e s were
Merck reagent grade acids. Platinum f o i l served as a counter
electrode while Hg/HgCl^ and Hg/HgS0 were used as a reference.
4
A l l potentials are given against the saturated calomel electrode.
Hydrogen Adsorption on the Low-Index Surfaces. The data on the

hydrogen electrosorption on the low-index planes of Pt d i f f e r i n
some d e t a i l , as w i l l be discussed below with the help of r e s u l t s
for stepped surfaces.
Voltammetry curves f o r a l l three low-index surfaces are
given i n F i g . 1. Hydrogen adsorption at P t ( l l l ) , the process at
-0.25 < Ε < -0.05 V i n F i g . 1, i s not affected by the nature of
the anion (such as SO 2-, C10 ~ or F-) (12) . The lack of a well
4
defined peak, i n the drawn-out curve of F i g . 1 c l e a r l y indicates

a strong l a t e r a l repulsion between adsorbed hydrogen adatoms.
This i s probably a consequence of a p a r t i a l l y charge on the
adsorbed hydrogen adatoms which, i n turn, does not allow the

34. MARKOVIC E T A L . Hydrogen Electrosorption and Formic Acid Oxidation 499
Figure 1. C y c l i c voltammetry f o r Pt single c r y s t a l s i n 0.05 M

H S 0 S w e e r a t e 5 0
2 4* P mV/s.

coverage to reach a f u l l monolayer (12). Hydrogen adsorption on

the P t ( l l l ) plane could be described by the following equation:
ί ΐ _ λ ) +
H+ +\e > Η . (D
ad
w h e r e ^ i s a p a r t i a l charge transfer c o e f f i c i e n t .
In contrast to curve i n F i g . 1, two small peaks on a f l a t
portion of the curve at E=-0.025 V and E=-0.15 V have been
observed by several authors (4-6) . Our data to be shown i n the
next section strongly suggest that such peaks are due to a
stepped surface with a small step density, while a well-ordered
P t ( l l l ) surface should give a curve as i n F i g . 1.
The i n t e r p r e t a t i o n of voltammetry curve f o r the Pt(100)
surface poses some problems, e.g. the o r i g i n of the peak at
E=-0.15 V (Fig. 1) . Markovic et a l . (12) ascribed t h i s peak to
hydrogen adsorption on p a r t i c u l a r surface imperfections, the
(111)-oriented step s i t e s The height of t h i s peak varies from
one set of data to another
surface structure. Furthe
below with the data for stepped surfaces.
The sharp and narrow peak at -0.15 V on the Pt(110) plane
indicates on a coupling of hydrogen adsorption/desorption and
HSO^- and S0 2- desorption/adsorption. This w i l l be further
4
discussed i n connection with the data for stepped surfaces.

Positive to the hydrogen adsorption region, the curve for
the P t ( l l l ) surface shows "anomalous peaks" which, according to
the predominant view, are due to sulphate adsorption (li, 13) .
C l a v i l i e r ascribed these peaks to adsorption of 1/31 of a
monolayer of strongly-bound hydrogen. The charge associated with
these peaks i s 75 jaC cm-2, which corresponds to 1/31 of a
monolayer of a completely discharged univalent species. Such a
1
discharge i s possible for oxy-anions such as HS0 ~ and S0 2-, 4 4
since t h e i r adsorption i s very strong at (111) s i t e s . This I i s due

to the compatibility of t h e i r tetrahedral structure with (111)
surface symmetry (14). I t was assumed that one oxy-anipn can
cover at least 3 Pt atoms. Such adsorption can r e s u l t i n ι almost
complete discharge of the overlayer of anions (14). A sizable
discharge of S0 2-, HSO - on Au(111) can be also deduced from the
4
shape of C-E curves (15), which suggests that the (111) symmetry
i s more important i n t h i s p a r t i c u l a r case than the nature of the
electrode material. A strong adsorption of S0 2- and HS0 ~ on 4 4
P t ( l l l ) i s also r e f l e c t e d i n the beginning or oxide formation

which, on t h i s plane, i s s h i f t e d to high p o s i t i v e p o t e n t i a l s
(Fig. 1) . A sharp r e v e r s i b l e p a i r of peaks at E=0.2 V (which
merge with the process at E=0.15 V) require a two-dimensional
order, since they do not occur at stepped surfaces with
(111)-oriented terraces (12). This unusual p a i r of peaks require
further study which i s outside of scope of t h i s paper.
A d i r e c t evidence of the way of tetrahedral anion adsorption
at three-fold s i t e s and the degree of hydratation i s not
available at present. However, a strong i n d i c a t i o n of such
adsorption of sulphates i s found i n voltammetry on gold (14) and
i n our data for platinum surfaces (12). A pronounced difference
between the sulphate and perchlorate adsorption e f f e c t s i s

34. MARKOVIC ET AL. Hydrogen Electrosorption and Formic Acid Oxidation 501
p a r t i a l l y due to t h e i r d i f f e r e n t hydratation on the surface. There

are indications that sulphates are hydrated by only two, while
perchlorates by 7-8 water molecules (14). A high hydratation of
perchlorates may be cause of a small difference between
adsorption of these anions and f l u o r i d e s .
Two other small peaks appear at E=0.45 and 0.7 V on the
P t ( l l l ) surface. They are shifted to more negative p o t e n t i a l s
H S 0
with increasing 2 4 concentration, suggesting t h e i r l i n k with
anion adsorption. A peak at 0.35 V for the Pt(100) surface, where
one would expect the so-called double-layer region for Pt, i s
also i n t r i g u i n g . I t remains to be seen whether or not i t i s due
to sulphate adsorption on the (111)-oriented imperfections.
The curve for Pt(110) surface shows a wide double layer
region, indicating that the anion adsorption i s completed
concurrently with hydrogen desorption. The anions are strongly
held i n the "troughs" of the Pt(110) surface, i . e . i n the
2(111)-(111) terrace-step s i t e s This point w i l l be touched upon
connection with the steppe
H S 0
i n 2 4 c l e a r l y show a
surface at very negative p o t e n t i a l s (15).
A pronounced s t r u c t u r a l s e n s i t i v i t y of the oxidation of Pt
surfaces i s also seen i n F i g . 1. The reaction takes place at the
most p o s i t i v e p o t e n t i a l on P t ( l l l ) . This i s probably due to
e f f e c t i v e blocking of the surface by oxy-anions with the t r i g o n a l
symmetry, compatible with the (111) o r i e n t a t i o n . A detailed
analysis of t h i s reaction on Au(111) has been recently performed
by Angerstein-Kozlowska et a l . (14). No such blocking i s possible
for the Pt(100) and Pt(110) surfaces with four-fold and two-fold
symmetries. Consequently, the oxidation commences at more
negative p o t e n t i a l s , probably predominantly determined by the
surface energy as found with Au (16).
Hydrogen Adsorption on Platinum Single C r y s t a l Stepped Surfaces.

Few data are available f o r hydrogen adsorption on stepped surface
(12, 17, 20-22). The reaction on several surfaces from the [lio]
zone has recently been analyzed i n some d e t a i l (12). F i g . 2 shows
voltammetry curves for hydrogen adsorption i n a l l three zones of
the stereographic t r i a n g l e . For the [ l i o ] zone (Fig. 2a) the
reaction i n the region -0.25 < Ε < -0.075 V has been ascribed to
hydrogen adsorption on the (111)-oriented terraces. The peak at
-0.025 V has been found due to adsorption on the step s i t e s of
the (111)-(100) or (100)-(111) intersections of terraces and
steps f o r surfaces v i c i n a l to the (111) and (100) planes,
respectively. The t r i g o n a l s i t e s formed by intersections on the
(111) and (100)-oriented steps and terraces are responsible f o r a
strong adsorption of oxy-anions at steps. I t appears that upon
anion desorption, hydrogen adsorbs f i r s t at the (100)-oriented
s i t e s (12). This size of t h i s peak at -0.025 V i s proportional to
the step density. Hydrogen adsorption i s concurrent with the
bisulphate/sulphate desorption. The s i m i l a r i t y of these s i t e s ,
which can bee seen from models i n F i g . 3, causes the appearance
of the peak at almost the same p o t e n t i a l i n the whole zone.
For surfaces v i c i n a l to the (111) plane (Fig. 2a) i n the
p o t e n t i a l region 0.15 < Ε < 0.5 V a broad peak has been ascribed

Figure 2A. C y c l i c voltammetry for the single c r y s t a l surfaces

laying on the 111 zone l i n e . Sweep rate 50 mV/s.

ι 1 1 Γ
U50uAcm-2 0.05M HjSO*
#
Β
I ι ι ι ι I
-0.4 0 (M 0.8 E / Y 1.2
Figure 2B. Cyclic voltammetry f o r the single c r y s t a l surfaces

laying on the 100 zone l i n e . Sweep rate 50 mV/s.


34. MARKOVIC E T A K Hydrogen Electrosorption and Formic Acid Oxidation 505
Figure 3. Models f o r the stepped surfaces, with tetrahedral

anions adsorbed on the (111) trigonal sites for a)
n(lll)-(100), b) n(100)-(lll) , c) n(100)-(100) and d)
η(111)-(111) terrace-step o r i e n t a t i o n s .

to bisulphate/sulphate adsorption on the (111)-oriented terraces

(12). Its size i s inversely proportional to the step density. No
such peak i s seen f o r the Pt(311) surface whose structure, being
2(111)- (100), cannot accommodate the tetrahedral anions i n the
terrace. Such anions, adsorbed i n the step, block the whole
2-atom long terrace (12).
Voltammetry curves f o r surfaces from the [lOOJ zone are
displayed i n F i g . 2b. These are the (210), (310) and (610) faces,
which i n Lang et a l . (23) notation are 2(100)-(100), 3(100)-(100)
and 6(100)-(100), respectively. The curve for the (320) surface,
on the other side of the (210) orientation which i s the "turning
point" of the zone, i s also shown.
A common feature of these curves i s a peak at -0.025 V, the
same p o t e n t i a l as for the [ l i o ] zone. This peak has been
explained above by p a r t i c u l a r atomic arrangements i n the step.
The question a r i s e s whether the same arrangements are formed i n
t h i s zone? A close inspection of the stepped surfaces from t h i s
zone (Fig. 3) shows tha
can be obtained by a combinatio
terraces and steps. Again, a t r i g o n a l symmetry of Pt atoms can be
formed, providing s i t e s f o r a strong adsorption of bisulphate or
sulphate. Although three-fold binding s i t e s are found i n the
[lOO] zone, the surface coordination, surface energy and o r b i t a l
orientation are d i f f e r e n t shape. The peak occurs, however, at
almost the same p o t e n t i a l . The size of the peak i s proportional
to the step density, as has been checked by combining our data
with the data of Motoo and Furuya (22) who reported a d d i t i o n a l
three surfaces v i c i n a l to the (100) plane.
The peak associated with a strongly bound hydrogen at
E*0.15 V i n F i g . 2b decreases as the terrace width decreases,
giving no i n d i c a t i o n of i t s presence for the Pt(210)=2(100)-(100)
or 2(110)-(100) surface. The highly active s i t e i s provided by
the (100) o r i e n t a t i o n , which decreases with decreasing terrace
width. For the Pt(210) surface adsorption on the terrace i s
apparently strongly affected by the anion adsorption i n the step,
which blocks the 2-atom wide terrace. Consequently, no s i t e s f o r
a strong adsorption of hydrogen are a v a i l a b l e .
On the basis of the models i n F i g . 3 and comparison with the
peak f o r the [ l i o ] zone, the reaction i n the p o t e n t i a l range
-0.25 < Ε < -0.15 V could be ascribed to the hydrogen adsorption
on the (111)-oriented step s i t e s .
The behaviour of the Pt(110) surface, as discussed above, i s
largely determined by a strong adsorption of anions i n the steps
of i t s 2(111)-(111) structure. The same i s v a l i d f o r v i c i n a l
surfaces such as Pt(320), which gives a sizable peak at the same
p o t e n t i a l as Pt(110).
For most of the surfaces from the [lTo] zone, F i g . 2c,
hydrogen adsorption i s predominantly associated with the single
peak occurring at almost the same p o t e n t i a l for a l l the surfaces
investigated. That peak, in the potential region
-0.25 < Ε < -0.1 V, i s determined by hydrogen adsorption, coupled
with anion desorption, from the (111)-(111) or (110)-(111)
terrace-step s i t e s (Fig. 2c). They coincide with the peak f o r the

Pt(llO) surface. As explained above, t h i s surface behaves as the

" f u l l y stepped" surface with the o r i e n t a t i o n 2(111)-(111).
The coupling of H adsorption with HS0 - and S0 2- desorption 4 4
can be written i n the following way:
+ + A ( z ) _ + ( e H ( 1 _ > H ) + + z ( 2 )
y" ad ~^ y W > y ad * ~
Evidence for t h i s coupling was obtained by a comparison of the
data for sulphuric and p e r c h l o r i c acids (12).
The reaction at -0.1 < Ε < 0.15 V seems to be associated
with hydrogen adsorption on the (111) oriented terrace s i t e s for
the surfaces v i c i n a l to the (111) plane. This can be deduced from
a comparison with the P t ( l l l ) surface. A small peak at E«*0.35 V,
seen for the Pt(332) and Pt(221) surfaces, i s due to
bisulphate/sulphate adsorption on the (111)-oriented terraces.
This point has been discussed i n d e t a i l f o r the Pt(332) and
Pt(755) surfaces (12).
I d e n t i f i c a t i o n of Peak
Low Index Planes. Besides the major objective f o r studying
e l e c t r o c a t a l y s i s on single c r y s t a l stepped surfaces mentioned
above, these studies o f f e r a wealth of information on the
behaviour of p o l y c r y s t a l l i n e surfaces, of p r e f e r e n t i a l l y oriented
surfaces and, as we suggested recently (12), of disordered
low-index surface.
A single sweep into the oxide formation with the P t ( l l l )
surface causes a considerable change of voltammetry curve for a
well-ordered surface, as can be seen i n F i g . 4a. Two new small
peaks are seen on the curve of the o r i g i n a l P t ( l l l ) . These peaks
can be seen on the curves f o r surfaces by believed to be
"well-ordered" by several authors (10, 17, 22). To unravel the
o r i g i n of the two peaks at E=-0.15 and -0.075 V, i t i s necessary
to be able to introduce, i n a c o n t r o l l e d manner, deviations from
the perfect well-ordered l a t t i c e structure. This i s offered by
the use of the stepped surfaces. F i g . 4b shows that the sharp
peaks of the Pt(755)=6(111)-(100) and Pt(332)=6(111)-(111)
coincide with the above peaks. This strongly suggests that these
peaks are due to the introduction of the (100)- and
(111)-oriented steps upon c y c l i n g into the oxide formation
region. Introduction of steps, i . e . , more active s i t e s on the
well-ordered (111) surface, i s also seen i n the oxide formation
region which now commences at much less p o s i t i v e p o t e n t i a l . I t
appears that the surface energy plays important r o l e i n surface
oxidation (15), although the lack of sulphate adsorption at the
top step s i t e s c e r t a i n l y has an e f f e c t . Also, the sharp peak at
E=0.2 V i s l o s t and the peak of sulphate adsorption is
diminished. A l l these processes are now t y p i c a l f o r a stepped
surface.
The curve f o r Pt(100) shows some features which could be due
to the presence of the surface imperfections. Defect formation on
f a m e o r b
the Pt(100) surface by an Η ^ Λ ^ l Y electrochemical
oxidation may not be s u r p r i s i n g , considering r e s u l t s from the
gas-phase (24) which showed that the reaction of 0 with surfaces

Figure 4. C y c l i c voltammetry f o r well ordered ( - - - - ) and

disordered ( ) P t ( l l l ) , f o r well ordered Pt(755) and Pt(332)
i n 0.05 M H SO . Sweep rate 50 mV/s.

from the [lOo] zone produced reconstructions. I t remains t o be

seen how much cooling i n H prevents reconstructing.
The e f f e c t of a single p o t e n t i a l excursion into the oxide
region causes a considerable decrease of the peak of strongly
bound hydrogen and an increase o f the peak a t E=~0.15 V (Fig.
5a). At the same p o t e n t i a l a small peak i s seen for the Pt(100),
prepared as described above. A s i m i l a r , or even larger, peak i s
seen with a l l the curves published so f a r (21, 22, 23). The
curves for vicinal ( Pt(11,1,1)=6(100)-(111) and
Pt(610)=6(100)-(100) ) surfaces (Fig. 5b) show much larger peaks
at the same p o t e n t i a l s . These data strongly suggest that a small
Peak at E=-0.16 V f o r Pt(100) i s due t o the contribution of the
(111) step s i t e s .
Oxidation of Formic Acid. The oxidation of formic a c i d on Pt has

been the subject of numerous studies on p o l y c r y s t a l l i n e (26) and
single c r y s t a l (8-11) electrodes However no consensus on the
mechanism has been reache
It i s accepted tha
broken:
HCOOH > -COOH + H+ + e-
I t i s also agreed that further reaction goes through two p a r a l l e l

pathways,
^»CO + H+ + e-
-COOH
poisoning species
one leading to a formation of C 0 2# the other to a formation of

strongly bound species, which may be eventually be oxidized to
CO a t high p o s i t i v e p o t e n t i a l s . The H-C bond i s broken f i r s t ,
unlike i n the gas phase where 0-H bond reacts f i r s t (27). This
electrochemical behaviour has been confirmed by comparison of the
kinetics of DCOOD, DCOOH and HCOOH on p o l y c r y s t a l l i n e Pt modified
by Pb (28) and on Pt(100) and Pt(110) electrodes (29).
A long disputed issue o f the nature o f strongly bound
species i n t h i s reaction has been recently revived with the
v i b r a t i o n a l spectroscopy studies of Bewick e t a l . (30) using
EMIRS technique and of Kunimatsu and Kita (31) using p o l a r i z a t i o n
modulation IR-reflection-absorption technique. These data
indicated the only CO i s a strongly bound intermediate. Heitbaum
et a l . (32) on the other hand advocate COH, and most recently HCO
(33), as the poisoning species on the basis o f d i f f e r e n t i a l
electrochemical mass spectroscopy (DEMS).
To allow for CO formation i n the H adsorption region one can
modify the reaction proposed e a r l i e r for formation of COH (31):
COOH + H > CO + H 0 o (3)

a a a 2
Outside the hydrogen adsorption region CO can be formed by the
reaction (3):

Figure 5. C y c l i c voltammetry f o r Pt(100) before ( - - - - ) and

after ( ) disordering of the surface and f o r ordered
P t ( l l , l , l ) and Pt(610) surfaces i n 0.05 M H SO.. Sweep rate 50
2
mV/s.

2COOH > -CO + H.O + CO (4)

a a /.
The oxidation of formic a c i d was the f i r s t e l e c t r o c a t a l y t i c
reaction which c l e a r l y showed a pronounced influence of the
structure on i t s kinetics and mechanism (8-10). Despite these
studies, a thorough understanding of the reaction mechanism on
various planes has not been obtained. This applies e s p e c i a l l y to
the negative-going sweeps f o r the Pt(100) and Pt(110) planes
a f t e r reversal at 1.1 - 1.2 V. Upon "activation" of the electrode
at these p o t e n t i a l s , the Pt(110) surface on the negative going
sweep immediately (once the oxide layer i s reduced) gives high
current density (Fig. 6). For Pt(100), on the other hand, one
obtains a gradual increase of the current as the p o t e n t i a l
becomes more negative, i . e . the current increases with decreasing
the overpotential for the reaction. The Pt(100) surface (Fig.6a)
i s blocked, most probably by CO, up to the p o t e n t i a l of the oxide
formation. Upon sweep r e v e r s a l the reduction of a p a r t i a l l y
oxidized surface takes
fast r i s e of the curren
surface, one sees a gradual increase of the current as the
p o t e n t i a l becomes more negative.
The Pt(110) surface exhibits a quite d i f f e r e n t behaviour.
F i r s t , the positive-going sweep gives a large peak commencing at
~0.65 V. This indicates that upon oxidation of the blocking
species the reaction takes place at a high rate at that high
overpotential. Upon sweep reversal s i m i l a r high currents are
observed. This behaviour, e s p e c i a l l y the cathodic sweep, contrasts
with the behaviour of the Pt(100) surface. The P t ( l l l ) plane
shows no a c t i v a t i o n e f f e c t , i . e . no poisoning species seem to be
formed on that plane. The sweeps i n anodic and cathodic
directions almost retrace, with the current peak at 0.5 V. This
peak was found a consequence of anion adsorption (29). I t i s
noteworthy that the oxidation of CHÔH i s less structure
sensitive (9).
Anion adsorption i s apparently determining the negative
going sweeps for P t ( l l l ) and Pt(100). This w i l l be i l l u s t r a t e d by
following discussion. For Pt(110), the i n d i r e c t arguments given
H S 0
in the 2 4 voltammetry section indicate that sulphate
desorption occurs at very negative p o t e n t i a l s , while the
oxidation of HCOOH i n the cathodic sweep takes place at much more
negative p o t e n t i a l s on t h i s surface than on the others. The
adsorption of sulphates at those potentials (0.7 V) i s c l e a r l y
very strong. There i s no d i r e c t data available on the adsorption
of sulphate on Pt single c r y s t a l surfaces. For Au, on the other
hand, there e x i s t s a considerable body of experimental work (15,
34) . These data show a pronounced role of crystallographic
orientation on adsorption of sulphate. The data of Strbac et a l .
(15) corroborate the conclusions reached f o r Pt based on hydrogen
adsorption and i t s r e l a t i o n to adsorption of anions. These data
show that at Pt(110) sulphate adsorption i s largely completed at
Ε < 0.05 V.
The oxidation of HCOOH at Pt(110) at E-vO.65 V i n sweeps i n
both d i r e c t i o n s now appears as a contradiction to the above
analysis. Why doesn't sulphate block the reaction, since they are

Figure 6. Oxidation of HCOOH on the Pt(100) and Pt(llO) single

c r y s t a l surfaces i n 0.5 M H SO . Sweep rate 50 mV/s.

strongly bound a t these potentials? Oxide formation requires more

p o s i t i v e potentials and can be ruled out as a p o s i t i v e "trigger"
of the reaction. From the above data i t follows that the Pt(llO)
surface behaves as " f u l l y " stepped surface with the orientation
2(111)-(111), the anions are probably strongly adsorbed i n
"troughs" of that surface. Their repulsion prevents the
additional adsorption of tetrahedral anions on "ridges" the top
s i t e s . HCOOH can, however, react with these s i t e s , r e s u l t i n g i n
current peaks a t Ε 0.65 V. The question arises as to why the
reaction "waits" f o r such p o s i t i v e potentials? This i s due to
immediate poisoning with CO a t lower p o t e n t i a l . CO i s oxidized a t
the same p o t e n t i a l as HCOOH on that plane (35).
From gas phase measurements CO i s known to prefer top s i t e s
on a l l three low index faces, with the CO molecule perpendicular
to the surface and bonded through the carbon end of the molecule
except a t high coverages (27). I t i s l i k e l y that HCOOH and COOH
are adsorbed i n a s i m i l a r way I t i s not l i k e l y that they could
"enter" the "troughs"
Pt(100) on the other hand
reduction, anions are immediately adsorbed on that "flat"
surface. They block adsorption o f HCOOH. Adsorption o f anions
decreases as p o t e n t i a l becomes more negative. The oxidation of
HCOOH commences and the rate increases as a t more negative
p o t e n t i a l s , i . e . at lower overpotential. A competition between
anions and HCOOH adsorption explains t h i s apparently anomalous
behaviour. The explanation of the "anomalous" behaviour o f the
Pt(110) surface can be also found i n the data f o r stepped surface
v i c i n a l to the (100) and (110) orientations.
F i g . 7 gives the curve f o r the Pt(11,1,1)=6(100)-(111).
Introduction o f steps i n the (100) f l a t surface causes the
appearance of a new peak i n cathodic sweep a t Ε 0.75 V. The peak
grows as the step density increases (29).
Sulphate i s strongly adsorbed i n the steps o f these surfaces
just as i n the "troughs" of the (110) plane. The top step s i t e s
should be again available f o r the oxidation of HCOOH, as strongly
indicated by F i g . 7. The data f o r the Pt (332)=6(111) - (111)
surface provide further support of t h i s analysis. As with P t ( l l l )
t h i s surface shows no poisoning e f f e c t (as do other low index
planes) (Fig. 7), giving a peak i n anodic sweep. However, the
(111)-(111) terrace-step combination gives the s i t e s o f the (110)
geometry. This causes the appearance of the peak at 0.7 V, as on
Pt(110). F i g . 8 shows a strong s t r u c t u r a l dependence on surfaces
from the 3 zones.
General discussion and conclusions.
Both the data on hydrogen adsorption and formic acid
oxidation show pronounced s t r u c t u r a l s e n s i t i v i t y , thus confirming
a paramount r o l e of surface structure i n e l e c t r o c a t a l y t i c
reactions. I t can be concluded that each crystallographic
orientation represents a d i s t i n c t electrochemical (chemical)
e n t i t y . The investigation of stepped surfaces seems t o be
necessary to reach an understanding o f these systems on a
molecular l e v e l . Hydrogen adsorption shows dependences on the
terrace orientation, step orientation, and step density. A l l the

τ 1 1 Γ
1 . ι ι ι I
0.0 OA 0.8 1.2 E/V
Figure 7. Oxidation of HCOOH on the P t ( l l , l , l ) and Pt(332)
single c r y s t a l stepped surfaces i n 0.5 M H SO . Sweep rate 50
mV/s.


peaks observed with voltammetry are directly due to surface

structure, rather than to induced heterogeneity. The same
conclusions hold for the oxidation on formic acid. On the basis
of the anodic sweep, the most active surface appears to be
Pt(lll), due to the lack of its poisoning.
Although the structure of some of the surfaces used has been
checked by LEED, i t appears necessary to prove by that technique
that the flame-annealing-hydrogen cooling method gives ordered
surfaces. The systematic changes of hydrogen adsorption and of
HCOOH oxidation with step density indicate on a high probability
that the surface structures were well-ordered and well-oriented.
Further work involving a fast transfer from the UHV into the cell
seems desirable.
Acknowledgments
The authors are indebted to the Research Fund of S.R
Serbia, Yugoslavia an
contract 553 for financia
Literature Cited
1. F.G.Will, J.Electrochem.Soc., 112 (1965) 481.
2. A.T.Hubbard, R.M.Ishikawa and J.Katekaru, J.Electroanal.Chem.,
861 (1978) 271.
3. E.Yeager, W.E.O'Grady, M.Y.C.Woo and P.Hagans,
J.Electrochem.Soc., 125 (1978) 348.
4. P.N.Ross, J.Electroanal.Chem., 150 (1983) 141.
5. D.Aberdam, R.Durand, R.Faure and F.El-Omar, Surf.Sci., 171
(1986) 303.
6. J.Clavilier, J.Electroanal.Chem., 107 (1980) 211.
7. N.Marković, M.Hanson, G.McDougal and E.Yeager,
J.Electroanal.Chem., 214 (1986) 555.
8. R.R.Adžić, W.O'Grady and S.Srinivasan, Surf.Sci., 94 (1980)
L191.
9. R.R.Adžić, A.V.Tripković and W.O'Grady, Nature (London) 196
(1982) 137.
10. J.Clavilier and G.Sun, J.Electroanal.Chem., 199 (1986) 479.
11. R.R.Adžić, A.V.Tripković and V.B.Vešović,
12. N.M.Markovic, N.S.Marinkovic and R.R.Adžić,
13. D.M.Kolb, Zeitschrift fur Phys.Chem. Neue Folge, 154 (1987)
179.
14. H.Angerstein-Kozlowska, B.Conway, A.Hamelin and
L.Stoicoviciu, Electrochem.Acta, 31 (1986) 1051;
15. S.Štrbac, R.R.Adžić and A.Hamelin, J.Electroanal.Chem., in
press.
16. R.R.Adžić and S.Štrbac, J.Serb.Chem.Soc., 52 (1987) 587.
17. P.N.Ross, J.Electrochem.Soc., 126 (1979) 67.
18. C.L.Scortichini and C.N.Reilley, J.Electroanal.Chem., 139
(1982) 247.
19. A.N.Tripković and R.R.Adžić, J.Electroanal.Chem., 205 (1986)
335.

20. B.Love, K.Seto and J.Lipkowski, J.Electroanal.Chem., 199

(1986) 259.
21. J.Clavilier, D.Armand, S.Sun and M.Petit,
22. S.Motoo and N.Furuya, Ber.Buns.Ges, 101 (1987) 624.
23. B.Lang, R.W.Joyner and G.A.Somorjai, Surf.Sci., 30 (1972)
440.
24. P.Blakely and G.A.Somorjai, Surf.Sci., 65 (1977) 419.
25. J.Clavilier and D.Armand, J.Electroanal.Chem., 199 (1986)
187.
26. See e.g. R.R.Adžić, Advances in Electrochemistry and
Electrochemical Engineering, vol. 13, H.Gerisher ed., 159-260,
J.Willey, New York, (1985).
27. R.Madix, Advances in Catalysis, vol. 29, (1980).
28. A.Razaq and D.Pletcher, J.Electrochem.Soc., 129 (1984) 322.
29. R.R.Adžić and A.V.Tripković, unpublished.
30. A.Bewick and S.Pons In Advances in Infrared and Raman
Spectroscopy, Ed. R.E.Nexte
1984.
31. Kunimatsu and H.Kita, J.Electroanal.Chem., 218 (1987) 155.
32. J.Wilsau and J.Heitbaum, Electrochim.Acta, 31 (1986) 8.
33. O.Wolter, J.Wilsau and J.Heitbaum, J.Electrochem.Soc., 132
(1985) 1635.
34. A.Hamelin, Modern Aspects of Electrochemistry, Ed. B.Conway,
J.Bockris and K.White, vol. 16, Chapter 1, Plenum Press, New
York, (1985).
35. C.Lamy, J.M.Leger, J.Clavilier and R.Parsons,

Chapter 35
Mechanistic Aspects of the Electrochemical

Reduction of Carbon Monoxide and Methanol
to Methane at Ruthenium
and Copper Electrodes
David P. Summers and Karl W. Frese, Jr.
Materials Research Laboratory, SRI International, 333 Ravenswood

Avenue
Carbon monoxide an
The reduction of carbon monoxide a l s o s u f f e r s
d e a c t i v a t i o n by a surface species s i m i l a r t o that f o r
carbon d i o x i d e reduction but which forms at lower
temperatures. The reduction of carbon monoxide does
appear to proceed v i a a path s i m i l a r to that which the
reduction of carbon dioxide follows. Rates f o r methanol
reduction are extremely v a r i a b l e . Methanol reduction,
l i k e carbon dioxide reduction, both increases i n rate
with decreasing pH u n t i l the surface becomes blocked
with s u r f a c e hydrogen and is a l s o d e a c t i v a t e d by
increased temperature. For methanol, deactivation does
not occur by the formation of the same surface species.
Thus the reduction of methanol i s not b e l i e v e d to
proceed v i a a mechanism s i m i l a r to that f o r carbon
dioxide or carbon monoxide. Copper electrodes a l s o
reduce carbon monoxide to methane.
The goals of r e p l a c i n g f i n i t e world n a t u r a l gas reserves and

producing f u e l s from inorganic sources and s o l a r energy has been a
motivating f o r c e f o r studying the e l e c t r o c h e m i c a l reduction of
carbon dioxide to methane, e s p e c i a l l y i n l i g h t of increasing carbon
dioxide concentrations i n the atmosphere ( 1-3) . E l e c t r o c h e m i c a l
routes are a t t r a c t i v e i n that they are low temperature processes and
can be coupled to s o l a r energy sources. Carbon monoxide and
methanol are both possible intermediates i n the reduction of carbon
dioxide to methane and both are formed as side products i n the
reduction of carbon dioxide (2-3 and Kim, J . J . ; Summers, D. P.;
Frese, K. W., J r . J . E l e c t r o a n a l . Chem. i n p r e s s ) . Also, whether
they are intermediates i n carbon dioxide reduction, the reduction of
both carbon monoxide and methanol i s l i k e l y to proceed by s i m i l a r
pathways as the reduction of carbon dioxide and may have a s i m i l a r
intermediates and rate-determining-steps.
The electrochemical reduction of carbon monoxide also o f f e r s a
route f o r the production of f u e l s from inorganic sources. For
example, carbon monoxide i s formed from c o a l i n g a s i f i c a t i o n
0097-6156/88Α)378-0518$06.00/0

35. S U M M E R S AND F R E S E CO and Methanol Reduction to Methane 519
schemes. Carbon monoxide i s also l i n k e d to carbon dioxide by the

water gas s h i f t r e a c t i o n . The reduction of carbon monoxide to
methane i n the gas phase has been extensively studied but i t i s only
recently that any reports of the electrochemical reduction of carbon
monoxide have appeared (5 6 and Kim, J . J.; Summers, D. P.; Frese,
r
K. W., J r . J . E l e c t r o a n a l . Chem. i n press.) There are also only two

reports of the electrochemical reduction of methanol to methane
(ia)
The electrochemical reductions of carbon monoxide and methanol
to methane (Equations 1 and 2) have p o t e n t i a l s , under standard
c o n d i t i o n s , of +0.019 and +0.390 V vs SCE r e s p e c t i v e l y (or a
+
CO + 6 H + 6 e~ -» CH 4 + H0
2 (1)
CH3OH + 2 H +
+ 2 e" -* CH 4 + H0
2
(2)
r e v e r s i b l e p o t e n t i a l , unde
+ 0.248 V vs SCE r e s p e c t i v e l
CH3OH). S i m i l a r l y , the reductio o carbo dioxide to methane has a
p o t e n t i a l , under standard conditions, of -0.061 V vs SCE. At Ru
carbon dioxide i s reduced to methane at low overpotentials but with
low rates while at copper methane i s formed at high rates but with
high overpotentials Q and Kim, J . J . ; Summers, D. P.; Frese, K. W.,
J r . J . E l e c t r o a n a l . Chem. i n p r e s s . ) . The r e s u l t s presented here
show that copper e l e c t r o d e s can reduce carbon monoxide, and
ruthenium electrodes can reduce both carbon monoxide and methanol,
to methane under conditions s i m i l a r to those f o r the reduction of
carbon dioxide to methane. The data also i n d i c a t e that there are
s i m i l a r i t i e s i n the mechanism of reduction to methane between carbon
dioxide and carbon monoxide.
EXPERIMENTAL
The e l e c t r o l y s i s of carbon monoxide was conducted under 1 atm carbon

monoxide and methanol was e l e c t r o l y z e d under a nitrogen atmosphere.
Unless otherwise stated, e l e c t r o l y t e s were aqueous s o l u t i o n s of
e i t h e r 0.2 M reagent grade sodium s u l f a t e (Ru electrodes) or 0.5 M
Na2HP04 at pH 7.6 (Cu e l e c t r o d e s ) . A l l solutions were made with
d i s t i l l e d deionized water ( M i l l i p o r e ) . In the experiments with
ruthenium the pH was held constant by the addition of reagent grade
s u l f u r i c a c i d using a pH c o n t r o l l e r and a syringe pump except for
the data i n Table II i n which the pH v a r i e d from 4 to 5.5. All
e l e c t r o l y s i s experiments using Ru electrodes were conducted at ~60°C
f o r 5-6 hrs with reagent grade Na S04 unless otherwise noted while
2
a l l Cu experiments were conducted at room temperature and required

no pH c o n t r o l .
Ru electrodes were prepared as previously described by p l a t i n g
Ru metal onto spectroscopic carbon rods, except f o r the electrode
used f o r Auger analysis (before and a f t e r carbon dioxide reduction)
which was p l a t e d on T i (2.) . Cu electrodes were prepared from Cu
f o i l as previously described (Kim, J . J . ; Summers, D. P.; Frese, K.
W., J r . J . E l e c t r o a n a l . Chem. i n press.). Each entry i n the tables
and figures was obtained on d i f f e r e n t days with the electrode kept
i n ordinary laboratory a i r overnight between runs.

E l e c t r o l y s e s were performed using an Aardvark model PEC-1

p o t e n t i o s t a t and Keithley model 616 d i g i t a l electrometer, and a
microcomputer data a c q u i s i t i o n system f o r measuring current as a
function of time. A two compartment c e l l was employed to avoid
o x i d a t i o n of the carbon d i o x i d e r e d u c t i o n p r o d u c t s . All
e l e c t r o l y s e s were c a r r i e d out using a closed system as previously
described (2.) . The c i r c u l a t e d gas was bubbled through the solution
causing gentle a g i t a t i o n . The temperature was c o n t r o l l e d by placing
the e n t i r e system with the exception of the c i r c u l a t i n g pump i n a
heated enclosure. In a l l cases e l e c t r o l y t e volumes were 50 ml.
Samples were analyzed on a Gowmac model 750 gas chromatograph with a
FID detector. Samples were c o l l e c t e d f o r CH analysis from the gas
4
phase over s o l u t i o n . A column of Porapak Q (6ft) followed by

Porapak R (3ft) at 50 C was used f o r CH4/CO analysis.
Auger spectra were obtained with a Perkin-Elmer PHI Auger
spectrometer. Auger samples were removed under p o t e n t i a l control,
r i n s e d with water, and allowed to dry before mounting on sample
holder.
Carbon Monoxide Reduction at Ruthenium. Carbon monoxide can be

reduced to both methane and methanol under c o n d i t i o n s n e a r l y
i d e n t i c a l to those f o r the reduction of carbon dioxide (Table I, A l l
experiments, using one electrode, are presented i n the order they
were performed).
The rate and faradaic e f f i c i e n c y of methane formation from
carbon monoxide appears lower than from carbon d i o x i d e . For
comparison, at 60 °C, -0.545 V vs SCE, pH 4, and 60 °C a t y p i c a l
7 1
rate f o r carbon dioxide reductions i s 1.5 χ 10~ mol cm"^ h r " with
a faradaic e f f i c i e n c y of 20-30 %. Carbon monoxide i s 40 times less
soluble i n water than carbon dioxide (at 1 atm) . However the
surface coverage w i l l depend on the p a r t i a l pressure which i s the
same (1 atm) f o r both carbon monoxide and carbon d i o x i d e .
A d d i t i o n a l l y , carbon monoxide probably adsorbs more strongly than
carbon dioxide and so should have a higher coverage than carbon
d i o x i d e at the same p a r t i a l pressure. Indeed a c l e a r anodic
s t r i p p i n g peak can be seen at +0.15 V vs SCE (pH 3) f o r carbon
monoxide adsorbed on the Ru surface at 1 atm (60 °C) while exposure
to carbon dioxide produces no peak. Since these rates are too slow
to be d i f f u s i o n controlled, transport l i m i t a t i o n cannot account f o r
the differences i n rate. It i s not known i f the lower rate from
carbon monoxide i s simply due to the blockage of surface hydrogen
s i t e s necessary f o r hydrogénation of intermediates to methane or i f
there i s a fundamental d i f f e r e n c e i n rate. The rate of methane
formation from carbon dioxide decreases (along with the t o t a l
current) when carbon monoxide i s added (Table II) consistent with
the blocking of the surface by more-slowly-reduced carbon monoxide.
When the temperature i s raised to 75 °C a decrease i n the rate
of carbon monoxide reduction i s observed with a p a r a l l e l decrease i n
the faradaic e f f i c i e n c y . When the electrode i s used a second time
f o r carbon monoxide reduction at 60 °C, a f t e r i t was used f o r
e l e c t r o l y s i s at 75 °C, (last entry i n Table I) i t shows considerable
deactivation. The reduction of carbon dioxide also shows a s i m i l a r

Table I. Rate and Faradaic E f f i c i e n c y of C H 4 and C H 3 O H formation from CO at
a
Electroplated Ru Electrodes
Methane Methanol
c d 8 c d 8
Time PH j b
Ε Τ Eff Rate χ 10 Eff R a t e χ 10
-2
0 -2 1 2 1
(hr) (UA cm ) (V vs SCE) (°C) (%) (mol cm h r " ) (%) (mol cm" h r " )
6.3 3 845 -0.54 60 1.3 6.6 N.M. N.M.

20.3 3 538 -0.54 60 2.1 7.0 ~5 -25
18.3 4 101 -0.54 75 5.8 3.7 -15 -14
*6.0 4 141 -0.54 60 N.D. N.D. N.M. N.M.
a) A l l e l e c t r o l y s e s were i n 0.2 M reagent grade Na2S04.

b) Average current density based on geometrical area.
c) Faradaic e f f i c i e n c y f o r methane formation.
d) Average rate of methane formation.

Table I I . The E f f e c t of CO on the Electrochemical Reduction of CO2

a
to Methane at Electroplated Ru Electrodes
d
CO added Rate χ 10
c 8
Eff
1
(ml) (UA -2
cm ) (mol cm" hr" )
2
(%)
0 107 9.3 18.6

35 72 4.9 14.7
0 79 7.5 20.2
50 63 3.6 12.4
a) A l l e l e c t r o l y s e s times are 5-6 hrs i n 0.2 M reagent

grade Na2S0 at 60°C and -0.545 V vs SCE with an
4
i n i t i a l pH of 4. CO was added d i s p l a c i n g an equal

volume of CO2 from the 1.3 1 CO2 reservoir (see
experimental).
b) Average current densit based geometrical
c) Rate of methan
d) Faradaic e f f i c i e n c
d e a c t i v a t i o n though, i n t h i s case, a decrease i n the rate i s not

seen u n t i l higher temperatures, ~90 °C (2) .
There are s i m i l a r i t i e s between d e a c t i v a t i o n of Ru by carbon
dioxide and by carbon monoxide. The Auger electron spectrum of the
surface of the electrode (Ru on Ti) deactivated by carbon dioxide
reduction at 90 °C i s very d i f f e r e n t from that taken before
e l e c t r o l y s i s (Figure 1). The primary signals f o r Ru and C overlap
but by comparing the s i z e of the secondary Ru peaks at s l i g h t l y
lower energy i t can be seen that the spectrum taken before
deactivation shows mostly a Ru s i g n a l while the spectrum taken a f t e r
deactivation shows mostly a C s i g n a l and v i r t u a l l y no Ru s i g n a l . If
+
the surface i s subjected to A r sputtering a l l s i g n a l s attenuate
with respect to those f o r Ru i n d i c a t i n g that we are observing a
surface carbon species. This has been interpreted as the formation
of e i t h e r g r a p h i t i c carbon or d e a c t i v a t i n g C H species on the
n m
electrode surface (2) .

The Auger e l e c t r o n spectrum of the surface of the electrode
deactivated by carbon monoxide reduction at 75 °C has a spectrum
nearly i d e n t i c a l to that of the electrode deactivated during carbon
dioxide reduction, showing the presence of enough surface carbon to
+
almost t o t a l l y block the Ru s i g n a l (Figure 2) . Ar sputtering
restores the spectrum of a clean Ru surface, again i n d i c a t i n g
surface carbon. This implies that the reduction of carbon monoxide
proceeds v i a d i s s o c i a t i o n to surface carbon atoms just as the
reduction of carbon dioxide does. However, the temperature of
deactivation i s lower f o r carbon monoxide than f o r carbon dioxide
i n d i c a t i n g that i t i s easier to s p l i t the carbon monoxide to carbon.
Methanol Reduction at Ruthenium. The reduction of methanol to

methane does occur as shown by the data i n Table I I I . The data f o r
each electrode are presented i n the order that they were c o l l e c t e d .
Rates can be higher f o r methanol reduction compared to carbon
dioxide reduction though faradaic e f f i c i e n c i e s are lower. Unlike
carbon dioxide reduction, the rate of methane formation i s extremely

35. S U M M E R S AND FRESE CO and Methanol Reduction to Methane 523
After Carbon | After Carbon Dioxide

Dioxide 1 Reduction at 90 °C
Reduction at 1
60 °C I
•
LU Ru I
S R u
Ru
•σ
Ru (+trace C)
C (+trace Ru) 1
200 300 1 1
1
Electron Energy (eV)
Figure 1. Auger e l e c t r o n spectrum of the surface of a Ru

electrode before and a f t e r deactivation by reduction of carbon
dioxide at higher temperatures (-90 °C i n 0.2 M Na2S0 at pH 4 4
and -0.545 V vs SCE).
4\rwii
Ν
Ru
LU After Reduction Ru K »
p of Carbon
Monoxide at Ru (+ trace C)
75 °C 1
200 300
After Reduction of
Methanol at 90 °C
C (+ trace Ru)
1
200 300
Electron Energy (eV)
Figure 2. Auger e l e c t r o n spectrum of the surface of two Ru

electrodes a f t e r deactivation by reduction of carbon monoxide and
methanol at higher temperatures (75 and 90 °C respectively i n 0.2
M Na S0 at pH 4 and -0.545 V vs SCE ). The presence of Κ on the
2 4
+
surface must r e s u l t from the adsorption of K ions present as an
impurity i n the e l e c t r o l y t e .

Table I I I . Rate and Faradaic E f f i c i e n c y of C H 4 Formation from CH3OH

a
at Electroplated Ru Electrodes
b c d 8
experiment [CH3OH] pH j Ε Τ Eff Rate χ 10
2 2 1
(mM) (LA cm" ) (V vs SCE) (°C) (%) (mol cm" h r " )
electrode #1
1 75 4 255 -0.,54 60 5.,0 23. 6
2 75 4 220 -0..54 70-75 6.2 25. 5
3 75 4 408 -0.,54 90 5.,0 38.,0
4 75 4 147 -0..54 60 0.,8 2.2
electrode #2
1 75 4 255 -0..54 60 1..9 9..0
2 1 4 178 -0..54 60 1..8 5..9
3 500 4 165 -0..54 60 1..6 4..8
4 200 4 121 -0,.54 60 1,.6 3..6
5 200 5.2 60 -0 .61 60 0 5 0 5
6 200 3
7 200 1.7
electrode #3
1 1 4 485 -0 .54 60 0 .3 2 .5
2 75 3 907 -0 .54 60 0 .3 4 .6
3 75 4 146 -0 .54 22 0 .3 0 .7
4 75 4 296 -0 .70 60 0 .8 4 .7
a) A l l e l e c t r o l y s e s were i n 0.2 M reagent grade Na2S04«

b) Average current density based on geometrical area.
c) Faradaic e f f i c i e n c y f o r methane formation.
d) Average rate of methane formation.
v a r i a b l e from one electrode to the next. However the a c t i v i t y of

each electrode i s r e l a t i v e l y constant from experiment to experiment.
This i n d i c a t e s that the mechanism f o r methanol reduction i s
s e n s i t i v e to some, as yet unknown, surface condition that does not
a f f e c t the reduction of carbon dioxide which shows much more
reproducible rates.
Like the reduction of carbon dioxide to methane, the rate of
reduction of methanol to methane increases with temperature (see
experiments 1-4, e l e c t r o d e #1 i n Table III) (2.) . Unlike the
reduction of carbon dioxide, the f a r a d a i c e f f i c i e n c y does not
increase i n d i c a t i n g that the formation of methane has an a c t i v a t i o n
energy s i m i l a r to the competing process ( H 2 formation). Like carbon
monoxide and carbon dioxide reductions, the r e a c t i o n deactivates
when run at excessive temperature. However, i n the case of methanol
reduction, even at 90 °C the rate i s s t i l l i n c r e a s i n g i n d i c a t i n g
that methanol reduction i s the least prone to deactivation. There
i s some deactivation since e l e c t r o l y s i s at 60 °C, a f t e r e l e c t r o l y s i s
at 90 °C, leads to s i g n i f i c a n t l y reduced rates (Table III) . An
electrode deactivated during methanol reduction does not show the
presence of a large amount of surface carbon (Figure 2) i n d i c a t i n g a
d i f f e r e n t deactivating species. The lack of surface carbon and the
higher temperature of deactivation implies that, contrary to carbon
monoxide and carbon dioxide reduction, methanol reduction does not
involve d i s s o c i a t i o n to surface carbon. At 60° C the reduction of

35. SUMMERS AND FRESE CO and Methanol Reduction to Methane 525
methanol also shows a slow deactivation from one experiment to the

next (see below) that i s not seen f o r carbon dioxide reductions at
the same temperature (2.) . Species such as COH j are possible poisons ac
(£) .
The f i r s t four experiments with electrode #2 (Table III) were
run at d i f f e r e n t methanol concentrations. Dropping the concen-
t r a t i o n from 75 mM to 1 mM and from 500 mM to 200 mM does lead to a
decrease i n the rate of reduction, but less than would be expected
f o r such a large change i n concentration. Also, there i s a steady
drop i n the rate across a l l the experiments i n d i c a t i n g a slow
deactivation of the electrode so that not a l l of the decrease i s due
to concentration changes. In increasing the concentration from 1 mM
to 500 mM there i s even a small decrease i n rate. Thus there does
not appear to be a strong dependence on methanol concentration
implicating the importance of a surface chemical step.
The influence of pH i s more prominent than e i t h e r the e f f e c t s
of d e a c t i v a t i o n or methanol concentration Th dat (experiment
4-7 on electrode #2, Tabl
methane formation fro
greater a c i d i t y u n t i l a maximum at pH ~3 i s reached whereupon the
rate begins to decrease (Figure 3) . This i s nearly i d e n t i c a l to
r e s u l t s seen (Figure 4) f o r carbon dioxide reduction to methane
(2.) . This i s interpreted as i n d i c a t i n g that the reaction proceeds
at a f a s t e r rate as the hydrogen coverage increases due to f a s t e r
hydrogénation of surface intermediates, but that excessive surface
hydrogen coverage blocks carbonaceous intermediates (hence the
decrease at lower pH). Again the importance of a surface chemical
step i s implied.
Carbon Monoxide Reduction at Copper. At copper electrodes carbon

monoxide i s thought to be an intermediate i n the reduction of carbon
d i o x i d e and i s formed as the major product with n i t r i c a c i d
pretreated electrodes (2. and Kim, J . J . ; Summers, D. P.; Frese, K.
W., J r . J . E l e c t r o a n a l . Chem. i n press.). As the data i n Table IV
i n d i c a t e s , methane can be formed by carbon monoxide reduction at
Table IV. Rate and Faradaic E f f i c i e n c y of CH 4 Formation from CO at

Cu Electrodes
a b c 6
Electrolyte pH j Ε Eff Rate χ 10
2 2 1
(0.2 M) (niA cm" ) (V vs SCE) (%) (mol cm" h r " )
Na HP0
2 4 6..1 5 -1..53 3..64 1..13
Na HP0
2 4 6..1 14 -1..72 0..54 0..46
Na HP0
2 4 7..3 5 -1..8 0..61 0..19
Na HP0
2 4 7,.4 10 -1..83 0..91 0,.56
Na HP0
2 4 7,.3 10 -2,.0 2,.1 1,.33
KHC0 3 9 .5 26 -1,.98 1,.5 2,.43
a. Average current density based on geometrical area.

b. Faradaic e f f i c i e n c y f o r methane formation.
c. Average rate of methane formation.

Figure 4. The e f f e c t of pH on the average rate of methane

formation from carbon dioxide. In 0.2 M Na2S0 at 60 °C and at4
constant over p o t e n t i a l (-0.545 V vs SCE at pH 4).

35. SUMMERS AND FRESE CO and Methanol Reduction to Methane527
copper electrodes under similar conditions to those at which methane

is formed from carbon dioxide. Just as copper gives higher current
densities but poorer overvoltages for carbon dioxide reduction than
ruthenium, the reduction of carbon monoxide at copper electrodes
shows higher rates and larger overvoltages than at ruthenium
electrodes. Again, as with ruthenium electrodes, the reduction of
carbon monoxide is slower than the reduction of carbon dioxide along
with lower faradaic efficiencies (the major other product is
hydrogen) (Kim, J . J . ; Summers, D. P.; Frese, K. W., Jr. J •
Electroanal. Chem. in press.). Total currents are also lower,
consistent with the blocking of the surface with carbon monoxide.
However, in this potential region the reduction of carbon dioxide is
diffusion controlled and the ratio of the rates of carbon dioxide
reduction and carbon monoxide reduction (30-60 in favor of carbon
dioxide) is within experimental error of the ratio of solubilities
(-40 in favor of carbon dioxide). Thus lower solubility can not be
dismissed as the source of lower rates for carbon monoxide
reduction.
Acknowledgments
The Authors acknowledge the support of the Gas Research Institute.
Literature Cited
1) Catalytic Activation of Carbon Dioxide; W. M. Ayers, ed.; ACS
Symposium Series No. 363; American Chemical Society: Washington,
DC, 1988
2) Summers, D. P.; Frese, K. W., Jr. Langmiur 1988,4,51.
3) Hori, Y.; Kikuchi, K.; Murata, Α.; Suzuki, S. Chem. Lett.
1986,897.
4) Cooke, R. L . ; MacDuff, R. C.; Sammells, A. F. J. Electrochem.
Soc. 1987,134,1873.
5) Summers, D. P.; Frese, K. W., Jr. J. Electrochem. Soc.
1988,135,264.
6) Hori, Y.; Murato, Α.; Takahashi, R.; Suzuki, S. J. Amer. Chem.
Soc. 1987,109,5022.
7) Stenin, V. F.; Podlovchenko, Β. I. Elektrokhimiya 1967,3,481.
8) Yasil'ev, Y. B.; Bagotsky, V. S. J. Appl. Electrochem.
1986,16,703.
9) Summers, D. P.; Frese, K. W., Jr. SRI Annual Report, April 30,
1987, GRI Contract No. 5083-260-0922, SRI Project PYU 7142.

Chapter 36
Surface Organometallic and Coordination

Chemistry of Iridium, Platinum,
and Gold Electrocatalysts
Manuel P. Soriaga, G. M . Berry, M . E. Bothwell, B. G. Bravo, G. J. Cali,

J. E. Harris, T. Mebrahtu, S. L. Michelhaugh, and J. F. Rodriguez
Department of Chemistry, Texas A&M University, College Station,

TX 77843
The interactio organi

inorganic ligands with Ir, Pt and Au
electrocatalysts has been studied in parallel to
help establish the interfacial organometallic or
coordination chemistry of these electrocatalysts
in aqueous solutions. As a f i r s t study, iodide,
hydroquinone, 2,5-dihydroxythiophenol, and 3,6-
dihydroxypyridazine were employed as model
surface ligands because they are reversibly
electroactive and exhibit variable a f f i n i t i e s
towards the subject electrocatalysts. Under the
present conditions, chemisorption has been found
to be directly analogous to oxidative addition,
and desorption similar to reductive elimination.
Consequently, surface coordination of an
electroactive center overwhelmingly favors i t s
oxidized state over i t s reduced form. If the
redox center is only indirectly attached to the
surface via an electrochemically inert anchor,
substrate-mediated interactions between the
electroactive moieties may arise if the redox
center i t s e l f i n t e r a c t s strongly with the
electrode surface. It seems plausible to view
the phenomenon of substrate-mediated adsorbate
-adsorbate interactions in terms of mixed-valence
metal complexes.
The m o d e l i n g o f i n t e r m e d i a t e s f o r m e d f r o m t h e i n t e r a c t i o n
o f o r g a n i c compounds w i t h t r a n s i t i o n - m e t a l s u r f a c e s b a s e d
on a n a l o g i e s t o homogeneous o r g a n o m e t a l l i c c o m p l e x e s h a s
b e e n a t t e m p t e d i n t h e p a s t (.1). A l t h o u g h t h e e x t e n s i o n o f
t r a d i t i o n a l concepts o f molecular c o o r d i n a t i o n chemistry
t o s u r f a c e compounds i s a s o u n d a n d l o g i c a l p r o p o s i t i o n ,
e a r l y s t u d i e s were o n l y m a r g i n a l l y s u c c e s s f u l b e c a u s e
d e t a i l e d s t r u c t u r a l a n d r e a c t i v i t y i n f o r m a t i o n on t h e
0097-6156/88/0378-0528$06.00/0

36. SORIAGA ET AL. Ligand Interaction with Electrocatalysts 529
s u r f a c e complexes had b e e n u n a v a i l a b l e u n t i l r e c e n t l y (2.) .

E x p e r i m e n t s b a s e d upon modern s u r f a c e a n a l y t i c a l methods
have now e s t a b l i s h e d t h a t t h e i n t e r a c t i o n o f i n o r g a n i c and
organic compounds w i t h transition-metal surfaces has
s e v e r a l commonalities with the bonding of such l i g a n d s to
metal centers i n molecular and m e t a l - c l u s t e r complexes
Q ) . T h e o r e t i c a l treatments c u r r e n t l y e x i s t which support
the empirical assertions , and studies of
o r g a n o m e t a l l i c c h e m i s t r y a t t h e g a s - m e t a l i n t e r f a c e have
p r o l i f e r a t e d (5-7). U n f o r t u n a t e l y , s i m i l a r i n v e s t i g a t i o n s
f o c u s e d on t h e e l e c t r o d e - s o l u t i o n i n t e r f a c e a r e meager.
R e s u l t s d e r i v e d f r o m g a s - s o l i d s t u d i e s c a n n o t be a d o p t e d
directly to electrocatalytic phenomena i n view of
experimental parameters which are unique only to the
e l e c t r o c h e m i c a l e n v i r o n m e n t . D i f f e r e n c e s i n s t r u c t u r e and
r e a c t i v i t y b e t w e e n s u r f a c e i n t e r m e d i a t e s f o r m e d i n vacuum
and u n d e r e l e c t r o c h e m i c a l c o n d i t i o n hav bee documented
(8-9). S u r f a c e complexe
interface are mor
c o m p l e x e s most p r o b a b l y b e c a u s e t h e e l e c t r o d e s u r f a c e i s
i n i t i a l l y c o v e r e d by w e a k l y c o o r d i n a t i n g e l e c t r o l y t e and
s o l v e n t m o l e c u l e s (j)) . R e a c t i o n s b e t w e e n s u r f a c e l i g a n d s
and the electrode surface thus involve displacement
r e a c t i o n s very s i m i l a r to those i n molecular coordination
chemistry.
Table 1. Surface-Cluster Analogies
Electrode Surfaces C l u s t e r Complexes

Chemisorption Synthesis
Adsorbate O r i e n t a t i o n Mode o f C o o r d i n a t i o n
Competitive Chemisorption Ligand S u b s t i t u t i o n
A d s o r b a t e Exchange L i g a n d Exchange
Adsorbate R e a c t i v i t y Ligand R e a c t i v i t y
Electrocatalysis Homogeneous C a t a l y s i s
B a s e d upon a n a l o g i e s b e t w e e n s u r f a c e and molecular

coordination chemistry o u t l i n e d i n Table 1, we have
r e c e n t l y set f o r t h t o i n v e s t i g a t e the i n t e r a c t i o n of
s u r f a c e - a c t i v e and r e v e r s i b l y e l e c t r o a c t i v e m o i e t i e s w i t h
t h e n o b l e - m e t a l e l e c t r o c a t a l y s t s Ru, Rh, Pd, I r , P t and
Au. Our i n t e r e s t i n t h i s c l a s s o f compounds i s b a s e d on
the f a c t that chemisorption-induced changes i n t h e i r redox
p r o p e r t i e s y i e l d important information concerning the
coordination/organometallic chemistry of the electrode
s u r f a c e . F o r example, a l t e r a t i o n o f t h e r e v e r s i b l e r e d o x
p o t e n t i a l b r o u g h t a b o u t by t h e c h e m i s o r p t i o n p r o c e s s i s a
measure o f t h e s u r f a c e - c o m p l e x f o r m a t i o n c o n s t a n t o f t h e
o x i d i z e d s t a t e r e l a t i v e t o t h e r e d u c e d form; s u c h b e h a v i o r
i s e x p e c t e d t o be d e p e n d e n t upon t h e e l e c t r o d e m a t e r i a l .
In t h i s p a p e r , we d e s c r i b e r e s u l t s o b t a i n e d when i o d i d e ,
h y d r o q u i n o n e (HQ), 2 , 5 - d i h y d r o x y t h i o p h e n o l (DHT), and 3,6-
dihydroxypyridazine (DHPz), a l l r e v e r s i b l y e l e c t r o a c t i v e

and s u r f a c e - a c t i v e , a r e made t o r e a c t u n d e r identical

conditions with smooth p o l y c r y s t a l l i n e I r , P t and Au
e l e c t r o d e s i n aqueous s o l u t i o n s . These r e s u l t s w i l l be
viewed i n terms of t r a d i t i o n a l concepts o f o r g a n o m e t a l l i c
and c o o r d i n a t i o n chemistry.
Experimental
Smooth p o l y c r y s t a l l i n e Au, P t and I r t h i n - l a y e r e l e c t r o d e s

were u t i l i z e d ( 1 0 - 1 1 ) . E l e c t r o d e s were c l e a n e d between
t r i a l s by s e q u e n t i a l e l e c t r o c h e m i c a l o x i d a t i o n above 1.2 V
[ A g / A g C l (1 M CI") r e f e r e n c e ] and r e d u c t i o n b e l o w -0.2 V
i n 1 M H 2 S O 4 ; s u r f a c e c l e a n l i n e s s was v e r i f i e d w i t h t h e a i d
o f c y c l i c v o l t a m m e t r y i n t h e same m o l a r s u l f u r i c a c i d
s o l u t i o n . E x p e r i m e n t s were c a r r i e d out i n 1 M H 2 S O 4 , 1 M
NaC104 b u f f e r e d a t pH 7 and 10, and i n 1 M NaOH; s o l u t i o n s
were p r e p a r e d w i t h p y r o l y t i c a l l tripl distilled
(12-) . S u r f a c e r e a g e n t
(HQ), 2,5-dihydroxythiopheno [DH (12.)], 3,6
dihydroxypyridazine (DHPz).
C o o r d i n a t i o n o f t h e i o d o l i g a n d o n t o t h e I r , P t and
Au s u r f a c e s was a c c o m p l i s h e d by e x p o s u r e o f t h e clean
e l e c t r o d e t o 1 mM N a l f o r 180 s e c o n d s a t t h e same pH a t
which subsequent experiments were t o be performed.
Unadsorbed iodide was rinsed away with supporting
e l e c t r o l y t e . We d e t e r m i n e d t h e a b s o l u t e s u r f a c e c o v e r a g e
2
o f i o d i n e Tj (mole cm" ) by means o f t h i n - l a y e r c o u l o m e t r y
in 1 M H2SO4 u s i n g two reactions a t t r i b u t a b l e to the
2
surface iodine, (i) (mole cm" ) i s o b t a i n a b l e from the
c h a r g e f o r o x i d a t i o n o f a d s o r b e d i o d i n e t o aqueous I O 3 "
ri = (Q " Qb)ox,l/5FA (1)
where Q i s t h e t o t a l charge f o r o x i d a t i o n of both i o d i n e

and m e t a l s u r f a c e , Q fe i s the charge f o r o x i d a t i o n of the
m e t a l s u r f a c e , F i s t h e F a r a d a y , and A i s t h e active
surface area (UL, 1_4_) . The use o f an n - v a l u e o f 5 i n
Equation 1 implies that iodine i s zerovalent in the
chemisorbed s t a t e , ( i i ) Tj i s a l s o p r o p o r t i o n a l t o t h e
c h a r g e f o r r e d u c t i o n o f aqueous I O 3 " t o aqueous I 2
^ = (Q - Qb)red,I0 -/5FA 3
(2)
where (Q-Qb) i s t h e c o r r e c t e d c a t h o d i c c h a r g e . S i n c e the

n-value of 5 i n Equation 2 i s independent of the valency
o f s u r f a c e i o d i n e , t h e q u a n t i t y I (Q-Qb) red, 1 0 3 " I must e q u a l
I (Q-Qb)ox,1 I i f the surface-coordinated iodine is
zerovalent.
For the diphenolic compounds, absolute surface-
packing-density measurements were b a s e d upon d i f f e r e n t i a l
t h i n - l a y e r c o u l o m e t r y (j))
r = [ (Q - Qb) - (Qi - Qib) 1/nFA (3)

where (Qi-Qib) a
(Q-Qb) t
n d
r e s p e c t i v e l y , denote t h e
background-corrected f a r a d a i c charges f o r the d i p h e n o l - t o -
q u i n o n e r e d o x p r o c e s s f o r t h e u n a d s o r b e d s p e c i e s a f t e r one
filling (during which s a t u r a t i o n c h e m i s o r p t i o n of the
diphenol occurs) and m u l t i p l e f i l l i n g s ( d u r i n g w h i c h no
a d d i t i o n a l chemisorption takes place) o f the t h i n - l a y e r
c e l l . The n - v a l u e f o r t h e r e d o x r e a c t i o n o f s o l u t i o n
s p e c i e s was d e t e r m i n e d from t h e r e l a t i o n
n = (Q - Q ) / F V C ° b
(4)
where V i s t h e volume o f t h e t h i n - l a y e r c e l l and C° i s the

bulk concentration o f diphenol.
Surface Coordination
o f i o d i n e a t Au, P t
(15-9). P r e v i o u s s t u d i e s w i t single and p o l y c r y s t a l l i n e
P t (15-7) showed t h a t aqueous i o d i d e u n d e r g o e s s p o n t a n e o u s
oxidation upon chemisorption t o form a monolayer o f
zerovalent iodine:
I +
(aq) + H a q ) ( -> I (ads) + l/2H (g)
2
(5)
This o x i d a t i v e chemisorption r e a c t i o n a l s o o c c u r s on I r
and Au s i n c e , i n a d d i t i o n t o e v i d e n c e d e s c r i b e d below, i t
was f o u n d t h a t I (Q-Qb) red, 1 0 3 - I i s e q u a l t o I (Q-Qb) ox, 11 •
Although rinsing of the pretreated surface with
typical s o l v e n t s a t open c i r c u i t d o e s n o t damage t h e
iodine layer, application of sufficiently negative or
p o s i t i v e p o t e n t i a l s removes t h e c h e m i s o r b e d s p e c i e s . D a t a
which i l l u s t r a t e t h e c a t h o d i c s t r i p p i n g o f chemisorbed
i o d i n e a r e shown i n F i g u r e 1 where c a t h o d i c c u r r e n t and Tj
at Pt a r e p l o t t e d simultaneously as f u n c t i o n s o f t h e
a p p l i e d p o t e n t i a l . The d e c r e a s e i n Tj i s c l e a r l y c o r r e l a t e d
with the appearance o f the r e d u c t i o n peaks; the m u l t i p l e
r e d u c t i o n peaks s i g n i f y a coverage-dependent process.
R e s u l t s f o r Au and I r a r e s i m i l a r t o t h a t shown i n F i g u r e
1 except that the cathodic stripping process i s pH-
dependent a t I r and P t but not a t Au. T h i s i s d e m o n s t r a t e d
i n F i g u r e 2 which g i v e s p l o t s o f E i / 2 , the p o t e n t i a l a t
which T i = 0 . 5 r i , a s a f u n c t i o n o f pH. I n t h e c a s e o f
/ I t i a x
Au, E 1 / 2 i s -0.50 V, a v a l u e w h i c h may be i d e n t i f i e d w i t h

the redox p o t e n t i a l E ° i ( d ) f o r the
a S surface-coordinated
I _
1(ads)/ (ads) couple. The pH-independence o f E ° K i ) , a c S
coupled with results from coulometric measurements,

i n d i c a t e s t h a t t h e r e d u c t i v e e l i m i n a t i o n o f i o d i n e f r o m Au
i s a simple one-electron process:
I _
l(ads) + e" f-> I~(ads) «-> (aq) (6)
In t h e cases o f P t and Ir, coulometric measurements o f t h e

cathodic peaks yield an n - v a l u e of 2 f o r cathodic

d e s o r p t i o n o f i o d i n e . T h i s outcome, c o u p l e d w i t h t h e f a c t s
that ( i ) E 1 / 2 a t b o t h s u r f a c e s i s pH-dependent and t h a t
( i i ) I r a n d P t , i n c o n t r a s t t o Au, have s t r o n g a f f i n i t i e s
towards surface hydrogen at sufficiently negative
p o t e n t i a l s , suggests t h e f o l l o w i n g r e d u c t i v e e l i m i n a t i o n
reaction:
+ 7
I (ads) + H ( a q) + 2e" <-> H d s ) ( a + I'(aq) ( )
I t i s p o s s i b l e t o o b t a i n an e s t i m a t e o f E°i( i ) a t P t ac S
and I r f r o m t h e p l o t o f E i / 2 - v s . - p H (20) . I f E q u a t i o n 7 i s
correct, the Ei/2-vs.-pH p l o t should y i e l d a s t r a i g h t l i n e
w i t h a s l o p e o f -0.0296 a n d an i n t e r c e p t K p r o p o r t i o n a l t o
E°i(ads) :
K = E° I ( a d s ) + E
where p i = - l o g C j - , with C i -
( a q ) being the solution ( a q )
c o n c e n t r a t i o n o f t h e desorbed iodide. At E 1 / 2 , C i - ( ) a q
equals 0.5Tj (A/V).

r m a x E°H(ads) i s potential f o r t n e
u n d e r p o t e n t i a l d e p o s i t i o n o f hydrogen, a v a l u e not unique

f o r a p o l y c r y s t a l l i n e s u r f a c e . I f E° ( } ) i s simply taken H ac S
as t h e p o t e n t i a l a t which t h e f r a c t i o n a l coverage o f
chemisorbed hydrogen i s o n e - h a l f , then i t i s approximately
e q u a l t o -0.1 V f o r b o t h P t and I r i n m o l a r s u l f u r i c a c i d .
S u b s t i t u t i o n o f t h e s e and t h e K v a l u e s from F i g u r e 2 i n t o
Equation 8 y i e l d s E ° ) « -0.36 V f o r P t a n d « -0.32 V
I ( a d s
f o r I r . The s l o p e s o b t a i n e d f o r P t a n d I r were -0.028 a n d

-0.029, r e s p e c t i v e l y , i n a c c o r d a n c e w i t h E q u a t i o n 7.
The E°i( } ) v a l u e s o b t a i n e d h e r e i n d i c a t e t h a t , upon
ac S
surface coordination, t h e redox potential of the

i o d i n e / i o d i d e c o u p l e i s s h i f t e d i n t h e negative direction
by a b o u t 0.90 V on Au, 0.7 6 V on P t , a n d 0.72 V on I r .
These c h e m i s o r p t i o n - i n d u c e d redox p o t e n t i a l s h i f t s c a n be
e m p l o y e d t o e s t i m a t e t h e ratio o f the formation constants
f o r s u r f a c e c o o r d i n a t i o n o f i o d i n e and i o d i d e :
RT In [K f f I /Kf,i-] = -F[E° ( a d s ) - E<> (aq) ] - AG° d (9)
where K f i a n d K f i - a r e t h e r e s p e c t i v e f o r m a t i o n c o n s t a n t s
f f
for s u r f a c e - c o o r d i n a t e d i o d i n e and i o d i d e , E ° ( i ) and S O
E
°(ads) a r e t h e r e s p e c t i v e redox potentials f o r the
12 ( a q ) / I " (aq) a n d I ( a d s ) / I " (ads) c o u p l e s , a n d AG°d i s t h e
energy involved i n the I 2 ( a q ) (aq) _ > 2 1
dissociation (2JLJ .
S u b s t i t u t i o n of experimental values into Equation 9 y i e l d s
2 8 2 6
a formation-constant r a t i o of 2 x 1 0 f o r Au, 1 x 1 0 for
2 5
Pt, and 2 x 1 0 f o r I r . These e x c e e d i n g l y l a r g e v a l u e s
s i g n i f y overwhelming p r e f e r e n c e by t h e s u b j e c t metals f o r
s u r f a c e c o o r d i n a t i o n o f z e r o v a l e n t i o d i n e over iodide.
Comparison o f t h e K f i / K f i - v a l u e s i n d i c a t e s t h a t t h i s
f f
p r e f e r e n t i a l s u r f a c e c o o r d i n a t i o n d e c r e a s e s f r o m Au t o P t

1.3
-8' •
-1.1 -0.
E/V vs. AgCl

Figure 1. C a t h o d i c c u r r e n t a n d Tj as f u n c t i o n s of
p o t e n t i a l f o r an I - c o a t e d P t i n 1 M NaC104 b u f f e r e d a t
2
pH 10. A r e a o f e l e c t r o d e , A = 1.04 cm ; sweep r a t e , r =
2 mV/s; t e m p e r a t u r e , T = 298 K.
pH
F i g u r e 2. P l o t o f E 1 / 2 , t h e p o t e n t i a l a t w h i c h Tj i s a t
= 2
half-maximum as a f u n c t i o n o f pH. A^ u 1.07 cm ; A j = r
2
1.40 cm . O t h e r c o n d i t i o n s were as i n F i g u r e 1. The
s o l i d l i n e s represent the l i n e a r l e a s t squares f i t .

t o I r , a t r e n d w h i c h may be q u a l i t a t i v e l y r a t i o n a l i z e d i n
terms o f the a c c e p t o r p r o p e r t i e s o f t h e z e r o v a l e n t metal.
Surface Organometallic Chemistry o f Hydroauinone. Previous

studies (°L) h a v e e s t a b l i s h e d t h a t t h e i n t e r a c t i o n of
aqueous HQ with smooth polycrystalline Pt is
concentration-dependent. Below 0.1 mM, HQ undergoes
spontaneous o x i d a t i o n t o form a c h e m i s o r b e d monolayer o f
6
f l a t - o r i e n t e d (TJ ) benzoquinone (BQ) s i m i l a r t o t h a t i n t h e
homogeneous coordination of benzoquinone to
tris(triethylphosphine)Pt(0) Q):
C H4(OH) (aq)
6 2 -> 6
Tl -C H 06 4 2 (ads) + H 2 (g) (10)
Above 1 mM, C-H a c t i v a t i o n o c c u r s t o f o r m a c h e m i s o r b e d

l a y e r o f e d g e - b o n d e d (2,3-TI ) h y d r o q u i n o n e a n a l o g o u s t o o-
2
benzyne o r g a n o m e t a l l i compound formed w i t h Pt d O

c l u s t e r s (2.) :
C H (OH) (aq)
6 4 2 -> 2
, 3-Tl -C H
2
6 2 (OH) 2 (ads) + H 2 (g) (11)
E q u a t i o n s 10 and 11 i n d i c a t e t h a t t h e r e d o x p o t e n t i a l o f
t h e HQ/BQ c o u p l e i s s h i f t e d i n t h e n e g a t i v e d i r e c t i o n when
*n -chemisorbed b u t s h i f t e d i n t h e p o s i t i v e d i r e c t i o n when
6
2,3-ii -bonded. T h i s o r i e n t a t i o n - d e p e n d e n t s h i f t i n redox

2
p o t e n t i a l i s n o t u n e x p e c t e d by a n a l o g y with molecular
o r g a n o m e t a l l i c compounds. F o r example, t h e r e d o x p o t e n t i a l
f o r the r e v e r s i b l e , o n e - e l e c t r o n r e d u c t i o n of duroquinone
i n a c e t o n i t r i l e i s s h i f t e d from -0.90 V ( v s . SCE) t o -0.69
V i n b i s ( d u r o q u i n o n e ) N i (0) a n d t o -1.45 V in (1,5-
cyclooctadiene)(duroquinone)Ni(0) (22).
Figures 3 and 4, respectively, show thin-layer
c u r r e n t - p o t e n t i a l c u r v e s f o r p o l y c r y s t a l l i n e Au and I r i n
m o l a r s u l f u r i c a c i d b e f o r e and a f t e r e x p o s u r e t o a 2 mM HQ
s o l u t i o n . F o r smooth Au, no c h a n g e s i n t h e voltammetric
curves are seen. In c o m p a r i s o n , a prominent anodic
o x i d a t i o n peak i s o b s e r v e d f o r I r a f t e r p r e t r e a t m e n t w i t h
HQ. These o b s e r v a t i o n s , w h i c h i n d i c a t e t h a t I r i s r e a c t i v e
t o w a r d s HQ b u t Au i s n o t , a r e c o n s i s t e n t w i t h what i s
known f r o m t h e l i t e r a t u r e on homogeneous o r g a n o m e t a l l i c
c h e m i s t r y (21) : I r and P t complexes a r e r e a c t i v e t o w a r d s a
v a r i e t y o f o r g a n i c compounds, whereas Au i s i n e r t .
Surface Coordination of 3.6-Dihydroxypyridazine. Room-

t e m p e r a t u r e T D H P Z - V S . - l o g C c u r v e s f o r DHPz a t Au and Pt
e l e c t r o d e s i n 1 M H 2 S O 4 and i n 1 M NaC104 b u f f e r e d a t pH 7
a r e shown i n F i g u r e 5. I t i s i n t e r e s t i n g t o n o t e t h a t T D H P Z
v a l u e s i n d e p e n d e n t o f c o n c e n t r a t i o n and pH a r e a t t a i n e d a t
P t , whereas pH-dependent i s o t h e r m s a r e o b t a i n e d a t Au. At
pH 7, t h e r p v a l u e s a t P t and Au a r e i d e n t i c a l [0.66(6)
D H 2
2
nmole c m " ] . In 1 M H 2 S O 4 , however, TDHPZ on Au i s
profoundly concentration-dependent.
E a r l i e r e x p l o r a t o r y s t u d i e s (2.) o f t h e i n t e r a c t i o n o f
DHPz w i t h smooth p o l y c r y s t a l l i n e P t i n d i c a t e d t h a t , a t

4->
c
QJ
E/V vs. AgCl

Figure 3. T h i n - l a y e r c u r r e n t - p o t e n t i a l c u r v e s i n 1 M
H2SO4 f o r Au b e f o r e and a f t e r e x p o s u r e t o 2 mM HQ.
E x p e r i m e n t a l c o n d i t i o n s were as i n F i g u r e s 1 and 2.
Clean and HQ-Coated Iridium

81 1 1
' 1 1 1 1
1 1 1
' 1 1 1
' 1 1 1 1
1 1 1 1
1 1 1 1
1
1 ... 1 ... 1 ... t ... 1 ... 1 1

r
-10
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
E/V vs. AgCl
Figure 4. T h i n - l a y e r c u r r e n t - p o t e n t i a l c u r v e s in 1 M
H2SO4 f o r I r b e f o r e and a f t e r e x p o s u r e t o 2 mM HQ.
E x p e r i m e n t a l c o n d i t i o n s were as i n F i g u r e s 1-3.

room t e m p e r a t u r e , c h e m i s o r b e d DHPz i s b o u n d t o o n l y one

n i t r o g e n h e t e r o a t o m e v e n i f t h e two n i t r o g e n s i n DHPz a r e
c h e m i c a l l y e q u i v a l e n t . T h i s i s i n agreement w i t h t h e f a c t
t h a t , i n complexes w i t h z e r o v a l e n t P t , p y r i d a z i n e i s T ^ - N
c o o r d i n a t e d a t ambient t e m p e r a t u r e s (2.) .
The pH-independence o f T D H P Z a t P t i n d i c a t e s t h a t t h e
d r i v i n g f o r c e f o r c o o r d i n a t i o n o f the n i t r o g e n heteroatom
t o t h e P t s u r f a c e i s much l a r g e r t h a n t h a t f o r p r o t o n a t i o n
even i n m o l a r a c i d . T h i s b e h a v i o r i s i n c o n t r a s t t o t h a t
o f p y r i d i n e , where p r o t o n a t i o n o f t h e n i t r o g e n h e t e r o a t o m
i n m o l a r a c i d h i n d e r s N - c o o r d i n a t i o n t o t h e s u r f a c e (j)) .
Such a d i f f e r e n c e i n c h e m i s o r p t i o n c h a r a c t e r i s t i c s may be
related to the fact that the b a s i c i t y of the nitrogen
h e t e r o a t o m i n p y r i d i n e (pK^ = 8 . 8 ) i s much g r e a t e r t h a n
t h a t o f t h e n i t r o g e n s i n p y r i d a z i n e (pKfc = 11.8) (22.) .
The f a c t t h a t r p D H z on Au i s i d e n t i c a l t o t h a t on P t
a t pH 7 i s e v i d e n c e t h a
a l s o f o r m e d on Au a
isotherm on Au a t pH 0 i s n o t s t e p w i s e u n l i k e those
e x h i b i t e d by compounds a t t a c h e d i n m u l t i p l e o r i e n t a t i o n a l
s t a t e s , a n d ( i i ) i t h a s a l r e a d y b e e n shown a b o v e t h a t
h y d r o q u i n o n e , t h e h o m o a r o m a t i c a n a l o g u e o f DHPz, i s n o t
c h e m i s o r b e d on Au, i t c a n be a r g u e d t h a t T ^ - N s u r f a c e -
coordination o f DHPz o c c u r s on Au a t pH 0 e v e n a t
c o v e r a g e s b e l o w t h e s a t u r a t i o n v a l u e . I t c a n be i n f e r r e d
f u r t h e r t h a t t h e d r i v i n g f o r c e s f o r p r o t o n a t i o n a n d Au-
surface-coordination of the N heteroatom are equally
c o m p e t i t i v e i n molar a c i d .
The u n f e t t e r e d N - c o o r d i n a t i o n o f DHPz t o t h e P t
s u r f a c e even i n m o l a r a c i d c l e a r l y i n d i c a t e s t h a t t h e
s u r f a c e - c o o r d i n a t i o n s t r e n g t h o f DHPz i s l a r g e r on P t t h a n
on Au. T h i s i s c o n s i s t e n t w i t h t h e f a c t t h a t , a l t h o u g h
a n a l o g o u s DHPz-Pt c o o r d i n a t i o n c o m p l e x e s e x i s t , none has
been r e p o r t e d f o r Au.
Surface Coordination of 2 5-dihydroxythiophenol• F i g u r e 6

r
shows c y c l i c c u r r e n t - p o t e n t i a l c u r v e s f o r DHT c h e m i s o r b e d
a t maximum c o v e r a g e a t P t a n d Au i n 1 M H 2 S O 4 . These
voltammetric c u r v e s were o b t a i n e d i n t h e absence o f
u n a d s o r b e d s p e c i e s ; hence, t h e peaks a r e due o n l y t o r e d o x
of t h e s u r f a c e - c o o r d i n a t e d DHT. The a r e a s u n d e r t h e s e
c u r v e s y i e l d r T v a l u e s o f 0.56(4) nmole cm"" a t P t and
D H
2
2
0.54(4) nmole cm" a t Au. T h i s , a l o n g w i t h t h e f a c t t h a t
t h e r e d o x p e a k s a p p e a r a t t h e same p o t e n t i a l r e g i o n where
unadsorbed DHT reacts, signifies a vertical S-TI - 1
o r i e n t a t i o n i n which t h e d i p h e n o l i c group i s p e n d a n t ( r i c c a
2
= 0.57 nmole cm" ) . The h a l f - w i d t h o f t h e r e d o x peak i s
0.21 V a t P t a n d 0.13 V a t Au. S i n c e t h e modes o f
attachment and p a c k i n g d e n s i t i e s are i d e n t i c a l at both
s u r f a c e s , t h e peak b r o a d e n i n g a t P t c a n o n l y be a t t r i b u t e d
t o substrate-mediated adsorbate-adsorbate i n t e r a c t i o n s .
F i g u r e 7 shows c u r r e n t - p o t e n t i a l c u r v e s f o r P t a n d Au
precoated with DHT at h a l f coverage. At P t , no
q u i n o n e / d i p h e n o l redox r e a c t i o n i s observed. C l e a r l y ,

0.8
0.0
1
i
-5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0
-Log C
F i g u r e 5. C h e m i s o r p t i o n i s o t h e r m s f o r DHPz a t Au and P t
a t pH 0 and pH 7. E x p e r i m e n t a l c o n d i t i o n s were as i n
F i g u r e s 1-3.
E/V vs. AgCl

F i g u r e 6. T h i n - l a y e r v o l t a m m e t r i c c u r v e s i n M H 2 S O 4 f o r
t h e q u i n o n e / d i p h e n o l r e d o x o f DHT chemisorbed at f u l l
c o v e r a g e on P t and Au. Sweep r a t e s : r A = 3 mV/s;
u r P = 2
t
mV/s. O t h e r c o n d i t i o n s were as i n F i g u r e s 1-3.

-0.1 I—•—•—•—i—•—.—•—i—•—•—•—i—•—I
0.0 0.2 0.4 0.6
E/V vs. AqCl

F i g u r e 7. T h i n - l a y e r v o l t a m m e t r i c c u r v e s i n 1 M H 2 S O 4
f o r t h e q u i n o n e / d i p h e n o l r e d o x o f DHT c h e m i s o r b e d a t
h a l f c o v e r a g e on P t and Au. E x p e r i m e n t a l c o n d i t i o n s were
as i n F i g u r e s 1-3.

direct diphenol-Pt interaction has taken place at

submonolayer coverages. I t may be n o t e d t h a t t h e peak
width a t Au i s unchanged i n g o i n g from full to half
coverage of DHT. These results indicate that, at
submonolayer c o v e r a g e s , DHT r e m a i n s e x c l u s i v e l y S - T ^ on Au 1
b u t b e h a v e s as a s u r f a c e c h e l a t e on P t i n w h i c h b o t h
s u l f u r and d i p h e n o l g r o u p s a r e b o n d e d d i r e c t l y t o t h e
s u r f a c e . The q u i n o n e / d i p h e n o l r e d o x a c t i v i t y a t P t s t a r t s
to disappear at r / r ~ 0.8.
m a x The tilt angle of the
s u r f a c e - c h e l a t e d DHT p r o b a b l y v a r i e s w i t h c o v e r a g e .
These r e s u l t s s u g g e s t t h a t t h e c r i t i c a l f a c t o r i n t h e
s u b s t r a t e - m e d i a t e d i n t e r m o l e c u l a r i n t e r a c t i o n s which occur
w i t h i n t h e c l o s e - p a c k e d DHT l a y e r i s t h e i n h e r e n t s t r o n g
r e a c t i v i t y of the d i p h e n o l i c moiety w i t h the Pt s u r f a c e .
The i n t e r a c t i o n o f a d s o r b a t e s w i t h e a c h o t h e r t h r o u g h t h e
m e d i a t i o n o f the s u b s t r a t e i s o f fundamental importance i n
surface s c i e n c e . Th theoretical treatment however
involves complicate
p r e s e n t l y not w e l l - u n d e r s t o o
v i e w t h e p r e s e n t c a s e o f P t - s u b s t r a t e - m e d i a t e d DHT-DHT
i n t e r a c t i o n s i n terms o f mixed-valence metal complexes
(24.) . F o r example, i n t h e b i n u c l e a r m i x e d - v a l e n c e complex,
f
(NH ) Ru(II)-bpy-Ru(III)(NH )
3 5 (where bpy
3 5 is 4,4 -
bipyridine), t h e two metal centers are s t i l l able to
i n t e r a c t with each o t h e r v i a the d e l o c a l i z e d e l e c t r o n s
w i t h i n t h e bpy l i g a n d . The i n t e r a c t i o n between t h e R u ( I I )
and Ru(III) ions in this mixed-valence complex is
t h e r e f o r e l i g a n d - m e d i a t e d . The R u ( I I ) - R u ( I I I ) c o u p l i n g can
be w r i t t e n s c h e m a t i c a l l y a s :
Ru ( I I ) - b p y - R u (III) <-> Ru ( I I I ) - b p y - R u (II) (12)
By a n a l o g y w i t h E q u a t i o n 12, t h e DHT-DHT i n t e r a c t i o n s
mediated by t h e P t s u r f a c e may be r e p r e s e n t e d by the
following reaction:
Q-S-Pt-Pt-S-H Q <-> H Q - S - P t - P t - S - Q
2 2 (13)
where P t - P t d e n o t e s t h e P t s u r f a c e . O n l y one diphenol

(H Q) 2 and q u i n o n e (Q) s u b s t r a t e - m e d i a t e d p a i r i s d e p i c t e d
for s i m p l i c i t y . One can now v i s u a l i z e how the c o u p l i n g
between t h e H Q and Q c e n t e r s can be m e d i a t e d by t h e P t
2
surface.
Acknowledgments
Acknowledgment i s made t o t h e R o b e r t A. W e l c h F o u n d a t i o n
and t o t h e R e g e n t s o f T e x a s A&M U n i v e r s i t y f o r s u p p o r t o f
this research.
MPS wishes t o d e d i c a t e t h i s a r t i c l e i n memory o f
P r o f e s s o r Rebecca Soriaga-Paredes, l a t e Chairman of the
Department of Chemistry, de la Salle University
(Philippines) .

Literature Cited
1. Ugo, R. Catalysis R e v s . 1975, 11, 225.

Cornell University Press: Ithaca, NY, 1981.
3. Muetterties, E . L . B u l l . Soc. Chim. Belg. 1975, 84,
959.
4. S a i l l a r d , J . Y . ; Hoffman, R. J . Am. Chem. Soc. 1984,
106, 2006.
5. Albert. M.R.; Yates, J . T . , J r . A Surface Scientist's
Guide to Organometallic Chemistry; American Chemical
Society: Washington, D.C., 1987.
6. Friend, C.M.; Muetterties, E . L . J. Am. Chem. Soc.
1981, 103, 767.
7. Canning, N.D.S.; Madix. R . J . J . Phys. Chem. 1984, 88,
2437.
8. Wieckowski, A .
A.T.; Bent, B .
Chem. Soc. 1985, 107, 21.
9. Soriaga, M.P.; Binamira-Soriaga, E.; Hubbard, A.T.;
Benziger, J . B . ; Pang, K.W.P. Inorg. Chem. 1985, 24,
65.
10. Hubbard, A . T . C r i t . Rev. Anal. Chem. 1973, 3, 201 .
11. White, J . H . ; Soriaga, M . P . ; Hubbard, A . T . J.
12. Conway, B . E . ; Angerstein-Kozlowska, H . ; Sharp,
W.B.A.; Criddle, E . E . Anal. Chem. 1973, 45, 1331 .
13. Alcalay, W. Helv. Chim. Acta. 1947, 30, 578.
14. Rodriguez, J.F.; Mebrahtu, T . ; Soriaga, M.P. J.
15. Lane, R . F . ; Hubbard, A . T . J. Phys. Chem. 1975, 79,
808.
16. Stickney, J.L.; Rosasco, S.D.; Salaita, G . ; Hubbard,
A.T. Langmuir. 1985, 1, 89.
17. Felter, T . E . ; Hubbard, A . T . J. Electroanal. Chem.
1979, 1 0 0 , 473.
18. Rodriguez, J.F.; Soriaga, M.P. J. Electrochem. Soc.
1988, 135, 616.
19. Rodriguez, J.F.; Bothwell, M . E . ; H a r r i s , J.E.;
Soriaga, M.P. J . Phys. Chem. 1988, 92, 2702.
20. Soriaga, M.P. J . Electroanal. Chem. 1988, 2 4 0 , 309.
21. Cotton, F . A . ; Wilkinson, G. Advanced Inorganic
Chemistry; Wiley: New York, 1980.
22. Nesmeyanov, A.N. Dokl. Akad. Nauk. SSSR. 1976, 230,
1114.
23. Weast, R.C. Handbook of Chemistry: CRC Press: Boca
Raton, FL, 1986.
24. Creutz, C. Prog. Inorg. Chem. 1983, 30, 1.
RECEIVED June 27, 1988

Author Index
Abruna, H . D., 216 Koval, Carl A , 438

Adzicf, R. R., 497 Laguren-Davidson, Laarni, 8
Albarelli, M . J., 216 Leung, L.-W. H., 303
Anderson, J. E., 451 Lewis, Nathan S., 174
Anderson, Mark R., 383 Li, Jianguo, 338
Bange, K., 54 Lindner, T., I l l
Batina, Nikola, 8 Lipkowski, J., 484
Benziger, Jay B., 83 Love, B., 484
Berry, G. M , 528 Lu, Frank, 8
Blackwood, Daniel, 338 Marinkovic; N. S., 497
Bockris, J. O ' M , 351 Markovic; N . M., 497
Bommarito
Bothwell, M
Bradshaw, , , ,
Bravo, B. G., 528 Mebrahtu, T., 528
Cali, G. J., 528 Michelhaugh, S. L., 528
Campbell, Deborah J., 294 Moylan, Thomas E., 65
Carbonio, Raul, 257 Olson, John B., 438
Carr, R. G., 131 Parkinson, Bruce A., 438
Chandrasekaran, K., 351 Pemberton, Jeanne E., 398
Chooto, Pipat, 466 Penner, Reginald M., 174
Clavilier, J., 202 Pons, Stanley, 338
Coria-Garcia, Jose C , 398 Quate, Calvin F., 174
Corn, Robert M., 294 Rodriguez, J. R, 528
Corrigan, D. S., 303 Rodriguez, Rene' R., 369
Corrigan, Dennis A , 257 Roe, D. K., 233
Dovek, Moris M , 174 Ross, Philip N., Jr., 37
Ehlers, Charles B., 99 Salaita, Ghaleb N., 8
Evans, Dennis R , 383 Sass, J. K., 54,233
Fedyk, J., 431 Sawyer, Donald T., 466
Fierro, Cristian, 257 Scherson, Daniel A , 257
Finklea, H . O., 431 Schoofs, G. R., 83
Fischer, D. A , 131 Schwab, J., 431
Franchina, N., 83 Seki, H., 322
Frank, Douglas G., 8 Shu, Ching-Fong, 408
Frese, Karl W., Jr., 518 Somers, J., I l l
Gao, P., 303 Soriaga, Manuel P., 1,528
Gerischer, H., 233 Stern, Donald A., 8
Gland, J. L., 131 Stickney, John L., 99
Goodman, D. W., 154 Stimming, Ulrich, 275
Gosztola, D., 303 Stuve, E. M., 154
Gregory, Brian W., 99 Summers, David P., 518
Griffin, Gregory L., 369 Tornquist, Wade J., 369
Guillaume, Francis, 369 Tripkovic; A V., 497
Hansen, Galen J., 166 Wagner, Frederick T., 65
Hansen, Wilford N., 166 Weaver, M . J., 303
Hanson, Michael E., 141 White, J. H , 216
Harris, J. E., 528 Wieckowski, Andrzej, 245
Heben, Michael J., 174 Wrighton, Mark S., 408
Hubbard, Arthur T., 8 Xu, Q. Y., 451
Kadish, K. M . , 451 Yeager, Ernest, 141
Kollin, E. B., 131 Zaera, R, 131
Korzeniewski, Carol, 338 Zapien, Donald C , 8
541

Affiliation Index
Brookhaven National Laboratory, 131 Texas A & M University, 1,351,466,528

Case Western Reserve University, 141,257 University of Arizona, 398
Centre National de la Recherche Scientifique, 202 University of Belgrade, 497
Columbia University, 275 University of California—Berkeley, 37
Cornell University, 216 University of California—Riverside, 131
E. I. du Pont de Nemours and Company, 438 University of Cincinnati, 8
Exxon Research & Engineering Company, 131 University of Colorado, 438
Fritz-Haber-Institut der University of Delaware, 383
Max-Planck-Gesellschaft, 54,111,233 University of Georgia, 99
General Motors Research Laboratories, 65,257 University of Guelph, 484
IBM Research Division, 322 University of Houston, 451
Massachusetts Institute of Technology, 408 University of Illinois, 245
Princeton University, 83 University of Michigan, 338
Purdue University, 303 University of Minnesota, 369
SRI International, 518 University of Utah, 338,383
Sandia National Laboratories, 154 Universit f Wisconsin—Madison 294
Schott Glaswerke, 54
Stanford Synchrotron Radiation Laboratory
Stanford University, 174
Subject Index
Adsorption
chlorine on copper, 106-109
Absolute surface-packing-density electrolyte on copper, 106-109
measurements, calculation for oxygen on copper, 103,104/105
diphenolic compounds, 530-531 water on copper, 105-106
4-Acetylpyridine water on metals, 43,44/45
SER spectra, 388,390 Adsorption kinetics, CO, 376,377/378
structure, 385 Adsorption of acetic acid on Pt(lll)
Activation effects on electrochemical single-crystal electrodes
behavior of ordered platinum surfaces L E E D pattern of electrode, 250,252/
high oxygen coverage, 209-210 radiochemistry, 250,252/"
low oxygen coverage, 207,208^,209 vs. current-generating
Adatom oxidation, description, 372 process, 250-254
Adsorbate-covered surfaces, scanning vs. polycrystalline Pt
tunneling microscopy, 188,18Sy,190 electrode, 250,252/",254-255
Adsorbed azide at silver-aqueous interface Ambient gas, emersion, 167
adsorbate orientation, 309 4-(Aminomethyl)pyridine
changes, 310,311/ SERS spectra, 394,3%
potential difference IR spectros- structure, 385
copy, 305,30^,308-309 4-Aminopyridine
surface-enhanced Raman spectros- SERS spectra, 394,396
copy, 305,307/308-309 structure, 385
Adsorbed bipyridiniums Angle-resolved photoelectron spectra
cyclic voltammogram, 434,435,43^" Cu(110)-HCOO, 126,128f,129
electrochemical parameters of first Ni(100)-CO surface,118,llSy
redox wave, 433f ,434 P d ( l l l ) - C N surface, 122,123/
surface coverage vs. scan Aniline
rate, 434-435 coverage, 89
Adsorbed C O on Pt formation, 89
competitive adsorption, 371-372 polymerization, 97
configuration, 370 reflection IR spectra, 89,91/
frequency dependence, 370-371 temperature-programmed reaction spectra, 89,90/"

Affiliation Index
Brookhaven National Laboratory, 131 Texas A & M University, 1,351,466,528

Case Western Reserve University, 141,257 University of Arizona, 398
Centre National de la Recherche Scientifique, 202 University of Belgrade, 497
Columbia University, 275 University of California—Berkeley, 37
Cornell University, 216 University of California—Riverside, 131
E. I. du Pont de Nemours and Company, 438 University of Cincinnati, 8
Exxon Research & Engineering Company, 131 University of Colorado, 438
Fritz-Haber-Institut der University of Delaware, 383
Max-Planck-Gesellschaft, 54,111,233 University of Georgia, 99
General Motors Research Laboratories, 65,257 University of Guelph, 484
IBM Research Division, 322 University of Houston, 451
Massachusetts Institute of Technology, 408 University of Illinois, 245
Princeton University, 83 University of Michigan, 338
Purdue University, 303 University of Minnesota, 369
SRI International, 518 University of Utah, 338,383
Sandia National Laboratories, 154 Universit f Wisconsin—Madison 294
Schott Glaswerke, 54
Stanford Synchrotron Radiation Laboratory
Stanford University, 174
Subject Index
Adsorption
chlorine on copper, 106-109
Absolute surface-packing-density electrolyte on copper, 106-109
measurements, calculation for oxygen on copper, 103,104/105
diphenolic compounds, 530-531 water on copper, 105-106
4-Acetylpyridine water on metals, 43,44/45
SER spectra, 388,390 Adsorption kinetics, CO, 376,377/378
structure, 385 Adsorption of acetic acid on Pt(lll)
Activation effects on electrochemical single-crystal electrodes
behavior of ordered platinum surfaces L E E D pattern of electrode, 250,252/
high oxygen coverage, 209-210 radiochemistry, 250,252/"
low oxygen coverage, 207,208^,209 vs. current-generating
Adatom oxidation, description, 372 process, 250-254
Adsorbate-covered surfaces, scanning vs. polycrystalline Pt
tunneling microscopy, 188,18Sy,190 electrode, 250,252/",254-255
Adsorbed azide at silver-aqueous interface Ambient gas, emersion, 167
adsorbate orientation, 309 4-(Aminomethyl)pyridine
changes, 310,311/ SERS spectra, 394,3%
potential difference IR spectros- structure, 385
copy, 305,30^,308-309 4-Aminopyridine
surface-enhanced Raman spectros- SERS spectra, 394,396
copy, 305,307/308-309 structure, 385
Adsorbed bipyridiniums Angle-resolved photoelectron spectra
cyclic voltammogram, 434,435,43^" Cu(110)-HCOO, 126,128f,129
electrochemical parameters of first Ni(100)-CO surface,118,llSy
redox wave, 433f ,434 P d ( l l l ) - C N surface, 122,123/
surface coverage vs. scan Aniline
rate, 434-435 coverage, 89
Adsorbed C O on Pt formation, 89
competitive adsorption, 371-372 polymerization, 97
configuration, 370 reflection IR spectra, 89,91/
frequency dependence, 370-371 temperature-programmed reaction spectra, 89,90/"

INDEX 543
Anomalous processes, path to definitive

models, 52
Anomalous voltammetry of P t ( l l l ) Capacity, measurement techniques, 280
anomalous features, 40,41/,42 Carbon dioxide, electrochemical
deprotonation of inner layer on Pt reduction to methane, 518
surface, 45,48,4Sy Carbon monoxide
double-layer structure, 45,47/ adsorption on Pt, 484
hydronium ion inner layer, 45,46/ adverse effect on fuel cells, 484
Auger spectroscopy oxidation, 484-495
method of angle measurement, 14,16/" Carbon monoxide reduction at copper,
methods, 11,14 rate and Faradaic efficiency, 525r,527
packing densities of nicotinic Carbon monoxide reduction at ruthenium
acid, 14,15-16f,21f Auger electron spectrum, 522,523/
Pb underpotential deposition effect of CO on reduction of
films, 145,148f C 0 , 520,522/
2
signal ratios of nicotinic effect of pH, 525,52#"

acid, 14,15/ rate and Faradaic efficiency, 520,521/
Azide on silver, vibrational Catalytic polymerization
spectra, 333-334335/ limitations, 95
orientational changes 95
Charge distribution at metal

electrode-electrolyte interfaces
capacity-potential curves of gold vs.
temperature, 283,284/
impedance spectrum, 282,283/
Band shift, effect of electrode temperature dependence of electrode
potential, 325329330-331/ capacity, 282,284/285
Bead method, description, 38,40 Charge-transfer reactions
4-Benzoylpyridine Arrhenius plot of exchange current
SERS spectra, 394395/ density, 285-287,288/"
structure, 385 exchange current density, 286-287,288/
Bimetallic catalysts hydrogen evolution, 287-292
angle-resolved photoemission energy Chemisorbed states of compounds,
distribution curves, 157,15Sy,160 characteristics, 10-11
application, 156 Chemisorption of ethylene, ethylidyne
Auger spectrum after formation, 131-132
electrodeposition, 162,163/ Chlorine, adsorption on copper, 106-109
behavior of interface states, 160 CO adsorption
chemical properties, 156-158 competitive adsorption, 371-372
electrochemical vs. Auger configuration of adsorbed CO, 370
determination of Cu experimental procedures, 372
coverage, 162,163/ frequency dependence of adsorbed
electronic properties, 157,159-160 CO, 370-371
evolution of Cu desorption, 160,161/ on metal, model, 329
physical properties, 157 overview, 370
reaction rate vs. surface CO electrooxidation, mechanism, 316-319
coverage, 157,158/" Coadsorbed nitriles
temperature-programmed adsorption kinetics, 376377/378
desorption, 156-157,158/" competitive adsorption, 371-372
Bimetallic systems, effect of ensemble oxidation kinetics, 374375/376
vs. electronic effects on catalytic PM-IRRAS spectra, 372373/
properties, 155 Coadsorbed Sn atoms
4,4 '-Bipyridiniums cyclic voltammograms, 37837S{f
asymmetric, structure, 431-432 PM-IRRAS spectra, 37838QT381
electrochemical parameters for the Coadsorption, hydrophilic versus
first redox wave, 433/ hydrophobic, 70,72
surface coverage vs. scan rate, 434 Coadsorption of bromine and water on
Bromine coverage, Ag(110), work function change, 58,6Qf
determination, 58,59,6Qf Cobalt porphyrins
Bromine-water adsorption on Ag(110), reactions of low-valent C O with
proposed structure, 61,62/* methylene chloride, 458,45S^

Cobalt porphyrins—Continued Cyclic voltammetry—Continued

reactivity, 457-458 experimental procedures, 485
synthesis, 457 formic acid, 511,512r,513
Conical electrode-planar electrode, germanium porphyrins, 460,461/
current, 182,183/,184 H and 0 adsorption, 485,486/487
2 2
Controlled-potential electrolysis, hydrogen adsorption

equipment, 467 and evolution, 296,297-298/
Cooxidation, cyclic voltammo- on low-index surfaces, 498,49^,500-501
grams, 374,375/,376 on Pt single-crystal stepped
Copper, reaction scheme with O H ~ and surfaces, 501,502-504/505
0 , 477,479,482
2
iron oxyhydroxide system, 258,259/"
Copper components of electronics, isoquinoline, 344,345/
preparation, 99 mixed nickel-iron oxyhydroxides, 268,269/
Copper electrodes, surface poly[l-methyl-l'-(3-thiophene-3-propyl)-
chemistry, 99-109 4,4'-bipyridinium bis(hexafluoro-
Cryogenic ultrahigh vacuum model double phosphate)], 414-415,416/
layers, roles, 81-82 rhodium porphyrins, 453,454/
Crystal electrical annealing and cooling silver electrode, 295,297/
in an inert gas, characteristics, 249-250
Cu (5,4,l)CO cluster
10
calculation of fields, 332-333

schematic view, 332,335/
Cu electrodes, 519 Deprotonation of inner layer on Pt
Cu(110)-HCOO surface, model, 45,48,49/"
angle-resolved photoelectron Design of scanning tunneling microscopy
spectra, 126,128/129 design criteria, 177-178
N E X A F S , 124,125/ design for work under
photoelectron diffraction, 124,126,127/ solution, 178,18Q/;i81
photoelectron spectrum, 126,127/ goals, 177
Current tip design, 178,17S>f
potential dependence, 290,292 Diethyl 3-thenylmalonate, preparation, 410
See also Tunneling current Diffusion coefficient for charge transport,
Cu/Ru catalyst viologen(II)/(I) system, 420,422-423
angle-resolved photoemission energy 2.5- Dihydroxy-4-methylbenzylmercaptan,
distribution curves, 157,15Sy,160 cyclic voltammetry, 11—12/"
behavior of interface states, 160 3.6- Dihydroxypyridazine, surface
chemical properties, 156-158 coordination, 534,536,537/
electrochemical vs. Auger determination 2,5-Dihydroxythiophenol, surface
of Cu coverage, 162,163/ coordination, 536,537-538f,539
electronic properties, 157,159-160 Double-layer emersion
evolution of Cu desorption, 160,161/ existence, 166
physical properties, 157 implications, 167
reaction rate vs. surface mechanism, 167-172
coverage, 157,158/ role of water, 172
temperature-programmed Double-layer structure on P t ( l l l ) ,
desorption, 156-157,158/" model, 45,47/
Cyanide, dipole-dipole coupling Dyes, adsorption on metal
effects, 312,313/ dichalcogenides, 448
Cyanide adsorbed on Ag electrode
effect of isotopic composition on
bands, 325,328/" E
effect of potential change on
bands, 325,327/ Effective electrode potential,
PM-IRRAS spectra, 325,326/ control, 76-80
Cyclic voltammetry Electric field, calculation of
adsorbed C O oxidation, 48#487 effect, 332-333
adsorbed molecules, 11,12-13/ Electric field mechanism, potential
bipyridiniums, 432-436 dependent shift of vibrational
CO oxidation, 374,375/376 frequencies, 347
coadsorbed Sn atoms, 378,37S{f Electrical conductivity,
equipment, 467 HC10 • 5.5H 0, 280,281/282
4 2

INDEX 545
Electrocatalysis on single-crystal surfaces Electrolyte adsorption, on copper, 106-109

developments, 497-498 Electron energy-loss spectroscopy
progress, 497 assignments of bands, 14,22/,23
role of surface structure, 498-516 nicotinic acid, 14,17-2Qf
Electrocatalytic systems pyridine, 14,22/,34/35
problems in studying, 217-218 pyridinecarboxylic acids and
techniques, 217 diacids, 23,24-26/"
Electrochemical adsorption at catalytic Electron injection
electrodes, classification of CTRIPS spectra, 235,238/"
adsorption processes, 248 origin of high-energy light, 239
Electrochemical behavior, oscilloscope trace by trans-
charge-transfer reactions, 285-292 stilbene, 235,237/
Electrochemical experiments, reversible reduction of /ra/w-stilbene
apparatus, 156 at A u surface, 235,236/"
Electrochemical kinetics, Electron transfer between a molecule and
development, 438 a metal electrode, effect of both
Electrochemical oxidation of hydroxide ion orientation and distance, 431
effect of metal electrode, 468,469-471/ Electrooxidation mechanism of
mechanism, 476-477 benzaldehyde, single potential
potentiometric titrations, 468 alteratio IR
products, 466-467
redox potentials, 477,478/
Electrochemical phenomena, SERS, 384 porphyrins, 452-463
Electrochemical reduction of carbon Emersion, description, 166-167
monoxide Emersion into ambient gas
applications, 518-519 cyclic emersogram, 167,168/
at copper, 525,527 electrolyte cyclic potentiogram, 167,168/
at ruthenium, 520-526 influencing factors, 169
experimental procedures, 519-520 Emersion into ultrahigh vacuum
potentials, 519 applications, 169
Electrochemical research, goals, 216-217 factors influencing work
Electrochemically modulated IR function, 171-172
spectroscopy, description, 338 systematic shift of work
Electrochemistry function, 171-172
advantages, 1-2 work function of electrode vs.
applications, 1 emersion potential, 169,170/171
applications of scanning tunneling Emission of P-polarized light, hole
microscopy, 174-198 injection into metal electrodes, 241
cell, 219,220/" Ethylene, chemisorbed
disadvantages, 2 chemisorption, 131-132
equipment, 411 computer simulation for H 2
experimental procedure, 432 thermal desorption spectra, 138/139

instrumentation, 219 effect of temperature on ethylidyne
metalloporphyrins, 456-457 conversion, 135,13^"
structure-composition-reactivity Ethylidyne formation
correlations, 2-3 apparatus for N E X A F S
Electrochemistry of ferrocenes experiments, 132-133
capacitance of space charge layer vs. effect of temperature, 133,136/
potential, 443-444,445/ temperature dependence of rate
electrodes, 443 constants, 135,137/
Electrode potential thermal desorption
effect of potential vs. coverage on spectra, 135,137-138/139
shift, 329,331/ N-Ethyl-Vv"-octadecyl-4,4'-bipyridinium
effect on band shift, 325,329 diiodide, synthesis, 432
frequency shift from C N ~ on Exchange current density, Arrhenius
Au, 329331/ plot, 286,287,288/
vs. band intensity and band Extended X-ray absorption fine structure
position, 329-330 (EXAFS) at chemically modified
Electrode-solution interfacial phenomena electrodes
selection rules for interaction, 338 applications, 218
spectroscopic techniques, 338 description, 113
Electrode surface topography, scanning electrochemical instrumenta-
tunneling microscopy, 186,187/188 tion, 219,220/"

Extended X-ray absorption fine structure Gas-solid interfaces, techniques, 3

(EXAFS) at chemically modified Germanium porphyrins
electrodes—Continued cyclic voltammogram, 460,461/
experimental procedure, 221-222 electroreduction-oxidation
radial distribution functions for bulk reactions, 460,462
Ru(v-bpy) , 222,224/
3
electrosynthesis, 458,460
reagent preparation, 218-219, half-wave potentials for electron
spectra for bulk transfer steps, 460,462/
2+
[Ru(v-bpy>3] , 222,223/ overall mechanism of electrochemical
spectra for [Os(phen)(y-bpy) ] and 2
2+
conversion, 460,461/
[Os(phen)(v-bpy)2J , 22Sy,230 2+
Gold, reaction scheme with
spectra vs. wave vector for O H " , 477,481-482
2+
poly-[Ru(v-bpy) ] , 222,22^,227
3
X-ray instrumentation, 221
H
F
Hamiltonian, for cluster, 332-333

Ferrocenes, electrochemistry a
W S e - C H C N interface, 443-444,445
2 3
First-order perturbation theor

calculation of field for cluster, 333 N M R studies, 280
Flame-treated platinum, properties, 280
voltammetry, 204,205/206-207 Hemispherical electrode-planar
Formic acid, oxidation, 509,511-515 electrode, current, 182,183/184
Fourier transform IR (FTIR) spectroscopy High oxygen coverage, effect on
advantage, 352 electrochemical behavior of ordered
aspects in solution, 351-359 Pt surfaces, 209-210
C O photoelectrochemical
z High-resolution electron energy-loss
reduction, 359361,362f,363 spectroscopy
future applications, 367-368 CO plus water, 67,6Sy,70,71/
hydrogen evolution reaction on effect of H ,78,79f,80
2
iron, 35936QT ionic species, 73,75/

movable electrode, 351-352 Hole injection
optical arrangements, 352-353,354/ CTRIPS spectra, 239,24Qf,241
oxidation of methanol to C 0 , 352 2
P-polarized emission
polarization modulation, 353-358 spectrum, 241,242/"
SNIFTIRS approach, 353 Hydrogen adsorption and evolution at
Frozen electrolyte electrochemistry silver electrodes
advantages, 276 cyclic voltammogram, 296,297-29$/"
charge distribution at metal reaction mechanism, 296,299
electrode-electrolyte second harmonic signal, 296,297-298/"
interfaces, 280-285 surface coverage vs. electrode
charge-transfer reactions, 285-292 potential, 296,29$/"
electrochemical Hydrogen adsorption on disordered
instrumentation, 278,280 low-index planes, identification of
experimental setup, 276,277/278,279/" peaks, 507,508/,509,51QT
Hydrogen adsorption on low-index
surfaces, cyclic
G voltammetry, 498,49Sy,500-501
Hydrogen adsorption on platinum
Gas, ambient, emersion, 167 electrodes
Gas-phase adsorption model studies of current, 29930QT
electrode surfaces second harmonic signal, 299,300f
advantages, 55 surface coverage, 29930Q/301
coadsorption of bromine and water on Hydrogen adsorption on platinum
Ag(110), 58,61 single-crystal stepped surfaces
schematic of stages, 55,56,57/ coupling of H adsorption with HSO~ and
simulation of nonspecific adsorption S 0 * " desorption, 506-507
4
in vacuum, 61,63/64 cyclic voltammetry, 501,502-504/505

INDEX 547
Hydrogen adsorption on platinum Iodo ligand

single-crystal stepped surfaces—Continued coordination to transition metal
models for stepped surfaces, 530
surfaces, 501,505/506 surface coordination, 531,532,533/534
Hydrogen adsorption on Pt(lll), Ionic species
electrochemical vs. ultrahigh vacuum high-resolution electron
data, 76,77/78 energy-loss spectroscopy, 73,75/
Hydrogen evolution Arrhenius plot, 287,289/ temperature-programmed
F R E E C E , 287 desorption, 72-73,74/
potential dependence of activation Iron oxyhydroxide system
energy, 290-291 cyclic voltammetry of iron
surface concentration of hydrogen on phthalocyanine, 258,25Slf
iron, 359,36QT electrochemical behavior, 263
Tafel plot, 287,288^ electrochemical cell for in situ
temperature dependence of transfer Mossbauer measurements, 263,264/
coefficient, 287,28Sf/ ex situ Mossbauer parameters, 258,262/
Hydronium ion inner layer on Pt(lll) in situ Mossbauer
surface, model, 45,4^ parameters, 258,261/,263,264/
Hydrophilic coadsorption vs. in situ Mossbauer spectra, 263,265/
hydrophobic coadsorption, 70,7
Hydrophobic coadsorption vs.
hydrophilic coadsorption, 70,7
Hydroquinone phthalocyanine, 258,26Qf
cyclic voltammetry, 11,13/ potential step, 266,267/
surface organometallic potential sweep, 266,267/268
chemistry, 534,535/ redox process, 258
Hydroxide ion Irreversible electron transfer,
electrochemical oxidation, 466-471 current, 184-185
reaction with Ag, 477,480,482 Isonicotinamide
reaction with Au, 477,481-482 SERS spectra, 394
reaction with Cu, 477,479-482 structure, 385
Isonicotinic acid
I SERS spectra, 394
structure, 385
Icelike structures of water, Isoquinoline
formation, 43,44/45 assignments of the major IR bands, 344/
Ideal polarizable electrode, changes in intensity of vibrational
description, 439 modes, 347,34^,349
Ideal polarizable metal-solution cyclic voltammogram, 344345/
interfaces, kinetics of molecular mechanisms for potential-dependent
processes, 439 shift of vibrational frequencies, 347
Ideal polarizable semiconductor-solution normalized intensities of vibrational
interface, criteria, 440-441 bands, 348/349
Inert electrolytes, tunneling current, 181-182 orientations for adsorption on
Infrared band intensity-coverage mercury, 339,341342
relationships, background, 310,312 preparation, 342
Infrared reflection absorption SNIFTIRS spectra, 344345/347
spectroscopy superficial excess vs. potential bulk
characteristics of vibrational bands, 338,339/ concentration, 342343/
description, 338
polarization-modulation
approach, 304-305
potential difference IR
spectroscopy, 305
Infrared spectroscopy of electrodes,
history, 351 Kinetics of ethylidyne formation, by
Insoluble products, current, 184-185 N E X A F S , 132-139
Interfacial electrochemical behavior, Kinetics of molecular processes at ideal
temperature dependence, 275 polarizable metal-solution
Interfacial electron transfer, interfaces, processes controlling
description, 438 electrochemical current, 439
Iodine, absolute surface coverage, 530 Koopman's theorem, description, 112
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1155 16th St., N.W.
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Metalloporphyrins containing a metal-

carbon cr-bond—Continued
Light-emitting tunnel junction, synthetic methods, 451-452
principle, 241,243 Methanol, oxidation to C 0 , 363-367
2
Linear sweep voltammetry, underpotential Methanol reduction at ruthenium, rate

deposition of Pb on Ag, 142,144/,145,146/ and Faradaic efficiency, 522,524/
Lithium deposition on silver electrodes N-Methyl-N'-octadecyl-4,4'-bipyridinium
in acetonitrile diiodide, synthesis, 432
cyclic voltammogram, 295-297/ l-Methyl-l'-(3-thiophene-3-yl)propyl-4,4'-
second harmonic intensity, 295-296 bipyridinium bis(hexafluorophosphate)
Lithography, scanning tunneling microscopy electrochemical behavior, 412,414
electrochemical methods, 191,192f,193 oxidation, 409
nonelectrochemical methods, 190-191 preparation, 411
Long-period hydronium icelike model structure, 409
formation of network, 50 synthesis, 412-413
potential region, 51 Microelectrochemical transistors
Long-range surface order, sensitivity, 42-51 drain current vs. gate voltage, 427,428/
Low-energy electron diffraction (LEED) resistance vs. gate voltage, 423,426/427
Pb underpotential deposition schematic diagram, 423,425
films, 149,150-152/- Microelectrod
pyridine, 27,28-33/35
Low-energy electron diffraction-Auge
electron spectroscopy-X-ray Mixed mercaptan monolayers
photoelectronspectroscopy- cyclic voltammograms, 432-433,436/"
electrochemical system, schematic deposition, 432
diagram, 142,143/ electrochemical parameters for first
Low oxygen coverage, effect on redox wave, 433/
electrochemical behavior of ordered surface coverage vs. scan rate, 434-435
Pt surfaces, 207,20$/*,209 Mixed nickel-iron oxyhydroxides
2,6-Lutidine, IR spectrum, 92,93/94 application, 268
cyclic voltammograms, 268,269
in situ Mossbauer parameters, 270,272/
M in situ Mossbauer spectrum, 268,270,271/
isomer shift, 270 _
Mechanistic surface electrochemistry Molecular adsorption on single-crystal
potential difference IR spectros- metal surfaces
copy, 312,314,316-319 analytical techniques, 111-112
surface-enhanced Raman spectros- photoionization, 112-113
copy, 312,314-319 Molecular orbital mechanism, potential-
Mercaptan monolayers, mixed, See Mixed dependent shift of vibrational
mercaptan monolayers frequencies, 347
Mercury reflectance cell, schematic Molecule-based microelectrochemical
representation, 342,343/ devices, development, 409
Metal(s), adsorption of water, 43,44/45 Mossbauer spectroscopy
Metal catalysts, effect of impurities, 155 in situ, iron oxyhydroxide system, 257-268
Metal dichalcogenides mixed nickel-iron oxyhydroxides, 268-273
adsorption of dyes, 448 Multitechnique investigations of electrode
properties, 441 surfaces
redox processes at nonilluminated advantages, 9
aqueous interfaces, 444,446-447/ choice of technique, 9-10
structure, 441,442/"
surface stability, 441 N
with band gaps greater than
2 eV, 448-449 Near-edge X-ray absorption fine
Metal-solution interfaces that approach structure (NEXAFS)
ideality, advantages of mercury Cu(110)-HCOO surface, 124,125/
electrodes, 439-440 kinetics of ethylidyne formation, 132-139
Metalloporphyrins containing a metal- Ni(100)-CO surface, 113
carbon a-bond P d ( l l l ) - C N surface, 120,121/122
description, 451 Ni(100)-CO surface
electrochemistry, 456-457 angle-resolved photoelectron
electrosynthesis, 452-459 spectra, 118,11S>/"

INDEX 549
Ni(100)-CO surface—Continued Pd(lll)-CN

Koopman's theorem, 120 angle-resolved photoemission
N E X A F S , 115,116^,117 spectra, 122,123/
polarization dependence, 117-118,1 l^f bonding geometry, 120
Nicotinic acid N E X A F S , 120,121/122
Auger spectroscopy, 11,14,15—16/,21r PH
electron energy-loss spectros- effect on methane formation, 525,526/f
copy, 14,17-20f,22/ SER spectra, 385386f,390392f
Nonspecific adsorption vs. surface mole fraction, 385,387/388
description, 55 Photoelectrochemical reduction of C 0 2
simulation, 61,63/,64 absorption spectra, 359,361-362/;363

current density calculation, 363
mechanism, 359,363
O surface radicals, 359,362f,363
Photoelectron diffraction
+ +
O and C u or A g , concerted
z
Cu(110)-HCOO, 124
reduction, 468,473,475/,476 schematic representation, 113,114/115
JV-Octadecyl-4-pyridinyl-4'-pyridyl Photoelectron spectroscopy,
iodide, synthesis, 432 Cu(110)-HCOO 126,127/
Optical second harmonic generatio
applications, 294-295
description, 294
hydrogen adsorption and evolution at electrodes
silver electrodes, 296,298^,299 CTRIPS spectra for electron injection
hydrogen adsorption on platinum by toz/u-stilbene radical anion, 235,237/
electrodes, 299,30Qf,301 CTRIPS spectra for hole
lithium deposition on silver electrodes injection, 239,24Qf,241
in acetonitrile, 295-296,297/ description of studies, 233-234
Osmium (4-methylphenanthroyl)tris(4-vinyl- experimental procedure, 234-235
4'-methyl-2,2'-bipyridine) oscilloscope trace of electron injection
E X A F S spectra, 22Sy,230 by aww-stilbene, 235,237/
preparation, 218-219 P-polarized emission spectrum for hole
Osmium tris(4-vinyl-4'-methyl-2,2'- injection, 241,242/"
bipyridine) Platinized platinum, voltammetric
E X A F S spectra, 22S£230 surface analysis, 213,214/215
preparation, 218 Platinum(lOO)
Oxidation kinetics, CO, 374,375/376 orientation at stepped surfaces, 212,214/
Oxidation of carbon monoxide sites at stepped surfaces, 212-213
cyclic voltammetry, 485,486^487 terrace sites at stepped surfaces, 212
potential double-step experiments, 492-495 Platinum(lll)
potential single-step experiments, 487-492 anomalous voltammetry, 37-52
Oxidation of formic acid hard-sphere model for perturbed
CO formation, 509,511 metal, 210,211/
comparison of positive-going thermal reordering after
sweeps, 513,515/ polishing, 210,211/
first step, 509 Platinum single crystals
formation of C 0 , 509
2
characterization of structure, 37
formation of C O H , 509 conclusions of Will's research, 37-38
formation of strongly bound species, 509 Platinum(lll) single-crystal electrodes
single-crystal stepped surfaces, 513,514/ adsorption of acetic acid, 250-255
Oxidation of methanol to C 0 2
preparation, 485
adsorption spectrum, 363,364,365/ Platinum single crystals with oriented
comparison of in situ techniques, 366/ surfaces, cleaning and
mechanism, 367 characterization, 203
Oxygen adsorption, on copper, 103,104/105 Platinum surfaces
Oxygen coverage, effect on electrochemical characterization, 204
behavior of ordered Pt surfaces, 207-210 cleaning, 203-204
ordered, activation effects on
P electrochemical behavior, 207
Polarization dependence, Ni(100)-CO
Packing density, nicotinic acid, 14,21; surface, 117-118,115^

Polarization-modulated FTIR reflection Poly[l-methly-l'-(3-thiophene-3-yl)propyl-

absorption spectroscopy 4,4'-bipyridinium bis(hexafluoro-
advantages, 323 phosphates)]—Continued
Ag electrode in C N solution structure, 409
spectra, 32532^* thickness measurement, 412
effect of potential change on Poly(pyridine) film
bands, 325327/ IR spectrum, 93/94
schematic diagram of optics and preparation, 94
electrochemical cell, 323324/ Poly(pyrrole) film
spectra for azide on silver, 333-334,335/ IR spectra, 94
Polarization-modulated IR reflection preparation, 94
absorbance spectroscopy Poly(thiophene) films
coadsorbed nitriles, 372373/ formation on Pt foil, 88
coadsorbed Sn atoms, 37838Q/381 reflection IR spectrum, 8^,88
Polarization modulation Potential-difference IR spectroscopy
absorbance, 356 adsorbed azide at silver-aqueous
absorbance vs. distance, 356357/ interface, 305306/308
calculation, 356 applications to mechanistic surface
relative absorbance vs. film electrochemistry, 312314319
thickness, 356358/* C- k frequencie gold
schematic diagram of polarize
light, 354355/
Polarization-modulation technique, Potential double-step experiments
description, 304-305 comparison to current transients of
Poly(aniline) films single-step experiments, 492,493/
preparation, 89 description, 492
reflection IR spectra, 89,91/92 log of time vs. potential, 492,494/495
Polycrystalline Pt electrode, vs. P t ( l l l ) Potential single-step experiments
single-crystal electrode, 250 comparison to current transients of
Polycrystalline Pt surface, capacitive double-step experiments, 487
processes, 48,50 current-time transients, 487,488/*
Polymer films of aromatics influence of potential on current
aniline, 89-92 transients, 487,489f,490
experimental preparation, 84 log of maximum time vs.
formation, 83-84 potential, 490,491/
properties, 83 reaction rate, 490
pyridine, 92-95 Pure liquids, tunneling current, 181-182
pyrrole, 95 Pyridine
thiophene, 84-89 characterization of surface species by
Poly(3-methylthiophene), properties, 409 SERS, 385
Poly[l-methyl-l'-(3-thiophene-3-yl)propyl- effect of methyl groups on
4,4'-bipyridinium bis(hexafluoro- reactivity, 95,97
phosphates)] effect of pH and electrode potential
current vs. generator potential for on interfacial behavior, 385-396
microarrays, 420,421/ electron energy-loss spectra, 34/35
cyclic voltammetry of adjacent electrodes vs. electron energy-loss spectroscopy, 14,22/
oxidative potential, 417,41Sj/" low-energy electron
cyclic voltammetry vs. potential, 414,415/ diffraction, 27,28-33/35
cyclic voltammetry vs. scan rate, 414,416/ polymerization, 92
diffusion coefficient for charge reflection IR spectra, 92,93/
transport, 420,422f,423 structure of absorbed layer, 33/35
electrochemical growth, 412 3-Pyridinecarboxaldehyde
electrochemical process, 414,418/* distribution of species vs. pH, 390391/
generation and collection for intensity ratio vs. SCE, 390393/394
microarrays, 417,41S|f,420 SERS, 384
generation and collection vs. SERS spectra vs. pH, 390392/"
temperature, 423,424/* structure, 385
log of generator and collector vs. electrode potential and pH, 384
current, 423,424/* Pyridinecarboxylic acids and diacids,
microelectrochemical electron energy-loss spectros-
transistors, 423,425-428 copy, 23,24-26/*

INDEX 551
3,4-Pyridinedicarboxylic acid, Rubidium tris(4-vinyl-4'-methyl-2,2'-

reactions, 23,27 bipyridine)—Continued
4-Pyridylcarbinol E X A F S spectra, 222,223/
fraction protonated, 388/ E X A F S vs. wave vector, 222,226/",227
properties, 384 Fourier filter window, 222,225
SERS spectra vs. electrode preparation, 222
potential, 388,38S"f radial distribution, 222,224/
SERS spectra vs. pH, 385,386/" S
structure, 385
surface mole fraction vs. pH, 385,387/,388 Scanning tunneling microscopy
3-Pyridylhydroquinone, cyclic adsorbate properties, 188,18S>/;i90
voltammetry, 11,12/" applications, 174-175
Pyrrole atomic resolution images, 193
IR spectra, 94 description, 174
polymerization, 94 design for electrochemical
temperature-programmed reactions, 94 applications, 177-181
electrochemical application, 175
electrochemical methods for
lithography, 191,192/",193
Radioelectrochemistry electrod surfac
adsorption of acetic acid on P t ( l l l
single-crystal electrodes, 250-25
diagram of cell, 246,247/ surface, 195,197/198
diagram of electrode for adsorbate images of electrochemically deposited
measurement, 246,247/ metal electrode surfaces, 195-196/"
preparation of electrodes, 249-250 images of electrode surfaces under
surface concentration vs. counting potentiostatic control, 194-195
rate, 246-247 imaging of nonpolar organic liquids, 194
Rate constants for nucleation, nonelectrochemical methods for
determination, 494/495 lithography, 190-191
Redox processes at nonilluminated metal pure liquids and inert
dichalcogenide-aqueous interfaces electrolytes, 181-182
band diagram, 444,447/ reversible redox species, 182-184
current-voltage behavior, 444,448 silver deposition, 195
Tafel plots, 444,446/ structural information, 175-176
Reduction of methanol topography of Pt electrodes, 194
at ruthenium, 522,524-525/,52ty" topography of surfaces, 193-194
effect of methanol concentration, 525 tunneling current, 181
effect of pH, 525,526f use as surface vibrational
rate vs. temperature, 524-525 spectroscopic tool, 176-177
Reversible or quasireversible redox use for surface electronic information, 177
species, tunneling current, 182,183/184 Self-consistent field wave functions
Rhodium porphyrins calculation of cluster field, 329-333,335/
cyclic voltammograms at Pt degree of confidence, 329
electrode, 453,454/ effect of field on frequency, 333
electrosynthesis, 452-453 localized bonding of adsorbed
factors influencing reaction rate, 456 molecules, 329332
reaction sequence, 453 Sensitivity to long-range surface order
reaction with terminal alkenes and adsorption of water on metals, 43,44/45
alkynes, 456,457 examples, 42
reactions of low-valent Rh with formation of ordered networks in double
methylene chloride, 458,45Sy layer, 50-52
redox potentials and U V - v i s spectral Silicon porphyrins
data, 453,454/,456 electrosynthesis, 460
Room-temperature electrochemistry, oxidation-reduction
comparison with ultrahigh vacuum mechanisms, 460,463-464
spectroscopy, 80-81 Silver, reaction scheme with OH~
Ru electrodes, preparation, 519 and 0 , 477,480,482
2
Rubidium tris(4-vinyl-4'-methyl-2,2'- Single-crystal electrodes, preparation, 498

bipyridine) Single-potential alteration IR spectroscopy,
+
effect of oxidation on 3 electrooxidation mechanisms of organic
state, 227,228/",230 molecules, 316,317/318-319

Sn adatoms, competitive adsorption, 372 Surface electrochemistry—Continued

Solid electrode surfaces techniques, 3-4
defining the surface state, 10 use as electrode, 202-203
progress in investigative techniques, 9 Surface electronic structure, techniques, 112
Solid-electrolyte interface, advances in Surface-enhanced Raman scattering (SERS)
understanding molecular 4-acetylpyridine, 388,390
phenomena, 54-55 advantages, 322
Solvation stoichiometrics, Ag electrode in C N solution
determination, 73,76 spectra, 325,326/"
Specific adsorption, description, 55 4-(aminomethyl)pyridine, 394,396
/ra/w-Stilbene 4-aminopyridine, 3%
CTRIPS spectra for electron applications, 383-384
injection, 235,238/" 4-benzoylpyridine, 394,395/
oscilloscope trace of electron cell design, 396
injection, 235,237/ characterization of surface species, 385
voltammogram for reversible reduction discovery, 322
at A u surface, 235,23^/" experimental procedure, 396-397,399-400
Structural characterization, H 0 in absence of
2
voltammetry, 206-207 2 +
P b , 400-401,402/",404/
Structural information of electrochemicals 0 i f
by scanning tunneling
microscopy, 175-176
Subtractively normalized interfacial Fourier isonicotinic acid, 394
transform IR (FTIR) spectroscopy mechanisms, 398-399
description, 353 3- pyridinecarboxalde-
orientations for adsorption of isoquinoline hyde, 390392-393/394
on mercury, 339341/342 4- pyridylcarbinol, 384-389
potential region of adsorption, 353 Surface-enhanced Raman spectroscopy
schematic representation of adsorbate orientation, 309
instrumentation, 342345/ adsorbate surface binding geometries, 309
spectra for isoquinoline adsorbed azide at silver-aqueous
solution, 344,346/347 interface, 305,307/308-309
spectra of ring-bending mode of advantages, 304
p-difluorobenzene, 33934Qf applications to mechanistic surface
Surface analysis electrochemistry, 312314-319
voltammetry, 204,205/206 band intensities for monitoring
voltammetry of platinized electrochemical reactions of
platinum, 213,214/215 adsorbed species, 309-310,311/
Surface analysis chamber, C - N peak frequencies at gold
description, 155-156 electrode, 312,313
Surface chemistry of copper electrodes C—O stretching at gold
antechamber diagram, 100,102/* electrode, 314,315/316
Auger spectra of copper surfaces after Surface extended X-ray absorption fine
oxidation, 103,104/ structure, description, 113
description of copper sample, 100,103 Surface organometallic chemistry,
electrolyte adsorption, 106-109 hydroquinone, 534,535/
instrumental diagram, 99-100,101/ Surface structure, role in
oxygen adsorption, 103,104/105 electrocatalysis, 498-516
water adsorption, 105-106 Synchrotron radiation, surface electronic
Surface-cluster analogy, bonding, 4-5 structure determination, 112
Surface compositional changes
accompanying electrochemical processes
under steady-state conditions,
techniques, 314 T
Surface coordination
3,6-dihydroxypyridazine, 534,536,537/ Temperature-programmed desorption
2,5-dihydroxythiophenol, 536,537-538/539 CO plus water 67,68/"
iodo ligand, 531-532,533/534 ionic species, 72-73,74/
Surface electrochemistry 2,2',5,5'-Tetrahydroxybiphenyl, cyclic
at metal electrodes, 202 voltammetry, 11,13/
methodology, 245-246 Thermal desorption spectroscopy, water
multitechnique approach, 4 coverage determination, 58-59

INDEX 553
Thiophene Ultrahigh vacuum surface spectroscopy

electrophilic polymerization, 95 advantages and disadvantages, 65
factors influencing polymerization, 88-89 comparison with room-temperature
reflection IR spectra, 84,86/,87 electrochemistry, 80-81
surface-catalyzed polymerization, 84 effect of water and temperature, 65-66
temperature-programmed reaction Underpotential deposition of metals
spectra, 84,85/ Auger electron spectra, 145,148/
vibrational bands of derivatives, 87f experimental procedure, 141
3-(Thiophene-3-yl)propanol, influencing factors, 141
preparation, 410 low-energy electron
3-(Thiophene-3-yl)propionic acid, 410 diffraction, 149,150-152/"
3-(Thiophene-3-yl)propyl bromide, 411 voltammetry curves, 145,146/"
3-(Thiophene-3-yl)propyl-4,4'-bipyridinium voltammograms, 142,144/
hexafluorophosphate, preparation, 411 X-ray photoelectron
Transition metal oxides, spectroscopic spectra, 145,146-147/149
characterization, 257 Underpotential deposition process,
Tungsten diselenide-acetonitrile causes, 399
interfaces
doping densities, 441,443
electrochemistry of ferrocenes,
flat band potentials, 443
preparation, 441
Tunneling current
calculation, 181 Vibrational spectroscopy
irreversible electron transfer or applications, 303,369
insoluble products, 184-185 CO absorption studies, 370-381
pure liquids and inert Voltammetry
electrolytes, 181-182 structural characterization, 206-207
reversible or quasireversible redox surface analysis, 204,205/206
species, 182,183/184 surface analysis of platinized
spatial exclusion from tunneling gap, 185 platinum, 213,214/215
W
Ultrahigh vacuum
advantages, 54
coadsorption of bromine and water on Water
Ag(110), 58-61 adsorption on copper, 105-106
comparison to electrochemical adsorption on metals, 43,44/45
data, 56,59,61,62/" coverage determination, 58,59,60/
Ultrahigh vacuum electrochemical Well-defined electrodes for surface
systems, applications, 40 electrochemical measurements,
Ultrahigh vacuum modeling of preparation, 249-250
aqueous-metal interfaces Well-ordered P t ( l l l ) surface, capacitive
addition of ionic species, 72-76 processes, 48,50
control of effective electrode Work function vs. electrochemical
potential, 76-80 potential, 76-81
high-resolution electron energy-loss
spectroscopy of CO plus
water, 67,69-70,71/
X
hydrophilic vs. hydrophobic
coadsorption, 70-72
simulation of nonspecific adsorption
in vacuum, 61,63/64 X-ray instrumentation, description, 221
temperature-programmed desorption X-ray photoabsorption, schematic
of CO plus water, 67,68/ representation, 113,114/115
water plus neutral probe molecule, 66 X-ray photoelectron spectroscopy, Pb
Ultrahigh-vacuum-prepared P t ( l l l ) underpotential deposition
crystal, cyclic voltammetry curve, 38,39/ films, 145,146-147/149


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ACS SYMPOSIUM SERIES 378

Electrochemical Surface Science

Manuel P. Soriaga, EDITOR

Developed from a symposium sponsored

American Chemical Society, Washington, DC 1988

In Electrochemical Surface Science; Soriaga, M.;

Electrochemical surface science.

"Developed from a symposium sponsored by the

I. Soriaga, Manuel P.. 1949- . II. American Chemical

In Electrochemical Surface Science; Soriaga, M.;

1988 ACS Books Advisory Board

Harvey W. Blanch University of Iowa

Malcolm H. Chisholm James C. Randall

Alan Elzerman E. Reichmanis

Michael R. Ladisch Wendy A. Warr

In Electrochemical Surface Science; Soriaga, M.;

In Electrochemical Surface Science; Soriaga, M.;

methanation, and surface organometallic chemistry. The broad but

In Electrochemical Surface Science; Soriaga, M.;

June 30, 1988

In Electrochemical Surface Science; Soriaga, M.;

Electrochemistry: The Senior but Underused

Department of Chemistry, Texas A&M University, College Station,

In Electrochemical Surface Science; Soriaga, M.;

In Electrochemical Surface Science; Soriaga, M.;

b i o l o g i c a l systems, processes w i t h i n t h e boundary l a y e r

In Electrochemical Surface Science; Soriaga, M.;

In Electrochemical Surface Science; Soriaga, M.;

because o f t h e w i d e s p r e a d knowledge t h a t w h i l e metal

1. Muetteries, E . L . B u l l . Soc. Chim. Belg. 1975, 84, 959.

In Electrochemical Surface Science; Soriaga, M.;

14. Hansen, W.N.; Kolb, D . M . ; Lynch, D.W., E d s . ;

In Electrochemical Surface Science; Soriaga, M.;

41. Gordon, J.G.; Melroy, O.R.; Borges, G . L . ; Reisner,

In Electrochemical Surface Science; Soriaga, M.;

Molecular Adsorption at Well-Defined

Arthur T. Hubbard, Donald A. Stern, Ghaleb N. Salaita,

Reviewed here are surface electrochemical studies of

In Electrochemical Surface Science; Soriaga, M.;

N i c o t i n i c acid and related meta-carboxylic acids display

An era of remarkable progress i n the study of s o l i d electrode sur-

In Electrochemical Surface Science; Soriaga, M.;

s i t i v i t y and v i r t u a l l y unlimited frequency range by EELS (11). On

In Electrochemical Surface Science; Soriaga, M.;

(c) and none of the atoms i n the electroactive part of the

P r i o r to recording the current-potential curves i n Figure 1-A, the

In Electrochemical Surface Science; Soriaga, M.;

In Electrochemical Surface Science; Soriaga, M.;

In Electrochemical Surface Science; Soriaga, M.;

tenuation of substrate Auger signal by the adsorbed layer. Pack-

0.27 nmol/cnr based upon Ip /Ip°> or 0.27 nmol/cm based upon t

coulometric electrochemical data (16).

graphed versus n i c o t i n i c acid (NA) concentration ( C ^ ) at P t ( l l l ) .

T = (1-I /I °)/(9K) p t p (4)

adsorption of NA at -0.2V (vs. Ag/AgCI reference). Packing den-

In Electrochemical Surface Science; Soriaga, M.;

52 0.1 pH3.3, -0.2V,Pt(lll)

reference. B. Packing density of NA adsorbed at -0.2 V. Continued on next page.

In Electrochemical Surface Science; Soriaga, M.;

Figure 2. Continued. C. Packing density of NA adsorbed at +0.3 V.

|4 3.28 4#-2.03-»| I+L20-J09 |^-2.42 - * | l . 2 5 | 1.25 H ' 4 0

MOLECULAR AREA, X « 8.46 2

In Electrochemical Surface Science; Soriaga, M.;