Electraamdvtical Chemistry aml lnteJJacial Electrochemistry, 60 (1975) 259 266 259

Elsevier Sequoia S.A.. Lausanne Printed in The Netherlands

ELECTROCATALYSIS BY AD-ATOMS

PART I. ENHANCEMENT OF THE OXIDATION OF METHANOL ON

PLATINUM AND PALLADIUM BY G O L D AD-ATOMS

M. WATANABE and S. MOTOO

Departnlent q! Applied ('hemistr)', Facult.l' of' Engineerin¢l. Yamanashi Universit)'. Takeda-4. Kq/i¢ (Japan)
(Received 9ltl Septem[~er 1974: in revised form 4th Jalluttry 1975)

I. INTRODUCTION

According to the hi-functional theory ofelectrocatalysis proposed in previous

papers ~ ~', electrocatalytic activity for the oxidation of an organic substance is
expected to be enhanced by the cooperation of two kinds of metal atoms being
mixed on the atomic scale and having different adsorption properties, one for
organic species, one for oxygen containing species on the electrode surface in the
negative potential range.
Gold has been ascertained to adsorb no organic species v and to adsorb
oxygen containing species in alkaline solution at a more negative potential than
in acidic solution. Platinum and palladium are recognized to adsorb organic species.
Hence, based on the hi-functional theory of electrocatalysis, the existence of
gold ad-atoms is expected to enhance the electrocatalytic activity of platinum and
palladium electrode for methanol oxidation in alkaline solution but not in acidic
sofution.
In this paper, work based on the above mentioned expectation will be
described.

2. EXPERIMENTAL METHODS

The experiments were carried out in Pyrex glass cells at 40 C. All potentials
were measured with respect to a reversible hydrogen electrode (RHE). Electrolytic
solutions were prepared with triply-distilled water and analytical grade reagents of
NaOH or H 2SO4 and they were purified by pre-electrolysis. Alloy black electrodes
were prepared from titanium base Raney alloys as described previously ~.
The substrates for the ad-electrodes were prepared from annealed platinum
and palladium wires of 0.3 mm diameter, which were sealed into soft glasses so as to
expose a real surface area of about 1 cm 2. They were.etched with aqua regia before
use. Electrolytic solutions used for preparing the ad-electrodes were obtained by
dissolving HAuCI4'4 H20 to the concentration of l0 - 6 - 10 -5 mol 1-~ in 1 M
NaOH or 0.5 M H2SO4 solution. The electrolytic solution used for the measurement
of polarization characteristics was prepared by dissolving analytical grade CH3OH
in the 1 M NaOH or 0.5 M H2SO 4 mentioned above.
260 M. WATANABE, S. MOTOO

A Kowa 601-A function generator in conjunction with a Yanagimoto V-8

potentiostat was used to apply potential time sequence (p.t.s.). The resulting current-
potential (or time) curves were displayed on a Sony/Tektronix 434 oscilloscope and
Watanabe SR 651 surbocorder.
Notations used in this paper are as follows. Au(subs); clean gold substrate,
Au-Pt(subs) and Au-Pd(subs); platinum and palladium substrates with adsorbed
gold atoms respectively. O-Au(subs); oxygen adsorbed by gold substrate. HCO
Au-Pt(subs) and HCO-Au-Pd(subs); organic species HCO adsorbed by Au-
Pt(subs) and Au-Pd(subs). Ad-electrode Au-Pt(subs) and Au-Pd(subs); platinum
and palladium electrodes having adsorbed gold.

2.1. Preparation of ad-electrodes and determination of their surface composition

Gold was electrodeposited on a platinum electrode in 1 M NaOH solution
containing HAuC14. The amount of deposited gold was controlled by the time
interval the platinum was kept (z) at 0.05 V. After being rinsed in distilled water the
electrode was dipped in 1 M NaOH solution in order to determine 0gu. The
quantity of electricity (QAu Pt) corresponding to adsorbed hydrogen on platinum sites
was determined by applying an anodic pulse from 0.05 to 0.56 V on PTS-b-Pt.
Since hydrogen is hardly adsorbed by gold atoms on a platinum electrode surface,
surface coverage with gold (0A.) can be given by

30s 1.5V

- - - ~ PTS - o - R PTS-¢-~

PTS-b-Pt
2ov/s
Imin r ' " "°'~ /AO,56V
O,05V~~V VL

PTS-a-Pd PTS-b-Pd

1.4V30s 1,4V30s

, Train O,05V..j u ~. •--- o [ 'E RHEQ}' ~

Iv(w:

P T S - c - lad

~[ i
I min,
r

(
(-I
Fig. I. P.t.s. used for the electrodeposition of gold (a), the determination of 0A, (b), the measurement
of polarization (c) and the determination of 0org(b, c).

Fig. 2. Typical potential sweep curves on Pd (a) and Au-Pd(subs) (b) electrodes in 0.5 M H2SO4.
METHANOL OXIDATION ON Au ADSORBED ON Pt, Pd. I 261

OA. = (Q,_e,-QA~_pt ) .'Q,,__p, (1)

where Q._p, is the quantity of electricity corresponding to adsorbed hydrogen on
the platinum electrode free from gold.
Gold was electrodeposited on a palladium electrode in l M NaOH solution
containing HAuC14. After being rinsed in distilled water, the electrode was dipped
in 0.5 M HzSO 4 solution in order to determine the surface composition with
P T S - b - P d as shown in Fig. 1. Curves a and b in Fig. 2 show voltammograms on
the palladium and the ad-electrodes Au-Pd(subs), which were obtained with tri-
angular pulse on P T S - b - P d shown in Fig. 1.0a,, can be given by eqn. (2), because
O-Au(subs) is not formed by the anodic potential sweep up to 1.4 V, on the
PTS-b-Pd.
Oau = (Qo- Pa- Q~- Pa)/Qo- re (2)
where Qo Pd and Q~Pd are the quantities of electricity required for the reduction of
O-Pd(subs) and O-Au-Pd(subs) electrodes respectively.

2.2. Measurement of polarization characteristics

Polarization characteristics for the oxidation of methanol on alloy black
electrodes were measured at 40°C with the same method as mentioned previous-
ly 1~. The polarization measurement for ad-electrodes was made with PTS-c-Pt
and PTS-c-Pd shown in Fig. 1. Current density is represented in terms of #A real
cm-2. Current was recorded 1 rain after the potential was applied.

2.3. Determination of coverage of platinum sites with organic species

0,,r~ of platinum sites was determined with a cathodic pulse from the potential
at which electrodes had been electrolysed to -0.15 V on P T S - b - P t shown in
Fig. 1.

5o

0,6 d

A
u.I F
v
~ 0
" 0,5 B E 2,5
v
g °
> O.Z
la.i

02
I I
0,1 f io I oo o.pct,
m o'.s I.O
i/mA (I OtTs.(].) "1 Composition (at.ratio)

Fig. 3. Polarization curves on Pt-Au alloy electrodes in 1 M CH3OH 0.5 M HzSO 4 at 40°C. (A)
Au =0%, (B) 20%, (C) 40%, (D) 50?/0,(E) 60%, (V) 70%, (G) 80%.

Fig. 4. Activity-composition diagram on Pt-Au and Pd Au alloy black electrodes in 1 M CH3OH-1

M NaOH at 40°C. (O) Pt-Au (at 0.4 V), (@) Pd-Au (at 0.55 V).
262 M. WATANABE, S. M O T O O

0,,rg = (~QH -- QH)/~QH (3)

where QH and ~QH correspond to hydrogen adsorbed by platinum on the electrodes
having or not having adsorbed organic species respectively.

3. RESULTS AND DISCUSSIONS

3.1. Polarization characteristics of alloy electrodes

Figure 3 shows the polarization curves of Pt-Au alloy electrodes in alkaline
solution. To make clear the relation between activities and the alloy composition,
currents at 0.4 V as a measure of activity are plotted against composition in Fig. 4.
In this figure, currents at 0.55 V on Pd-Au alloy electrodes are also plotted. Current
density is here represented in terms of current per surface atom.
It is found that activity maxima are exhibited at atomic fractions of gold
0.4 and 0.6 for Pt-Au and Pd-Au alloy electrodes respectively. The activities are
enhanced about 2.5 times compared with those of elemental platinum and palladium
in alkaline solution. On the contrary no enhancements were exhibited in acidic
solution by alloying.

3.2. Polarization characteristics of ad-electrode enhancement by ad-atoms

Figure 5 shows the polarization curves of ad-electrodes Au-Pt(subs) in
alkaline solution (1 M NaOH-1 M CHaOH ). To make clear the relation between
activities and 0gu, currents at 0.4 V as a measure of activities are plotted in Fig. 6.
Figure 7 shows the same relation on ad-electrodes Au-Pd(subs). The surface com-
position at the activity maximum on ad-electrode coincides well with that on
alloy electrode for both Au-Pt and Au-Pd electrocatalytic systems. In addition,
the factor of activity enhancement is found to be about the same on both systems.
On the contrary, no enhancement was found to be exhibited in acidic solution
(0.5 M H2SO4-1 M CHaOH ) as was found on the alloy electrode. Figure 8 shows
50

IHGAF [ D B I
4O
0,7
u 30
-l-
0.6
ui
> ,~ 20
IM 0.5
~-,o'-
0.4
0,01 O. I 1,0 I0 0~) 015 I'
i/mA r e a l cm - 2 OA,
Fig. 5. Polarization curves on Au-Pt(subs) electrodes in 1 M C H 3 O H - I M NaOH at 40°C. (A) 0A,=0,
(B) 0.11, (C) 0.33, (D) 0.52, (E) 0.66, (F) 0.72, (G) 0.73, (H) 0.82, (I) 0.83.

Fig. 6. Correlation between activity of Au-Pt(subs) electrodes and 0A, at 0.4 V in 1 M CH3OH - 1 M
N a O H solution.
METHANOL OXIDATION ON Au ADSORBED ON Pt. Pd. I 263

75 0,2

%
u
50 "6
<~

O.
E
2.=
g
0
't
o15
Composition (eAu)
1,0 o12 o14 o16 o18
Coverage [gAu

Fig. 7. Correlation between activity of Au-Pd(subs) electrodes and 0ao at 0.55 V"(&) and 0.60 V (O)
in I M CH3OH-I M NaOH solution.

Fig. 8. Correlation between activity of Au-Pt(subs) electrodes and 0A. at 0.6 V in 1 M CH3OH-0.5 M
H2SO 4 solution.

the results on ad-electrode Au-Pt(subs). The activity decreases with increase of

0A u '

3.3. Coverage of Pt and Pd sites with organic species

Figure 9 shows the correlation between coverage with organic species and
surface composition on ad-electrode Au-Pt. This O,,rg is defined to be the coverage
of Pt sites with organic species as mentioned in section 2.3. 0,,rg remains constant
at 0.40 V and 0.55 V in the coverage range 0A. less than 0.50. In the coverage range of
OA, higher than 0.5, the gradual decrease of 0org takes place with increase of 0A,.
This may be caused by the change of site to site distance for their adsorption.

hO

~'o . , ~

i
05 ,0
eAu
Fig. 9. Correlation between coverage with organic species and 0Au in 1 M CH3OH-I +'d NaOH at
40°C. (O) 0.4V, ( A ) 0.55 V, (D) 0.75 V.
264 M. WATANABE, S. MOTOO

40[ ,.av'"'" ~,.75v bF i

ul ,~, i
20 .

fi
l

-I0

-20
I
I
-4( /
, L~-j i
0 l,O
E V(vs. RHE)

Fig. 10. Potential sweep curves on gold electrode (a) in 1 M NaOH, (b) in 0.5 M H2SO 4. (A) Adsorption
of oxygen containing species; (B) desorption of oxygen containing species.

3.4. Dependence of oxygen adsorption by gold on acidity

Figure 10 shows potential sweep curves with single triangular pulse on the
p.t.s, shown on the upper part of the figure. The curve observed in acid solution
(0.5 M H2804) differs from that observed in alkaline solution (1 M NaOH) in the
cathodic potential region (shaded area). In the alkaline solution, oxygen adsorption
begins from more negative potential than in the acid solution. Oxygen desorption
lasts to more negative potential in the alkaline solution than in the acid solution.
Both results indicate that oxygen can be adsorbed in the alkaline solution by gold
surface sites at about 0.8 V more negative than in the acid solution. On ad-
electrodes Au-Pt (subs) the same results were obtained, that is, oxygen can be
introduced on to the ad-electrodes by gold sites in the alkali solution in more
negative region than in the acid solution.
Oxygen adsorption takes place according to the following equation
H20 + Au-Pt(subs) = O-Au-Pt(subs) + 2 H + + 2e (4)
in acidic solution,
OH - + Au-Pt(subs) = O-Au-Pt(subs) + H + + 2e (5)
in alkaline solution.
The step (5) occurs at about 0.6 V more negative potential than does step (4).
This is one of the most important points connected with the activity enhancement.

3.5. Enhancement of activity through bi-functional electrocatalysis mechanism

Dissociative adsorption of methanol on platinum is generally accepted 8"9.
The adsorption is expressed as follows.
METHANOL OXIDATION ON Au ADSORBED ON Pt, Pd. I 265

CH3OH + 4 Pt(subs) = HCO Pt(subs) + 3 H-Pt(subs) (6)

The adsorbed hydrogen is oxidized as follows
H-Pt(subs) = Pt(subs) + H + + e (7)
On palladium, methanol is adsorbed through the same steps 1°.
CH3OH + 4 Pd(subs) = HCO Pd(subs) + 3 H-Pd(subs) (s)
H-Pd(subs) = Pd(subs) + H + + e (9)
Concerning the structure of HCO, there is no agreement s9. HCO which requires
one site to be adsorbed is assumed in this paper as described in the next paper 6.
As described in section 3.4, oxygen can be adsorbed in more negative potential
range by gold ad-atoms than by platinum substrate in an alkaline solution, but not
in acid solution. Gold ad-atoms have been proved to be uniformly dispersed in
atomic scale on platinum and palladium surface. These facts indicate that in an
alkali solution every HCO-Pt(subs) or HCO-Pd(subs) has O-Au-Pt(subs) or
O-Au-Pd(subs) in the nearest neighbour sites to react with. Accordingly, the gold
ad-atoms facilitate the oxidation on the ad-electrodes through the reaction steps
(10) and (11) in the alkaline solution.
HCO-Pt(subs) + O-Au-Pt(subs) = CO2 + H + + e + Pt(subs) + Au-Pt(subs) (10)
HCO-Pd(subs) + O-Au-Pd(subs) = CO2 ~- H + + e + Pd(subs) + Au-Pd(subs) (11)
The above mentioned discussion leads to the bi-functional mechanism of
electrocatalysis through surface reaction. The necessary conditions for the enhance-
ment of electrocatalytic activity of a substrate S by an ad-atom A for the oxidation
of reactant R are as follows. (1) Ad-atoms A must be dispersed uniformly in
atomic scale on the substrate surface. (2) Oxygen must be adsorbed by the ad-
atoms A at more negative potential than by the substrate S. (3) Reactant R must be
adsorbed by the substrate S and not by the ad-atoms A.

ACKNOWLEDGEMENT

The authors are indebted to Miss C. Kitano for her help.

SUMMARY

The ad-electrodes Au-Pt(subs) and Au-Pd(subs) have the same electro-

catalytic characteristics for methanol oxidation as the Au-Pt and Au-Pd alloy
electrodes. These findings indicate the surface composition to play predominant
roles in the methanol oxidation. The bi-functional theory provided and will provide
useful tools for the prediction of new electrocatalysts.

REFERENCES

1 M. Watanabe, T. Suzuki and S. Motoo, Denki Kagaku, 38 (1970) 927.

2 M. Watanabe, T. Suzuki and S. Motoo, Denki Kagaku, 39 (197l) 394.
3 M. Watanabe, T. Suzuki and S. Motoo, Denki Kagaku, 40 (1972) 205.
266 M. WATANABE, S. MOTOO

4 M. Watanabe, T. Suzuki and S. Motoo, Denki Kagaku, 40 (1972) 210.

5 M. Watanabe and S. Motoo, Denki Kagaku~ 41 (1973) 190.
6 M. Watanabe and S. Motoo, J. Electroanal. Chem., 60 (1975) 267.
7 B. M. W. Trapnell, Chemisorption, Butterworths, London, 1955.
8 B. I. Podlovchenko and E. P. Gorgonova, Dokl. Akad. Nauk SSSR, 158 (1964) 1416.
9 V. S. Bagotzky and Yu. B. Vassilyev, Electrochim. Acta, 12 (1967) 1323.
10 S. Takahashi, Thesis, Yamanashi University, 1972. High coverage with organic species (0orgy0.8)
is observed on palladium and palladium-gold alloy electrodes in 1 M CH3OH-I M NaOH solu-
tion at 40°C.
11 N. Furuya and S. Motoo, to be published.