TECHNICAL PAPERS

ELECTROCHEMICAL SCIENCE AND TECHNOLOGY

Electrochemical Oxidation of Glucose on Single Crystal and

Polycrystalline Gold Surfaces in Phosphate Buffer
Adii4*0 and
M. W. Hsiao, R. R. Ad±i4*0 and E.
E. B.
B. Yeoger*
Yeager*
Ernest B. Yea ger Center for Electroehemical
Electrochemical Sciences and the Department of Chemistry,
Case Western Reserve University, Cleveland, Ohio 44106, USA

ABSTRACT
The electrochemical oxidation of glucose has been studied in phosphate buffer (pH = 7.4) on single crystal and poly-
crystalline gold electrodes
electrodes using
using electrochemical
electrochemical techniques,
techniques,exexsitu
situNMR,
NMR,ininsitu
situF'TIR
FTIR spectroscopy,
spectroscopy,and
andisotope
isotopelabel-
label-
ing. Under these conditions, the results indicate that the rate determining step for the electro-oxidation of glucose is bond
breaking between the hydrogen atom and the C1 carbon atom. Gluconolactone appears to be an intermediate and sodium
gluconate is the reaction product. First order kinetics with respect to glucose were also found. Gold would be a useful
electrode for sensor applications, if the inhibition of the glucose oxidation by the adsorption of CL could be
C1 could be avoided.
avoided.

Introduction [110] and [110] zones.9 In this paper, further investigation

The electro-oxidation of glucose has been studied in of the kinetics and mechanism of the oxidation of glucose
recent years, principally because of interest in the devel- on gold single crystal surfaces in phosphate buffer is
opment of a glucose sensor for in vivo or in vitro measure- reported.
reported.
ments of glucose concentration in human blood.1'2 Experimental
Understanding of the reaction kinetics of glucose oxida- singlecrystals
Cylindrical single crystals (—8
(—8 mmmm diam,
diam, ——8—8
mmmm thick)
thick)
tion is far from complete. Vassilyev et al.3'4 reported that Cylindrical
were made of Au(99.99%) supplied by Metal Crystals and
the reaction kinetics of glucose oxidation depends upon Oxides, Ltd. (Cambridge, England), oriented by Laue
the nature of the electrode materials. The structural backscattering to better than 1° and cut by spark erosion.
dependence of the kinetics of electro-oxidation of small Mechanical polishing was done on a Buehler Whirliment
organic molecules is well documented.5'6 The adsorption of attachment using microcut 1200 paper followed by alumi-
reactant, intermediates, and/or products during the reac- na down to 0.05 p.m. Ultrasonic cleaning
pm. Ultrasonic cleaning in pure water was
tion may differ on various single crystal surfaces because used between each polishing step. The surface face was
of different adsorption sites. In addition, anodic film for- then electropolished in a cyanide bath.1° Before each
mation and the adsorption of various species, such as experiment, the electrode was annealed by heating in a
anions and hydrogen, are usually dependent on particular H2-air flame
112-air flameuntil
until red-hot,
red-hot, cooled
cooled slowly
slowly in
in air
air down to
single crystal surfaces and can have major effects on the —100°C, and protected by a drop of ultrapure water trans-
kinetics of various electrode reactions occurring on these ferred into the electrochemical cell.
surfaces. Accordingly, the oxidation of glucose is also Electrochemical experiments were carried out in a con-
expected to be structure sensitive. Indeed, Lamy et al.7 ventional three compartment Pyrex cell. The rotating disk
found different catalytic activities for glucose oxidation electrode (Pine Instruments, Co., disk area 0.459 cm2) was
al.8
on the three low index platinum surfaces. Popovic et al.9 attached to a Pine ASR-2 rotator. Measurements were
also reported a pronounced structural sensitivity of this 7.4 (0.0086 M NaH2PO4
reaction on low and high index platinum surfaces. The done using phosphate buffer, pH = 7.4
Pt(lll) surface has much higher activity than the other two
and 0.03 M Na2HPO4 prepared from Baker analyzed
low index planes as a consequence of a lower self-poison- reagents). The glucose concentration was 0.01 M.
Deuterated glucose was obtained from Aldrich Chemical
ing effect (CO adsorption) on this surface.8 Platinum has Co. Gold foil served as a counterelectrode. Solutions were
been the preferred electrode in most of these studies,
although gold displays a higher activity in neutral and deoxygenated using nitrogen gas. A saturated calomel
electrode (SCE) served as reference and all potentials are
alkaline electrolytes.3'9 The pronounced poisoning of the reported vs. SCE. A closed
closed stopcock
stopcock salt
salt bridge
bridge filled
filled with
with
platinum electrode by some intermediates and/or products
products electrolyte was used to separate the working and reference
apparently suppresses its intrinsic activity for the initial chamber to prevent contamination of the working cham-
stages of this reaction. C1 or Hg.
ber with CL
In a recent note it was shown that the oxidation of glu- FTIR measurements were made using an IBM instru-
cose is strongly dependent on the crystallographic orienta- ments IR-98AF Fourier transform infrared spectrometer
tion of the electrode surfaces.9 The Au(100) surface was with a liquid nitrogen cooled mercy cadmium telluride
found to be more active than the other two low index detector. The spectral resolution was 2 cm. The different
planes, as well as four other stepped surfaces from the
spectra were obtained by subtracting averaged replicate
* Electrochemical scans (e.g., 250) at the reference potential from average
°a Present
Member.
Society Active Member, replicate scans at a potential of interest. After switching
Address: Department of Applied Science, Chemical
Sciences Division, Brookhaven National Laboratory, Upton, NY the externally applied potential, a five mm time delay was
11973-5000.
11973-5000, initiated before data collection commenced, in order to
J. Electrochem. Soc., Vol. 143, No.3, March 1996 The Electrochemical Society, Inc. 759
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 760 J. Electrochem. Soc., Vol. 143, No. 3, March 1996 The Electrochemical Society, Inc.

allow the working electrode in the thin layer chamber to

attain equilibrium conditions. The angle of incidence of 0.1
0.1
the p-polarized radiation was 65°. The thin layer external
reflectance cell was fitted with a flat zinc selenide win-
dow. Prior to optical measurements, the electrode was
moved away from the window. The electrode surface was
cleaned by cycling the potential between hydrogen evolu- 0..
0..
tion and oxygen generation. After a clean surface was
obtained, the electrode was flushed against the window IV 10
for a complete series of spectroscopic measurements.
ber, whereLXR
ber, where tsR == R,ampi,
the form
Spectra are presented in the form of —tR/R vs. wave
of — wave num-
— R and R is the reference spectra
Rsampie —
I I- 0 0
at any chosen reference potential.
'H NMR spectra were obtained with a Varian Associate
XL-200 NMR spectrometer at room temperature.
Tetramethylsilane in CDC13 in a coaxial capillary tube was
used as an external standard.
Results and Discussion
Voltammetric measurements.— Voltammetry of three
low index planes of gold.—The voltammetry curves for
gold in a phosphate buffer in the absence of glucose show
adsorption processes which are strongly dependent on the
surface orientation (Fig. 1). The peaks observed in Fig. 1
are probably due
due to
to the
the formation
formationof
ofaaAu(OH)'
Au(0H)' layer
layer
which is a precursor of oxide formation, rather than the
OW can
phosphate adsorption. The chemisorption of OH- can take
take
place at potentials —0.1 to +0.3 V,
'V according to the fol- 04

lowing reactions
Au + 1120 Au0H° + H
H20 -°- AuOH H ++XeXe [1]
Au + OW -* -* AuOH
Au0H' — ++ Xe
)te - [2]
A comparison with the process in 0.1 M NaOH, which
can be described by reaction 2, yields a potential shift
which does not correspond to the value predicted for the
pH change of seven units, assuming the usual 60 mV shift
per the pH unit. Similarly, peak shift for phosphate
adsorption in 0.1 M H3P04 does not change approximately
with the total phosphate concentration. A qualitative cor-
relation for the oxidation of glucose on Au(100) and
Au(110) with
Au(110) with adsorption
adsorption of
of OW
OH in
in Fig.
Fig. 22 suggests,
suggests, howev-
howev-

I
I

PHOSPHATE BUFFER AU(110)

10 * ca2
hi
04
(.4
ItV
U

JAIJ(lll) I 10

0
.cLcI_ *1

-0.4
-0.4 0 0.4
0.4

AU (100)
Fig. 2. Electra-oxidation
Electro-oxidation ofof glucose (0.01 M
glucose (0.01 M (solid
(solid line)
line) on
(a), Au(100)
10) (a),
Au(1 10) (b), and
Au(100) (b), and Au(1
Au(111), (c) in
11), (c) in phosphate buffer
phosphate buffer
(pH 7.4) and
and voltammetry curvesininthe
voitammetrycurves theabsence o
absence of glucose
glucose (dashed
(dashed
Temperature== 298
0
line).
line). Temperature 298 K; sweep rate,
K; sweep rate, 50
50 mV/s.
mV/s.

LIV) vs. SCE

er,that it is very likely due to AuOH formation. Such a
-0.4
-0.4 0 0.4
0.4 correlation has been found in the oxidation of ethylene
glycol on Au(hkl)." Clarification of the nature of the peaks
Fig. 1. Voltammetry curves of the
the three
threelow
low index planes of gold in Fig. 1 in phosphate buffer has been obtained using
Fig.
in phosphate
phosphate buffer (pH 7.4). Temperature
(pH 7.4). Temperature = = 298 K; sweep rate, 50 in situ FTIR spectroscopy on
on the
the Au(100)
Au(l00) surface.'2'3
mV/s. Results show that phosphate adsorption occurs only at

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 J. Electrochem. Soc., Vol. 143, No.3, March 1996 The Electrochemical Society, Inc. 761

E 0.37 V vs. SCE which is more positive than the peak

potential in Fig. 1. It is, therefore, a reasonable assumption
that the observed peaks for the other two low index planes
are due to the formation of of an
an (OH)ath layer and
(Oll),th layer and that
that phos-
phos-
phate adsorption occurs at more positive potentials.
Voltammetry curves for the oxidation of glucose in
phosphate buffer (pH = 7.4) on the three low index sur-
faces of gold are shown in Fig. 3. Curves obtained in the
absence of glucose are also shown. A pronotmced structur- I
al sensitivity of both AuOH formation and glucose oxida-
tion is seen. The onset of glucose oxidation occurs at the
most negative
negative potential
potential for
for the
theAu(1
Au(110) surface, which
10) surface, which
also shows smaller peak current than the other two low
peaks are
index surfaces. Two peaks are seen
seen for
for Au(1
Au(110),
10), one peak
and a prepeak
prepeak for
for Au(1
Au(111)
11) and only one large peak
peak for
for
Au(100).
The formation of the gold oxide phase occurs on gold in
phosphate buffer at potentials more positive than those
those
used for the data in Fig. 2. As shown in Fig. 3, the oxida-
tion of glucose is suppressed to a large extent in the poten-
tial region of gold oxide formation. Poisoning of the Au
surface does not take place in the electro-oxidation of glu-
cose in phosphate buffer solution, as was found for Pt.
Hence, surface activation by oxide formation is not neces-
sary for this reaction. Origin of the peaks observed in in
Fig. 2 requires an explanation which is discussed below.
1
t
SI
U
measurements—The effects
Rotating disk measurements.—The effects of convection
have been examined with polycrystalline gold using the I
-q
rotating disk electrode. However, an increase in rotation
rate leads to a decrease in the peak current in this reaction
rather than the usual increase in the peak current (Fig. 4).
A persistence of the peaks upon rotation clearly show that
the peaks in Fig. 4 are not caused by a slow diffusion of
glucose. Figure 4 (insert) shows a negative slope in the plot
of current vs. the square root of rotation rate. This
response may be explained in the following way.
Let us assume the reaction A -+ B -+ C, where A is the
reactant, B is an intermediate, and C is the product. The
reaction intermediate (B} may diffuse away from the anode
into the bulk solution if it is not strongly adsorbed on the
electrode or if the adsorption-desorption kinetics are fast.
If the first and second step each involves one electron
transfer, the number of electrons per glucose reaching the
surface will be decreased.
Rotation increases the rate of mass transport of glucose
as well as of impurities and phosphate ions to the surface.
The impurities and/or phosphate anions may block the
electrode surface and inhibit the glucose oxidation. Fig-
ure 5 shows the voltammetry curves for a stationary Au zU
electrode and for a Au rotating disk electrode at 2500 rpm
in the absence of glucose. The voltammetry shows little
difference between the stationary and rotating conditions,
indicating that the solution is relatively free of impurities
which can adsorb on the electrode surface and inhibit the
reaction. It is quite unlikely, therefore, that the impurities
could account for this effect.
Phosphate buffer
buffer is
is composed
composedof of0.0086
0.0086M MNaH2PO4
NaH,P04 and
0.030 MM NaH2PO4.
NaH2PO4.Vakhidov
Vakhidovand
andBakirov15
Bakirov" used radioac-
radioac-
tive orthophosphoric
orthophosphoricacid acidlabeled
labeledwith
withaa32P
"P phosphorus
atom to show that the single charged phosphorus anion
(H,PO;)
(H2PO;) has
has aa greater
greater adsorbability
adsorbability than
than the
the multiple
charged anions
anions (HPO;2
(HPO;' and
and P0;')
P0;3)on
onmetals
metals(e.g.,
(e.g..Ni,
Ni,Cu,
Cu,
and Cd). Inhibition of glucose oxidation by phosphate Fig. 3. Elecfro-oxidalion
Electro-oxidalion of glucose on Au(1 10) (a), and Au(100)
anions has been clearly seen by the addition of phosphate (b),
(b), and
and Au(1
Au(1 11)
11) (c),
(c), under
under the
the same
same conditions
conditions as
as in
in Fig.
Fig. 22 except
except
to
to 0.1 M HC1O4 solution and by the lack of the reaction
reaction in
in potenlial limit.
for the positive potential limit.
0.1 M H3P04
H,P04 solution.'3'4
solution.13'4However,
However, for
for a given large con-
con-
centration of phosphates it is unlikely that their adsorp-
tion is controlled by diffusion. Their adsorption, therefore,
cannot account for the inverse rotation rate difference
observed in Fig. 5. The most plausible explanation is a dif- tion of a strongly bound intermediate. This question is
fusion of the reaction intermediate away from the surface, addressed later in the paper.
which decreases the current density with increasing rota- Mechanistic studies of the oxidation of glucose on
tion rate. The peak for a stationary electrode (Fig. 2) can gold—Oxidation of fructose and sodium gluconate.—The
be explained by either phosphate adsorption or by adsorp-
adsorp- mechanism of glucose oxidation is not yet fully under-
under-
stood. Because of the lack of a strong poisoning effect, a

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 I
762 J Electrochem.
J. Electrochem.Soc.,
Soc.,Vol.
Vol.143,
143,No.3,
No.3,March
March1996
1996The
TheElectrochemical
ElectrochemicalSociety,
Society,Inc.
Inc.

I I a
300

Fig. 4. Electra-oxidation
Electro-oxidation of glu- 0.3 —
0.3
cose (0.01 M) on the polycrys-
talline rotating disk electrode
(anodic sweep). The rotation was ('a
(a) 400 rpm, (b) 900 rpm, (c)
(c) 1600
1600 U
r I0 0 .20
20 30
3005
40
. .*
50 aS
30 50 70
50 80
0.2 — -C
rpm, (d) 2500 rpm, (e) 3600 rpm,
and if)
(0 4900 rpm. Temperature = I
I-I
298 K; sweep rate = 50 mV/s.
(Insert) Plot of current vs. the
square root of rotation speed at E 0.1
= 0.08 V.

0 E(V) vs. SCE

SIX

I
.1

-0.5 0 0.5 I.0

detailed study of the mechanism on gold is desirable. is inhibited and does not occur at a significant rate. The
Vassilyev et al.'5 proposed that the weakly bound hydrogen small difference between the curves in the absence and in
atom at the carbon C1C, atom
atom is
is the
the first
first to be detached from the presence of these molecules probably corresponds to
the molecule.
molecule. They
They assumed
assumedaarole
roleof
ofOHads
OH,d, on Au in fur- layer capacity.
changes of the double layer capacity.
ther oxidation of the adsorbed
adsorbed particle
particle to
to gluconic
gluconic acid.
acid. Figure 7 shows the voltametry curve for the oxidation of
Makovos andand Liu16.have
Liu'8 have investigated
investigated the reaction at the
the 0.01 M
0.01 MNa
Nagluconate
gluconate in
in phosphate
phosphate buffer on polycrystalline
polycrystalline
potential of oxide
oxide formation
formation on
onAu.
Au.Vielstich
Vielstichetatal.17
al." did
did gold electrode. No oxidation current was observed in Fig. 7
not find CO2
CO, formation
formation during
during glucose
glucose electro-oxidation at potentials negative to the oxide formation region.
region. This
This
on Au except in the oxide formation region using on-line result suggests that the oxidation of glucose in the gold
spectrometry
mass spectrometry. double layer region involves the hydrogen atom bound to
The present data indicate that in the double layer region first step
the carbon C, atom. The first step probably
probably involves
involves the
the
in phosphate buffer at pH 7.4, the extent of the oxidation adsorption of glucose followed by the oxidation of the
of glucose is small. Figure 6 shows a comparison of the hydrogen atom boimd to the carbon C, atom,
atom. viz
oxidation of fructose and Na gluconate on Au(100). Unlike
glucose, fructose does not have the H atom bound to the rOH
II \/AuOH
\/AuOH
irO
II \
II
carbon C1 atom. A comparison of the oxidation of these C — (I
I C—OHC-OH +H+e
+W+e
two molecules on gold offers information on the mecha-
reaction of
nism of the reaction. The reaction of sodium
sodium gluconate
gluconate
I
I
LROH
/\ II
LLR
I/ ads
[3]

provides insight into the oxidation of glucose. The oxida-

tion of fructose This was also proposed by Vassilyev et
at al.'8
0 OH Comparison between deutera fed and
deuterated and pro
pro tonated
tonated glu-
glu-
eose.—The replacement of an atom by one of its isotopes
cose.—The

[ RxCH2O
11 (A).FRIJCTOSE
(A)-FRIJCTOSE OOIM
(B) .- Na-GLUCONATE
Na-GLUcONATE O.OIM Au(IOO)
and sodium gluconate
0
II
Il-C
H-C
\
Na
7-
F-
F..

zU'
a
I-.
z 10 A
A cm•2
cm-2
01
Cd

I I I I I
-06 -04 -0.2 0.0 02 0.4 0.6

-0.5 0 0.5 1.0

1.1 E(V) vs SCE
E(V) vs

Fig. 5. Voltammetry curve of polycrystalline rotating disk elec- Fig.

Fig. 6. Voltammetry curves for Au(100) electrode in phosphate
frode
trode in
in the
the presence
presence of
of phosphate
phosphate buffer
buffer only.
only. The
The rotating
rotating rate
rate was
was buffer (dashed line) and in the presence of 0.01 M fructose
fructase (A), and
0 rpm (solid line), and 2500 rpm (dotted line); sweep rate, 20 mV/s; 0.01 M Na gluconate
gluconate (B).
(B). Temperature
Temperature == 298
298 K,
K, sweep
sweeprate,
rate,
temperature = 298 K. 50 mV/s.

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 J Electrochem.
J. Electrochem.Soc.,
Soc.,Vol.
Vol.143,
143,No.3, March1996
No.3,March 1996TheThe
Electrochemical Society,
Electrochemical Inc.
Society,Inc. 763

rrO
II
IrS\
fl C-OH
U
IL
'
'-H ath
ads

(reaction 3) may undergo desorption followed by a solu-

tion phase dismutation or dimerization reaction, or fur-
ther oxidized to become gluconolactone. The reaction of
the adsorbed radical with AuOH formed in a fast reaction

EN SSCL
EN C rrO
II
'J
(Eq. 1 or 2) has been proposed by Vassilyev et aL3'4

C-OH II taAuOHI
3!I C-OH
.J
r0
— II \C=O
AuOHl
C=O+H+e
+W+e
at.3'4

[4J
[41
.10
.1.0 -(I.
-(1.3 0 0.5 'U
IS
fl' R
H J R
H
Fig. 7. Voltammetry curves for Au polycrystalline electrode in
phosphate buffer (dashed line) and in the presence of 0.01 M Na
As the lactone readily undergoes hydrolysis, gluconic acid
lèmperature == 298
gluconate. Temperature 298 K,
K, sweep
sweep rate,
rate, 50
50 mV/s.
mV/s.
would be the final stable product
rO
has proved very valuable in the study of reaction mechan-
has I C=O. + H20 - R'-COOH
H'-COOH [5]
isms. Such isotopic substitution can cause a change of the
rate constant and can be used to confirm the mechanism. R
H
In a reaction in which the rate-determining step involves It is not certain, however, that the direct oxidation of the
the breaking of the C—H bond, replacement of the H with adradical is possible without the AuOH species (Eq. 4).
D will result in a primary isotope effect. If the ratio of the The inertness of fructose under the same conditions
reaction rates (kH/kD)
(kH/kfl) is 2 or more, it is evidence that the
the (Fig. 6), as compared with the oxidation of glucose, makes
hydrogen atom
bond to the substituted hydrogen atom isis being
being broken
broken inin reaction 4 (i.e., the further oxidation of H atoms other than
the transition state of the rate-determining step.'9 the aldehyde hydrogen) questionable. A major change of
In order to obtain further evidence that the reactive cen- the reactivity of the molecule may, however, be produced
ter of glucose oxidation is the carbon C1 atom, the hydro- by the radical formation (Eq. 3). However, infrared spec-
gen bound to the carbon C1 atom of glucose was replaced troscopy and proton nuclear magnetic resonance spectro-
by deuterium. Figure 8 shows a large difference in the scopic measurements indicate that the intermediate is glu-
peak current for the deuterated and protonated glucose. conolactone and the final product is sodium gluconate for
The ratio of the current of protonated to deuterated glu- the electro-oxidation of glucose in phosphate buffer (pH
cose in the glucose electro-oxidation is 2.3. This shows 7.4) in the Au double layer region.
that the hydrogen bound to the carbon C1 atom is oxidized
and the breaking of this bond is the rate-determining step Dependence of kinetics in glucose concentration—The
(Eq. 3) in the electro-oxidation of glucose. current (i) for glucose oxidation can be given by the
It remains to be seen whether a further electrochemical expression
oxidation of the adradical takes place. The adsorbed i = k[C,jm[1
k[Cjm[1 — O]f(E)
OYf(E) [6]
species
constant, EGG]
where k is the rate constant, [CG] isis the
the molar
molar concentra-
concentra-
tion of glucose, [0]
[01 isis the
the coverage
coverage of of AuOH
AuOH on on the
the gold
gold
surface, m and n are the reaction orders with respect to
glucose concentration and vacant sites, and f(E) is the
function of potential. The coverage of the surface with
AuOH (0) is constant at constant potential E.
Equation 6 involves the following assumptions: (i) glu-
cose is not specifically adsorbed on the gold surfaces in the
range of potential where the oxidation reaction occurs; (ii)
the back reaction is negligible; (iii) the reaction occurs
predominately by an outer-sphere electron transfer, i.e., CG
corresponds to the concentration in the outer Helmholtz
plane.
The reaction order with respect to CG was obtained from
m = ((5log i/ log
log i/S log CG)EO
CG)EO [7]
The behavior shown in Fig. 9 is similar to that observed
by several other
other researchers3"6'19'2°
researchers3"6'9'2° i.e.,
i.e., the
the current
current is a lin-
ear function of glucose concentration at low concentration
but appears to approach a limiting value at higher con-
centration (>102
(>10 M).
M).At
Atlow
lowconcentrations,
concentrations, the
the slopes
slopes
correspond to m = —1, corresponding to first order kinet-
ics. Vassilyev et al.3 reported that the reaction order (m) of
glucose oxidation on polycrystalline gold is approximate-
ly 0.6-0.7 from 0.1-0.46 V vs. SCE in phosphate buffer
solutions and 0.46 to 0.9 from —0.09 to 0.96 V vs. SCE in
1 M KOH.
1(V).1.
I(S) fl SCL
SCI Tafel plots.—Figure 10 shows the log i vs. E plots (Tafel
plot) for glucose oxidation for the three low index surfaces
Fig. 8. Electro-oxidation of glucose (0.01 M) on the polycrystalline in phosphate buffer solutions at room temperature. These
gold electrode (solid line), deuterium labeled glucose (dotted line), plots were obtained from an anodic scan of glucose oxida-
and voltammetry curves in the absence of glucose (dashed line). tion with the scan rate of 1 mV/s. All Tafel slopes are sim-
Temperature = 298 K, sweep rate, 50 mV/s. ilar; the slope between —0.4 V and —0.1 V vs. SCE is

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 764 J Electrochem. Soc., VoL 143, No.3, March 1996 The Electrochemical Society, Inc.

2-
1 -200mV
D -200mV
• -l5OmV
i5OmV oroD
ofl
1- a -lOOmV i.
1 AullO 0000
4
0 01 0
0 0•
0
00)
Au 110
—1

22
I-, • I • —2
—0.5 —0.4 —0.3 —0.2 —0.1
r
—00
—0.0 0.1
E/V vs. SCE
9.
0 DEl D
D DEl B

4
01
I
i
1. AulOO
Au 100
nD
0D

0 1.
0 0) 0
0 0

—1 0'
D'
2
—2
—2 .— —
—0.6 —0.4 —0.2 0.0 0.2
E/V vs. SCE

4
0)
0 Au 111
4

.2 o
2 0

—5 —4 —3 —2 —1

log [CI

Fig. dependence of glucose electro-oxidation for

Fig. 9. Concentration dependence for —2 - . . .- . V
--
Au(1 10), Au(100), and Au(1 11) in phosphate buffer at tempera- —0.6 —0.4 —0.2 0.0 0.2 0.4
0.4
hire = 298 K.
ture
E/V vs. SCE

117 mV/decade for Au(100), 118 mV/decade for Au(111), Fig. 10. Tofel electro-oxidation of glucose
Tafel plots (log i vs. E.) for elecfro-oxidation
and 105 mV/decade for Au(110). These values are close to (0.01 /4 in phsphate buffer
n phsphate buffer at temperature = 298 298KKfor
forAu(1
Au(1 10),
10),
the value —120 mV/decade, as expected for the transfer Au(100), and Au(1
Au(1 'I11).
1).
coefficient xx = —0.5
coefficient —0.5 with a first one-electron-transfer
rate-determining step (Eq. 3). A simple one-electron-
transfer process involving the glucose molecule separated adsorption, which is formed by the electro-oxidation
electro-oxidation ofof
from the electrode surface by layer of water;
water, i.e., outer glucose at
glucose atEE = +0.3
+0.3 V and E = +0.5 V in Fig. 11. Another
sphere electron transfer may also be operative. The glu- peak appears at 2345 cm' at a positive potential of +1.0 V
+ 1.0 V
cose molecule has relatively large dimension and it is pos- vs. SCE which is in the Au oxide region and is due to solu-
sible that this molecule can be positioned normally to the tion phase CO2. Vielstich et at.21
aL21 using on-line mass spec-
electrode surface and enter the outer Helinholtz
Helmholtz layer. A trometry also reported that CO2 was found only in the Au
Tafel slope about 120 mV was reported for the electro-oxi- oxide region during the electro-oxidation of glucose in
dation of glucose on polycrystalline gold in neutral buffer phosphate buffer. The detection of gluconolactone at
solution.4
solution.34 potentials cathodic to oxide film formation and of CO2 in
SNIFTIRS study of the oxidation of glucose—Figure 11 the anodic film region, were also observed in 0.1 M
shows SNIFTIRS spectra of Au electrode in phosphate HC1O4, 13
HC1O4.
buffer pH 7.4 at various anodic potentials in the presence Other peaks between 1250 and 800 cm1 (not shown)
of glucose. The band at —1750 cm' can be attributed to were attributed to phosphate adsorption on Au in phos-
the stretch vibration of carbonyl C=O (gluconolactone) phate buffer pH 7•41213
7,41213 The
The gluconolactone
gluconolactone peaks
peaks in
in phos-
phos-

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 J. Electrochem. Soc., Vol. 143, No.3, March 1996 The Electrochemical Society, Inc.
3000 2500 2000 1500
WAVENUMBERS, cm
Fig. 11. SNIFTIRS specfrum for the polycrystalline Au/solution
interface of 0.01 M glucose in phosphate buffer (pH = 7.4) at (a)
+0.3 V; (Ia) +0.5 V; (c) +1.0 V; reference potential = —0.5 V vs.
SCE; 250 scans.
phate buffer (Fig. 11) are essentially at the same frequen-
cy of 1751 2 cm1 and they do not change significantly
in the potential range examined. Therefore, it is difficult to
say whether these peaks correspond to the adsorbed
species or the solution phase species.
The production of CO or CO2 in the oxidation of glucose
would involve more than two electrons per glucose. No
additional bands were observed in the SNIFTIRS spectra
between 1800-2500 cm1, the region where CO and CO2
species produce strong infrared adsoprtion bands2223 for
glucose oxidation at potentials negative to the anodic film
formation. Therefore, based on the SNIFTIRS results, it
may be concluded that during glucose oxidation at the
potential negative to the Au oxide region in phosphate
buffer solutions the extent of the oxidation of glucose mol-
ecule is small.
1H NMR.—Table I shows the results of the ex situ 1H
NMR spectroscopy measurements of the product of glu-
cose (0.01 M) oxidation carried out for six days on poly-
crystalline Au foil at +0.3 V vs. SCE in deuterated phos-
phate buffer (pH = 7.4, ionic strength = 0.1). For the
electrolysis, the potential was stepped from —0.5 to +0.3 V
vs. SCE. The initial current was around 0.4 mA/cm2,
decreased to 0.2 mA/cm2 after 5 mm, and decayed to 0.75
sA/cm2 at the end of six days. The potential was then
stepped back to —0.5 V from +0.3 V for one mm, stepped
to +0.3 V again from which a decay current of 3 pA/cm2
was measured after five mm. Stepping the potential from
—0.5 to +0.3 V in the absence of glucose in phosphate
buffer resulted in a much smaller current, i.e., 0.2 p.A/cm2,
after only five mm.
The spectrum of the reaction product was taken at 200
MHz (using Varian Associates XL-200 NMR spectrometer)
at room temperature. Tetramethylsilane in CDC13 in a
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765
Table I. 1H NMR absorption chemical shifts of the product
of 0.01 M glucose electro-oxidation at a potential
+0.3 V vs. SCE in D20/phosphate buffer (pH = 7.4)
for six days (see text for details).
Structural type
a
b
C
S (ppm)
4.1
4M
3.7
i b
?''
NaOOC—C—1b—C—é—CH2OH
d 3.6 a cde
e 3.5
coaxial capillary tube was used as an external standard.
The 'H NMR spectroscopy indicates that the reaction
product is sodium gluconate on the basis of comparison
with the 'H NMR spectrum of sodium gluconate (Sigma
Chemical Co.) obtained at the same condition, and the lit-
erature spectrum in the Sadtler Index of Sadtler Research
Laboratories, Inc., Philadelphia, Pa.24 Several small peaks
observed at around 5.2, 4.6, and 3.4 ppm (not given in
Table I) are due to the residue of glucose remaining in the
electrolyte since the electrolysis was not completely
finished.
The glucose oxidation product obtained in aqueous
phosphate buffer system (other conditions identical) was
the same at that obtained in D20. At the end of the six
days, the water was removed using rotatory evaporation at
35°C. The residue was dissolved in D20. The 'H NMR spec-
trum of this sample was virtually identical to the one used
to obtain Table I. This confirms the stability of all of the
C-H bonds in the glucose molecule.
The electro-oxidation of glucose was also attempted in
two other ways. When the potential was cycled between
—0.5 and +0.55 V just before the gold oxide formation
region, an initially large current peak was observed at
0.55V, which diminished with time and virtually disap-
peared after six days. The 1H NMR spectrum of the prod-
uct of this glucose oxidation procedure was virtually iden-
tical to the data in Table I. When the potential was cycled
between —0.5 and +1.2 V (where Au-oxide forms), a pur-
ple-violet colored precipitate appeared after three days.
The LH NMR spectrum of the residue yielded no observable
peaks in the spectrum with either D20 or DMSO as the
solvent. This implies that glucose was electro-oxidized to
become CO2 and H20 under these conditions. This is in
agreement with our in situ FTIR data and on-line mass
spectral studies2' which showed the formation of CO2 for
glucose oxidation at potentials near and positive to the Au
oxide region.
The 'H NMR spectrum of gluconolactone (0.01 2W) dis-
solved in the D20/phosphate buffer solution was measured
and was found to be virtually the same as the literature
spectrum. The same gluconolactone/D20/phosphate buffer
solution was put into the cell used for the oxidation of glu-
cose. The potential was stepped from —0.5 to +0.3 V (after
the addition of gluconolactone to the D20/phosphate
buffer solution), and over a few minutes, only a small
anodic current (on the order of double layer charging)
passed. An aliquot was immediately withdrawn from the
cell and the 1H NMR spectrum of this sample was taken
and was found to be virtually identical to the data in
Table I. This indicates that gluconolactone spontaneously
and quickly hydrolyzes to sodium gluconate under the
conditions used in the study of glucose oxidation on Au
electrodes.
The Reaction Mechanism and Conclusion
The reaction kinetics of glucose electro-oxidation
exhibit a pronounced structural sensitivity on gold single
crystal surfaces. The onset of glucose oxidation occurs at
the most negative potential for the Au(110) surface which,
 766 J. Electrochem. Soc., Vol. 143, No.3, March 1996 The Electrochemical Society, Inc.

howevex shows smaller peak currents than the other two

however; two transferred to the electrode. Gluconolactone was desorbed
Au(11O),
low index surfaces. Two peaks are seen for Au(1 10), one from the electrode and hydrolyzed to form sodium glu-
peak and a prepeak for Au(111), and only one large peak conate in phosphate buffer or gluconic acid in acid solu-
for Au(100). tion (Eq. 8-4). The final product was determined by 'H
The formation
formation of
of an
an(OH)ath
(OH)ad.layer
layerininphosphate
phosphate buffer
buffer on NMB spectroscopy. The whole process involves the trans-
NMR
Au correlates approximately with the onset of the electro- fer of two electrons per glucose molecule (Eq. 8-5).
oxidation of glucose indicated from the voltammogram. If the interaction between the glucose and the gold elec-
This implies a possibility of a catalytic effect involving trode is relatively weak in this reaction, the mechanism of
(OH)ath species. glucose electro-oxidation can be proposed as below.
The electrochemical oxidation of glucose appears to pro- Mechanism II
ceed through a pathway involving the loss of the H atom
attached to the C, carbon atom. Evidence for such involves H20 -* AuOH'
Au + H2O AuOW' +H
}j++ Xe
Xe [9-1]
the inhibition of the oxidation of fructose which lacks such
a hydrogen atom and the substantial kinetic isotope effect rOH rrOH
when the hydrogen is replaced with deuterium.
Rotating disk experiments indicate a decrease in the IC/\ — II IIC\/
IC
I \/AuOH
I \/AuOH
— /\
I
+H+e
+W+e [9-2]
peak current with increasing rotation rate. The most logi-
cal explanation is the transport of reaction intermediate(s)
LBOH
I
LROH LBO
LROads
I
ads
away from the electrode into the bulk solution.
rrO LI-ii•
H-ii• rO
Gluconolactone has been identified as a reaction inter-
II II AuOH I \
mediate in phosphate buffer at potentials negative to Au
oxide formation during the oxidation of glucose by in situ
U
II C
'H
II /\C IIIH.—k C0+Ht+e
CO+W+e
/ [9-3]
I
FTIR spectroscopy. Hydrolysis of gluconolactone will then LLB
L.LR 0usd,
Oiiaas LB
LB
produce sodium gluconate in phosphate buffer solution.
'H NMR spectroscopy indicates that sodium gluconate is
the final product in the phosphate buffer solution (pH 7.4)
when the glucose electro-oxidation potentials are cathod- I\
rO
II CrO+H2O-+B'_COOH
Cr=O+H,O-+R'_COOH [9-4]
ic to oxide formation. If the oxidation potential encom-
passes the oxide formation region, the sodium gluconate LI B
can be further oxidized toto CO2
CO, and
and H,O.
H20.
Based on the results of this work, the following mechan- The overall reaction is
isms may be proposed for the electrochemical oxidation of
glucose on gold electrodes at potentials cathodic to the rO H
oxide formation region in acid and phosphate buffer solu-
tions. If a substantial interaction occurs between glucose
I
II
\/C+H,O
C+HO —*
AuOH
AuOH
—k R'-COOH+2W+2e
B'-COOH+2W+2e [9-5]
and the gold electrode, the mechanism for glucose electro- B OH
LB OH
oxidation may be
Mechanism I In Mechanism II, the first step is the same as in
-
Au + H20 -+ AuOH'
AuOH' +HH++XeXe [8-1] Mechanism I, formation of
of (OH)ad.
(OH),,,, on Au (Eq. 9-1). The
second step is the oxidation of the hydrogen from the
rOH rrO hydroxyl group bound to the C, carbon atom (Eq. 9-2)
instead of the hydrogen bound to the C, carbon atom
III \/AuOH
II
CC—k
—* C-OH +W+e
C-OH +H+e [8-2]
I
I
(Eq. 8-2). This process will be fast. One electron is trans-
ILROH
I\
J\ LR/
LR
I
I
I
[8-2]
ads
ferred to the electrode and a free radical species is formed
(Eq. 9-2). Further oxidation of this radical species then
takes place, and the remaining hydrogen in the hemiacetal
rrO\
II
n. rO
II AuOH I \
group was removed (Eq. 9-3). Gluconolactone was pro- pro-
duced and another electron was transferred to the elec-
JI C-OHR —* I C=O+H+e
'H C—OHR [8-3]
II
ILR
/ Jjads
'-ER
II BI
I[ R
I
trode. Also, the breaking of this (C-H) bond (Eq. 9-3)
should be the rate-determining step, as indicated by the
primary isotope effect. The hydrolysis of gluconolactone to

I'I\
rO
C=O + H20
1120 -. R'-COOH [8-4'
F8_41
form sodium gluconate (Eq. 9-5) in phosphate buffer or
gluconic acid in acid solution will be the same as in
Mechanism j.
I.
The activation energy for the formation
formation of
of the
the hydrogen
hydrogen
'-B
'-H bond between the AuOH with C-H group in Mechanism I
may be higher than AuOH with 0-H group in Mechanism
The overall reaction is II. The inertness of fructose
rO H
I \IC=O ++ H20
I AuOH
H,O — B'—COOH + 2H
— R'—COOH 2W ++ 2e [8-51
[8-5]
I
I
LR
/\
B OH
OH [OC(
B CH2O
B CH2O
The formation of (OH)ath on Au
(OH)a,, on Au is
is the
the first
first step for the elec- on Au in phosphate buffer makes Mechanism II less favor-
trochemical oxidation of glucose (Eq. 8-1). The oxidation able than Mechanism I. However, the intermediates
of glucose is assumed to be through the interaction involved in both mechanisms may diffuse into the bulk
group and
between the hemiacetal group and (OH)ads.
(OH),,,,. The
The hydrogen
hydrogen solution during the electro-oxidation of glucose as indi-
bound to C1
C, carbon
carbon atom
atom will
will be
be the
the first
first one to be oxi- cated by the rotating disk experiment.
dized on Au and the radical species is formed (Eq. 8-2). Only one of the intermediates in Mechanism I or
Such process is the rate-determining step and would Mechanism II was detected (e.g., gluconolactone) in this
explain the primary isotope effect. In this step one electron study. Therefore, a confirmation of the exact mechanism (I
was transferred to the electrode. The radical species is or II) is difficult. However; information was
However, significant information was
then further oxidized to form gluconolactone (Eq. 8-3) obtained here, adding to the understanding of the electro-
which was detected by in situ FTIR
FTIB spectroscopy in acid chemical oxidation of glucose on Au. Such information
and phosphate buffer solutions and another electron is should be helpful in designing an implantable glucose sen-

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 J. Electrochem. Soc.,
Soc., Vol.
Vol. 143,
143, No. 3, March 1996 The Electrochemical Society,
No.3, Society, Inc.
Inc. 767

sor to monitor the glucose concentration in the body

body for
for 11. B. Beden, I. Cetin, A. Kahyaoglu, D. Takky, and C.
the treatment of diabetes mellitus. 37 (1987).
Lamy, J. Catalysis, 104, 37
12. M. Razaq,
Raza4, M. Hsiao, R. R. Adzic, and E. B. Yeager,
Acknowledgments Unpublished material.
13. M. W. Hsiao, Ph.D. Thesis, Case Western Reserve
The authors thank C. Vitus for useful comments and University, Cleveland, OH (1990).
University,
acknowkdge the
acknowledge the support
support this
this research
research by the U.S. 14. M. W. Hsiao, R. R. Adzic, and E. B. Yeager, Electro-
National Institute of Health, the State of Ohio through the chim.
chim. Acta, 37, 357 (1992).
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Naval Research. 11, 261 (1975).
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Manuscript submitted March 23, 1995; revised manu- Bioenerg. 15, 157 (1986).
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Bolzan, T. Iwasita, and W. Vielstich, This
P Iwasita, This Journal,
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The Dissipated Energy of Electrode Surfaces: Temperature

Jumps from Coupled Transport Processes
Dick Bedeaux
Department of Physical and Macromolecular Chemistry, University of Leiden, 2300 Leiden, The Netherlands

Signe Kjelstrup Ratkje*

Department of
Department of Physical
Physical Chemistry, The Norwegian Institute of Technology,
Technology, The
The University
University of
of Trondheim,
Trondheim,
7034 Trondheim, Norway

ABSTRACT
Nonequilibrium thermodynamics for surfaces has been applied to the electrode surfaces of an electrochemical cell. It
is shown that the temperature of the surface differs from that of the adjacent electrolyte and electrode, and that a tem-
perature jump exists across the surface. Mathematical expressions are derived for the temperature profiles of two cells at
steady-state conditions. Methods for estimating transport coefficients for the coupled transport processes at the electrode
surface are discussed. Possible numerical results for the temperature profile, the overpotential, and the dissipated ener-
gy are reported. The results reflect the relative importance of heat conductivities, electric conductivities, and the Peltier
coefficients for the electrode surface phenomena in combination with bulk properties. Significant temperature jumps may
normal electrolysis
occur at normal electrolysis conditions
conditionsi03
io to
to io
io A
A m2,
m2, and for temperature jump
jump coefficients
coefficients which
whichare
aresmaller
smallerthan
thani03
io
J s' K2 m2. The overpotential may have contributions from the Peltier coefficients for the surface larger than the ohmic
contribution. The method of analysis gives new information useful for heat control of electrochemical cells, electrode
kinetic studies, and interpretation of overpotentials.

Infroduction reason why it is important to have access to the surface

The energy dissipated as heat in a process is equal to the
entropy production rate per unit volume, a, times the tem-
perature, T The dissipated energy can be regarded as lost
work. Its value is therefore a measure of the efficiency of
the energy conversion process. In a reversible process the
lost work is zero. The dissipated energy of an electrochem-
ical cell can be separated into the dissipation in the bulk
materials and the dissipation at the electrode surfaces. The
electrode surfaces are important, because they are sites for
the electrode reactions and overpotentials. Chemical reac-
tion kinetics depends on the temperature. This is one
* Electrochemical Society Active
Active Member.
Member
temperature. We show here that a temperature jump exists
across the surface, or that the surface temperature is
in principle different from the temperature of the
surroundings.
It is customary to calculate the dissipated energy at the
surface from the product of the overpotential and the elec-
tric current plus the joule heat. In this work we show that
the overpotential contains reversible parts, so-called
Peltier effects, in addition to irreversible parts. The Peltier
effects do not contribute to the entropy production at the
electrode surfaces, but they do affect the temperature pro-
file across the cell. Therefore it is important to address the
coupling of phenomena at the electrode surface. This has
not been done before. We see that the magnitude of the

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