Electrochmrca Acro.

Vol 37, No 8, pi 1333-1342, 1992 0013+686/92 $5 00 + 0 00

Pnnted Ill Gnat Bntam 0 1992 Fwgamon Press Ltd

“ON LINE” CHROMATOGRAPHIC ANALYSIS OF THE

PRODUCTS RESULTING FROM THE
ELECTROCATALYTIC OXIDATION OF D-GLUCOSE ON Pt,
Au AND ADATOMS MODIFIED Pt ELECTRODES-PART I.
ACID AND NEUTRAL MEDIA

K B KOKOH,J -M LBGER,B BEDENand C LAMY

Laboratolre de Chume I, URA-CNRS 350, Umvensk de Poltlers, 40, avenue du Recteur Pmeau,
86022 Poltlers Cedex, France

(Recemed 10 June 1991, m rewsedform 29 October 1991)

Abstract-Usmg smtable potential programmes, sustained electrolysis of aqueous solution of D-ghmSe,

m perchlorlc and phosphate buffered media were carried out on Pt, Au and adatoms (Pb, Tl, Bt) modified
Pt electrodes The reaction products m solution as well m the gas phase were analysed by HPLC and GC
chromatograptic techniques, and their concentration was followed vs the time of electrolysis It IS
confirmed that whatever the expenmental condltlons, glucomc acid 1sthe mam reaction product However,
many other carboxyhc acids (among which glucanc, glucuromc, tartanc, glyoxyhc, oxahc, glycohc and
formic aclds) were detected Theu concentration dlstrlbutlon was found to depend mainly on the catalytic
properties of the surface For example, with Bl adatom moddkd Pt, a sigruficant amount of @ucuromc
acid could be produced

Key words D-ghCOSe, electrooxldatlon, chromatography, adatoms, reaction mechamsms

INTRODUCTION occurs with very small concentrations of metal ions

The electrocatalytlc oxldatlon of D-glucose has
roused great interest for the last two decades, when
the ideas appeared for using glucose/oxygen fuel cells
as power sources for cardiac pace-makers or to
develop glucose sensors[ l-51
These electrochemical studies were mainly carned
out by voltammetnc methods on noble metal elec-
trodes Most of the works on glucose oxldatlon were
made on platinum electrodes and the main concern
was to study its anodlc oxldatlon m an electrolytic
medium similar to physlologlcal condltlons
Thus, Rao and Drake[6] investigated the electro-
oxldatlon of D-glucose m phosphate buffered
medium They found that glucomc acid 1s the
only reaction product formed and that It 1s
absorbed strongly on the electrode surface, so that
further oxldatton of D-ghCOSC IS inhibited Like
Skou[7,8], they assumed that glucomc acid could
not be oxidized
Furthermore, De Mele et al [9-131 studied the
oxtdatlon of D-glucose, glucono-b-lactone, glucomc
acid and other monosaccharides m phosphate
buffered medium at different temperatures This com-
parative analysis enabled the authors to find a re-
lationship between the electrochemical behavlour and
the structural charactenstlcs of these molecules
The effect of different adatoms (Tl, Pb and Bl) on
the catalytic actlvlty of noble metal electrodes
toward D-glucose oxldatlon was studied by
several authors[l4-201 Adsorption isotherms of the
systems Pt-Tl, Pt-Pb and pt-BI showed that the
maximum catalflc effect appeared for coverage val-
ues & _ 0 5 Moreover, the larger catalytic action
m the bulk The results also indicated that the
catalytic effect depended not only on the nature of
the adatoms, but also on stenc and structural charac-
tenstlcs In the presence of adatoms, the oxldatlon
current densities increased with the concentration of
D-glucose
The present work was aimed at studying the elec-
trocatalytlc oxldatlon of D-glucose on platinum and
gold electrodes modified or not by foreign metal
adatoms (Tl, Pb and Bl) m acid and neutral media
Analysis of the products was camed out by chro-
matographlc techniques (HPLC ond GC), m order to
follow the consumption of D-glucose, and the for-
mation of reaction products durmg prolonged elec-
trolysis using a suitable potential-time programme A
future paper ~11 present a similar study, but m
alkaline medium
EXPERIMENTAL
The expenmental methods, used m this work, were
cyclic voltammetry (cu), programmed potential elec-
trolysis (PPE), high performance hqmd chromatog-
raphy (HPLC) and gas chromatography (GC)
All the electrochenucal measurements were carned
out at room temperature in a two-compartment glass
cell (volume = 60 cm3 for each compartment, separ-
ated by a cationic exchange membrane) The support-
mg electrolyte (HC104 or KH,PO,/NaOH) was
prepared from Merck “Suprapur” products and
ultrapure water (Ml11 Q/Mdhpore System) The
other reagents used were D( +)-glucose (Merck) and
Tl, Pb and Bl perchlorate salts (Roc/hc)

EA 37/8-c 1333
1334 K B KOKOHet al

0 OL 08 12 E/V(RHE)

Fig 1 Voltammograms of a platmum electrode recorded at 0 05 V s-l, m 0 1 M HCIO, (---), at the

begmmng (- ), and at the end (- -), of the electrolysis of 0 2 M o-glucose The Inset shows the
potential programme used

Before each expenment, the solutions were deaer-
ated with ultrapure nitrogen (U Quality from L’Alr
Llqmde), while a mtrogen stream was mamtamed
over the solutlon durmg the measurements
The working electrode (WE) was a platinum gnd
(with an active area of 4Ocm*) or a gold gnd
(S = 50 cm*) used either pure or modified by foreign
metal adatoms A 90% platinum/lo% lndmm sheet
and a Hg/Hg, S04, K2 SO4 saturated electrode served
as counter and reference electrodes, respectively But
the electrode potentials given m this paper are all
referred to the rhe scale
Solution samples (10 pl), taken from the reactive
medium durmg the electrolysis, were immediately
analysed by HPLC Identlficatlon of the organic acids
was achieved by comparmg their retention time to
those of known acids The mobile phase was a
3 6 mM sulphunc acid solution, and the separation
was made on a BloRad Ammex HPX-87 H Column
thermostatted at 30°C A double detection was real-
ized using a vanable wavelength uu spectrometer
(Knauer) followed by a differential refractometer
(RI) (Knauer) Chromatograms were recorded with a
two channels integrator (chromate-integrator D2000,
Merck), the first channel for the uv slgnal and the
second one for the RI signal Carbon dloxlde m the
gas phase (le above the reactive medium) was
analysed by gas chromatography (Automatic
Glr&PG li) -
Previous mvestlgatlons showed that peak A
represents the dehydrogenation of the anomenc
carbon This reaction was shown to be adsorption
controlled, whereas peaks B and C represent
oxldatlon reactions limited by a mass transfer
phenomenon (dlffuslon)[21] (Fig 2)
However, the current densltles of ~-glucose oxi-
dation m acldlc medium are relatively low
(I,,, = 0 13 mA cm-* at 1 2 Vlrhe), showmg that D-
glucose IS not very reactive m acid medium
A suitable electrolysis programme was realized,
wrth an oxidation plateau chosen at 1 1 V/rhe, after
having checked that the other oxldatlon peaks led to
current intensities decreasing rapidly to zero after
about 10 mm
With the optimized programme qven m Fig 1,
D-glucose electrolysis could be followed up to 29 h,
dunng which the current density and the quantity of
electnclty were both recorded (Fig 3) At the begm-
mng of electrolysis, the current density, which
,-
‘E
20
\
G
0
-1

RESULTS

1 D-Glucose electrooxrdatlon on smooth platmum m -2

0 1 M HClO,
Figure 1 shows the voltammograms of a pure
platinum electrode (S = 40 cm*) m 0 1 M HClO,,
Hrlthout and Hrlth 0 2 M D-glucose In agreement wth -5 -L -1 0 1
previous work, three oxldatlon peaks are notlced (A, loqw v f’)
B and C) durmg the positive potential sweep and then Fig 2 Dependence of log I on log v for the oxidation at a
another peak (D) followed by a hump (E) durmg the Pt electrode of 0 1 M glucose m 0 1 M HClO, at 25°C A to
negative potential sweep D refer to the voltammetnc peaks of Rg 1
 Oxidation of o-glucose 1335

potential deposition (upd) of foreign metal adatoms,

from low concentrated soluhons of thar salts, in
80 order to increase the selectivity of ~-glucose ox+
datlon into products Adatoms are supposed to oc-
cupy preferably the polsomng rites of the electrode,
thus enabling the surface to keep its actWy much
longer than when it IS not mod&d
012 Foreign metal adatoms are deposlted onto the Pt
20
surface according to the reduction equation
0 0
M’++ze-+M
W ads 3 (1)
0 6 12 18 2C 30
t/h where z IS the lomc valence of the metal M
Fig 3 Vanatlons vs the electrolysis time of the current According to Sakamoto and Takamura[22], the
density (*) and the quantity of electnnty ( + ) dunng the coverage 8, of the electrode surface, by a foreign
electrolysis of 0 2 M n-glucose at 1 1 V/rhe metal adatom M, is defined as

reached 0 4 mA cmv2, decreased slowly durmg the
early five hours Then, It remains constant at 0 22 mA
cm-’ up to the end of the expenment The final
recorded quantity of electnclty, Qnp = 88 C, shows
that the D-glucose conversion yield remains very low
(3 3%)
As a result of chromatographlc analysis, the reac-
tion products, indicated m Fig 4, were detected
Traces of glucanc, glycohc and fomc acids, as
well as carbon &oxide, were also determined How-
ever, two products have remained unknown They
obviously exist as traces
2 D-Glucose oxrdatron on adatoms modljied Pt
electrodes m perchlorrc aced
(a) Determrnatlon of the Pt coverage Qy by cychc
voltammetry Pt electrodes were modified by under-
200 - -6
198 -
196 -
19c-
192 -
190 -
@,=-
QM
Qe-l’
where QM represents the quantity of electnclty whtch
corresponds to the adatoms dlssolutlon [reverse of
reaction (I)], and Q,,., IS the quantity of electnclty
necessary for the formation of a full monolayer of
metal adatoms But, the simple application of the
above formula may @ve overestimated values of &,,,
(close to the umty, or more than unity) because, for
some adatoms, it 1s very difficult to determme exactly
the freed area correspondmg to their dissolution
Therefore, we preferred to define all the parameters
from the hydrogen reDon, which IS very well-defined
on platinum and for which 1 electron-per-site can be
strictly assumed[23]
Thus, calculations based upon the hydrogen
region m the voltammograms of unmodified and
modified Pt electrodes (Fig S), allow us to calculate
O,, as follows
nM
Q =1-E!! (3)
M
Q",'
where Q”, 1s the quantity of electnclty determmed
when all the Pt sites are occupied by adsorbed
hydrogen, and Q! the quantity of electnclty necess-
ary to adsorb hydrogen atoms on the Pt sites free
from metal adatoms M

0 6 12 18 2C 30
t/h #” ._-. bl
! ‘-._

EA'IRHE)

0 6 12 18 24 30
t/h
Rg 4 Evolution, durmg the electrolysis at 1 1 V/h of
02M D-ghxose on a smooth platinum electrode m acid E/vIRHE)
medium (0 1 M HCIO,), of the concentration of (a) D-&I- Fig 5 Hydrogen regon of the voltammognuns of a plah-
case (*). glucomc acrd ( + ), glucurotuc acid (A) and (b) num electrode m aud mednun, m the absence (---). and m
oxalic acid (O), tartanc acid (0) the pnsence (-) of (a) Tl, (b) Pb and (c) BI adatoms
1336 K B KOKOHet al

Table 1 Platinum coverage @,, m the presence

of Tl, Pb and BI precursor salts m 0 1 M HClO, 200 c* 46
solution
198 -
Bulk concentration -C
Adatoms of the precursor salt @M H
\
u 196 -
Tl [Tl+] = lO-S M 0 27
Pb [pb2+] = 5 lo-’ M 047 -2
Bl [BIG+]= lO-J M 051 19c -

8, IS determined from voltammograms recorded

at 50mV s-’ and 25°C
0 6 12 18 24 30

The values of QM calculated from the voltam- t/h

mograms of Pt m the supporting electrolyte are
given m Table 1
(b) E$ect of adatoms on the electrooxzdatzon of
~-glucose Figure 6 shows the voltammograms of Pt
electrodes modified by foreign metal adatoms
recorded m 0 1 M HCIOl, m the absence and m the
presence of glucose Adatoms of Tl, Pb and Bl are
deposited at low potentials, which causes the shrmk-
age of the hydrogen region and the disappearance of
the glucose oxldatlon peak A obtained on unmodified
Pt electrodes
Durmg the posltlve potential sweep, the dlssolutlon
peak of adatoms IS observed at 0 9, 0 8 and 1 V/rhe,
Fig 7 Evolution, durmg the electrolysis of 0 2 M D-glucose
at 0 55 V/rhe on a Pt-Tl electrode, of the concentration of
D-glucose (t), glucomc acid ( + ), and formic acrd (W)
for Tl, Pb and Bl, respectively At vanance wth the
Tl and Pb adatoms (Fig 6a and b), Bl adatoms do
not modify much the behavlour of Pt m presence of
D-glucose (Fig 6c) The mam difference, compared to
unmodified Pt, 1s the increase of the oxldatlon peak
D, at 0 56 V/rhe, durmg the negative potential sweep
D-Glucose electrolyses were realized using a tnple-
pulse potential programme Only the potential of
the oxldatlon plateau was changed, according
to the nature of the adatom (E,,,, = 0 55 V/z-he,
E pl,pb= 0 65 V/rhe and Eptle, = 1 V/rhe)
Figures 7, 8 and 9 give the concentration depen-
dence on time, followed by chromatography of D-
glucose and its electrooxldatlon products Traces of
carbon dioxide were also detected, as well as low
amounts of two reachon products, which could not
be identified

202 - -5

0 6 12 18 2c 30
t/h

02

01

-01
i I I I
0 04 Qa 1.2 0 6 12 18 24 30
EA'IRHE) t/h
Rg 6 Voltammograms of a platmum electrode recorded at Fig 8 Evolution, durmg the electrolysis of 0 2 M D-glucose
0 05 V s-l, m acid medmm, with adatoms. \mthout D&U- at 0 65 V/rhe on a Pt-Pb electrode m and medium, of the
case (---), at the begmnm~(-), and at the end (- z-), concentration of (a) n-glucose (+), glucomc acid ( + ).
of the electrolysis of 0 2 M ~-glucose (a) Tl, (b) Pb, (c) BI glucuromc acid (A), (b) fornuc acid (m), glucar~c acid (a),
adatoms and tartanc acid (0)
 Oxidation of ~-glucose 1337

Consldermg the voltammogram shape, the

electrolysis was camed out using a triple--pulse
potential programme The best results were obtained
when the potential of the oxldatlon plateau was set
to 0 62 Vlrhe and held I5 s
Electrolysis was camed out for 19 h, durmg which
time the electrolytic solution was analysed by HPLC
at regular penods of time It turned out that D-glu-
cose was converted mto glucomc, glucuromc, oxalic,
glyoxyhc and tartanc acids (Fig 11) Traces of
0
glycohc and formic acids were obtained too, and one
10 20 30 40 50 60
reaction product has remained unknown
t/h
The voltammogram recorded at the end of
electrolysis (Fig 10) was entirely shifted to hgher
potentials Th1.s results from acldlficatlon of the
electrolytic medium due to electrooxrdatlon of
D-ghCOSC into its carboxyhc denvatlves

4 D-Glucose electrooxrdatron on gold m perchlorzc

acrd
The voltammograms recorded durmg electrolysis
are gven m Rg 12 At the begmnmg of the oxldatlon
reactlon, the voltammogram shows that the 0 2 M
L 0 I
0 10 20 30 40 50 60
D-glucose solution has a low reactivity on a Au
electrode (S = 50 cm*) m 0 1 M HCIO, acid medium,
t/h
although the current densltles are slightly higher than
Fig 9 Evolution, durmg the electrolysis of 0 1 M o-glucose those obtamed with pure Pt Consldermg that Au 1s
at 1 V/rhe on a Pt-Bl electrode m acid medium, of the
not active for hydrogen, a double-pulse potential
concentration of (a) D-ghCOSe (*), fomuc acid (U), glycohc
acid (V), (b) glucomc acid ( + ), glucuromc acid (A), and
programme was estabhshed Thus, the oxldatlon
oxalic acid (0) potential, which was fixed at 0 95 Vlrhe, was used
both for adsorbing and oxldlzmg D-ghCOSe and/or
the other organic species m solution The potential
3 D-Glucose oxzdatzon on Pt m buffered medwm pulse, for the electrode reactlvatlon by desorptlon of
The voltammograms of Pt were recorded m the polsomng speaes, was fixed at 1 7 V/rhe and held
buffered medmm (KH,PO,/NaOH, pH = 7 3) at durmg 0 5 s
room temperature (25”C), m the absence and m the At the be.gmnmg of the electrolysis, the measured
presence of 50 6 mM D-glucose (Fig 10) The same current density was about 0 12rnAcn-1~*, but It de-
oxldatlon peaks as m acid medmm can be seen, but creased strongly after one hour down to lo-* mA
m the present case, with a much greater mtenslty, cm-*, after which It becomes stable until the end
particularly durmg the negative sweep of the 25 h oxldatlon The recorded quantity of

0 c-4 08 12 l.6ENRHE)

Fu 10 Voltammograms of a smooth platinum electrode, recorded at 0 05 V s-I in neutral medmm, in

the absence of o-glucose (---), at the begmmng (- ) and at the end (- -) of the electrolysis of
50 6 mM ~-glucose
1338 K B KOKOH et al

52 -4
202c 25
al
-3 - 20
s 50

:K_
+ E zoo-
2 -15
2
-2
4 198- -10
-1
-0s

46
0 5 10 15
t/h
0.3
3 02
a solution The chromatographlc
01
0 5 D-Glucose electrooxldatlon on gold m buffered
0
5 10 15
t/h
l%g 11 Evolution, durmg the electrolysis of 50 6 mM
~-glucose m neutral medium @H = 7 3) at 0 62 V/rhe on a
platinum electrode, of the concentration of (a) D-ghCOSe
glucomc acid ( + ) and glucuromc acid (A), (b) glyoxyhc
acid (A), oxahc acid (0) and tartanc acid (0)
electnclty was QcXp= 47 5 C Such a low value reflects
that the degree of oxldatlon of D-glucose on a gold
electrode m acid medium IS small The voltam-
mogram, recorded at the end of the electrolysis, has
a shape which IS different from that obtamed at the
begmnmg of the reaction, showing that some changes
occurred m the composltlon of the electrolytic
0 196, -0
20 0 5 10 15 20 25
t/h
Fig 13 The changes observed dunng the electrolysis of
0 2 M ~-glucose m actd medmm at 0 95 V/rhe on a gold
electrode, m the concentration of o-glucose (*), glucomc
acid ( + ), fornuc acid (m), and glycohc acid (V)
analysis, given m
Fig 13, shows moreover that D-glucose IS oxidized
mto glucomc and formic acids Traces of glycohc
and tartanc acids are also obtained
medwn @H = 73)
20
Figure 14 shows the voltammograms of Au which
were recorded m the absence of D-glucose, at the
beginning and at the end of a 50 2 mM D-glucose
(*).
electrolysis m a buffered medium (0 1 M KH,PO,/
NaOH) The volume of solution m the working
electrode compartment was 13 cm3 The counter
electrode was glassy carbon
The oxldatron of D-glucose on a Au electrode starts
very early m the double-layer reson One can observe
four oxrdatlon peaks, two (A and B), durmg the
positive sweep and two others (C and D hardly
separated), durmg the negative sweep One can notice
that the oxldatlon peaks A and D are nearly super-
imposed, which would indicate small poisoning of
the electrode surface

‘5 1 E/V(RHE)

04 0.0 12 1.6ENRHE)
Fig 12 Voltammograms of a gold electrode recorded at 0 05 V s-l m acid medmm m the absence of
D-glucose (---), at the begmmng ( -) and at the end (- -) of the electrolysis of 0 2 M ~-glucose
The mset shows the potential programme used
 Oxldahon of D-ghaxse
-a2
I I
a4 an
Fig 14 Voltammograms of a gold electrode, recorded at 0 05 V s-l, m neutral m&urn m the absence
of D-glucose (---), at the begmnmg (-) and at the end (- -) of the electrolysts of 50 2 mM
D-glucose
~-Glucose electrolysis was performed usmg a
double-pulse potential programme Adsorption and
oxidation of the organic species were carned out at
0 87 V/rhe durmg 20 s, while the electrode reactl-
vation lasted 0 5 s at 1 82 V/rhe
Electrolysis was followed for 20 h, durmg which
time the vanatlons of the current densltles were
recorded as well
The first hours were characterized by an increase of
the current density (reaching 6 3 mA cm-*), which
not only proves that the rate of D-glucose oxldatlon
increases, when increasing pH, but that gold becomes
more active than platinum The concentrations of
D-glucose and of its oxldatlon products, were fol-
lowed by hqmd chromatogaphy (Fig 15) Apart
from glucomc and glucarlc aads, formic, glycohc
and tartanc acids were also detected at small
concentrations
J “\,/ oH-+Id-OH+H+
0 5 10 15 20
t/h
Fig 15 The changes observed dunng the electrolysis of
50 2mM D-Glucose m neutral me&urn at 0 87 Vlrhe on
a gold electkde, m the concentration of ~gh&xe (*),
gluconrc acid ( + ) and glucanc acid (0)
1339
‘.’
I 1
12 16 ENRHE
DISCUSSION
In agreement with the literature the results ob-
tamed m this work show that glucomc acid 1s the
mam reaction product of D-ghCOSC oxldatlon How-
ever, detailed chromatographlc analysis have also
proved that many other aclds, such as glucanc,
glucuromc, tartanc, glyoxyhc, formic, oxalic and
glycohc acids, as well as carbon dioxide, were also
formed, some of them m appreciable amounts
The modification of the Pt surface by upd adatoms
enabled us to increase the current densities and
therefore to increase the D-ghCOSC conversion yield
Besides, the dlstnbutlon of the oxldatlon products
was found to be modified by the metal adatoms,
particularly with B1, which led to an appreciable
increase m the formation of glucuromc acid (up to
11%) Moreover, it 1s noticeable that glucuronic acid
1s formed on platinum electrodes, whereas it 1s glu-
carlc acid which 1s formed on gold electrodes, as a
result of the oxldatlon of the C6 carbon of the
primary alcohol group
In conclusion, m accordance with previous
studles[7, 11,281 one may assume that the following
reaction mechanisms stand for the electrooxldatlon
of D-glucose into gluconic acid
+e-, (1)
i / \
\R/ 1
H I&
followed, at potentials high enough to oxidize the
surface, by
Pt + H20-+Pt4H + H+ + e- (2)
1340 K B
l&oH+Pt43H4LLo+2RfHO 2 1
d t
and, later on, by hydrolysis
RQ ~HIO-CH~OH-(CHOH)4-COOH
The detailed mechanism, however, must take mto
account the surface state of the electrode, particularly
I it 1s modified by adatoms It 1s likely that the
onentatlon of the adsorbate 1s affected by the pres-
ence of adatoms
Thus, the mechanism can be depicted as follows
(1) On smooth platinum electrodes Glucomc aad
results from the oxldatlon of the D-glucose anomenc
carbon Its formation occurs mto two mam steps, as
the reaction mechamsm scheme (Scheme 1) shows
The potential programme and the vanation of the
current density resulting from this oxldatlon are
mdlcated as well At the adsorption potential
( Eads= 0 2 V/rhe), the current 1s due to dehydrogena-
tlon of the anomenc carbon
At 1 1 V/rhe, hydrogen atoms are replaced by
hydroxyls and the orgamc adsorbate oxldatlon
releases the hydrogen of one OH group This
brings out the lactone desorptlon from the electrode
surface The decreasing of the oxldatlon current 1s
probably caused by the remammg species adsorbed at
the Pt surface, like gluconolactone[24,25] or carbon
monoxlde[26]
(u) On Pt electrodes modified by foreign metal
adatoms Accordmg to Furuya and Motoo[27], Tl
and Pb are metal adatoms which occupy two Pt sites
respectively, while three sites are necessary for Bl The
effect of the upd adatoms 1s to modify the superficial
1 -
2-
KOKOH et al
structure of the electrodes even before the adsorption
of the orgamc molecule In the voltammograms of
Fig 5, the Qsappearance of the oxldahon peak A, m
(3)
the hydrogen rep;lon, can be noticed This might be
due to the foreign adatoms reduction current on Pt,
which compensates for the positive current mtenslty
resulting from the adsorption of D-gbOSC
For the Pt-Tl system, the reaction mechamsm
for D-glucose oxldatlon mto glucomc acid can be
(4) postulated (Scheme 2)
At low potentials, the Tl adatoms are adsorbed
Tl,+,+ e- + Tl,
Then, electrolysis 1s reahzed at 0 55 V/rhe As the
adatoms remam adsorbed at this potential, one can
assume that the oxldatlon reaction proceeds on an
electrode structure such as
Tl Tl
i t-Pt-Pt
(m) On gold electrodes Nlkolaeva et al [28] postu-
lated that, on gold, the mechanism of the oxldatlon
of the D-glUCOSe into glucomc acid, was srmilar to
that on Pt electrodes, although gold has no hydrogen
region
Actually, the oxldatlon plateau m the double-pulse
potential programme IS used both to adsorb and to
oxldlze D-glucose Therefore, it can be assumed that
dehydrogenatlon of D-glucose occurs at the moment
of Its adsorptlon, this weakens the hydrogen bond of
the OH group, which leads to lactone desorptron
from the electrode surface Therefore, the mechanism
can be written as follows
Au+H,O+AU(OH),~,+H+ +e- (1)
AWW,,, + CsH,,Q --) AW,H,, Q&is + I-40 (2)
Au(C~H~~O~)~,,,+C~H~~O~+AU+H+ +e- (3)
t/s
Scheme I
 Oxldatlon of n-glucose 1341

1s -

c
aI

z
Y

055 - _____

t/s
Scheme 2

These mechamsms are valid both m acid and
neutral media, and at the oxldatlon potentials used
m this work
The glucono-b -1actone thus produced 1s probably
responsible m part of the electrode polsonmg, as far
as it remams chemlsorbed, preventing m this way any
subsequent D-glucose adsorption and oxldatlon, as
noted by Kokkmldls et al [19]
However, If gluconod-lactone desorbs from the
electrode surface and diffuses mto the solution, it
undergoes hydrolysis to yield glucomc acid, which m
its turn, 1s transformed little by httle mto the thermo-
dynamically more stable glucono-y -lactone[29, 301
0
C-OH - results mostly concern electrosynthesls (for produc-
b mg glucarlc and/or glucuromc acrds) rather than fuel
Glucono-b-lactone IS therefore a pnmary reaction
product, as Ernst ef al [25] has shown But, it was not
possible to check this hypothesis by hqmd chroma-
tography, because under our expenmental con-
dttlons, glucomc acid and Its two lactones (6 and y)
has the same retention time
The oxldatton of the alcohol group at the C,
carbon of D-glUCOSe leads to glucuromc acid The
mechanism of this reaction (Scheme 3) IS slmllar to
that of the oxldatlon of methanol into formic acid
As far as the degradation products are concerned,
they would result on the one hand, from the dssocla-
tlve chemlsorptlon of D-glucose or of Its denvatlves,
at the applied oxldatlon potential, and on the other
hand, from the secondary oxldatlon reactlons occur-
nng at the potential of the electrode cleaning pulse
As a concludmg remark, it can be said that these

t/s
Scheme 3
1342 K B KOKOH~~ al
cells research, because under our expenmental con-
ditions, the conversion of D-glucose mto carbon
dloxlde remains very low The results we have ob-
tamed certainly contnbute to a better understandmg
of D-@UCOSC oxldatlon Contrary to the literature, rt
IS now clear that glucomc acid IS not the sole and final
product of D-glUCOSC electrochemical oxldatlon
Acknowledgements-The authors wish to thank Drs H
Huser and E M Belgslr for helpful dIscussIons One of
them (K B K ) IS very grateful to the Repubhc of CBte
d’Ivolre for Its financial support dunng the preparation of
his Doctorat Thesis m Poltrers
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