ISSN 1023-1935, Russian Journal of Electrochemistry, 2007, Vol. 43, No. 7, pp. 776–781. © Pleiades Publishing, Ltd. 2007.

Original Russian Text © V.V. Kuznetsov, A.A. Kalinkina, T.V. Pshenichkina, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 815–821.

Electrochemical Properties of Composite Materials Based

on Platinum Modified with Molybdenum Compounds
V. V. Kuznetsovz, A. A. Kalinkina, and T. V. Pshenichkina
Mendeleev University of Chemical Technology, Miusskaya pl. 9, Moscow, 125047 Russia
Received July 7, 2006

Abstract—The composite coating Pt-MoOx is produced by an electrochemical technique under potentiody-

namic conditions on the surface of a preliminarily prepared electrode of glassy carbon. The inclusion of molyb-
denum into the composition of the obtained electrode deposit is confirmed by the data of cyclic voltammetry
and the secondary-electron emission spectra. In the cyclic voltammograms that are obtained in a 2 M solution
of sulfuric acid one can distinguish a pair of peaks at potentials equal to 0.46 V (anodic run) and 0.3 V (cathodic
run), which are connected with the redox transitions experienced by molybdenum compounds. It is discovered
that the obtained deposit possesses catalytic properties with respect to the oxygen reduction reaction. The num-
ber of electrons that are corresponding to the redox transitions experienced by molybdenum compounds is cal-
culated. It amounts to 0.27 electrons per molybdenum atom.

Key words: platinum, molybdenum oxide, electrodeposition, oxygen reduction

DOI: 10.1134/S1023193507070063

INTRODUCTION properties of the electrode material that was obtained

Synthesis of electrode materials that would possess
electrocatalytic properties is of interest for the optimum
of operation of various fuel cells. One of the basic prob-
lems that are investigated at present is the curtailment
of the consumption of platinum [1]. The possibility of
application of oxide materials in the composition of the
material of the working electrode of a fuel cell was
demonstrated in [2]. In so doing a number of require-
ments are placed upon the materials in question, includ-
ing in the first place satisfactory electroconductance
and good corrosion resistance in conditions of exploita-
tion. Besides, when using oxides in the composition of
electrocatalytic materials it is necessary to have their
noticeable catalytic activity with respect to reactions
that proceed in a fuel cell [3]. It is known that com-
pounds of molybdenum in the lowest degrees of oxida-
tion possess electrocatalytic activity with respect to a
number of electrode processes, such as electrochemical
oxidation of carbon monoxide, formaldehyde, and
methanol [4] and the reduction of iodate [5]. In [6],
composite coating êt-åÓéx was applied in the role of
an electrocatalytic agent in the reaction of anodic oxi-
dation of methanol. In this work it was demonstrated
that compounds of molybdenum that enter the compo-
sition of an electrode deposit take part in the process of
reversible recharge, which was testified to by the
appearance of additional peaks in a cyclic voltammo-
gram, which were absent for pure platinum. At the same
time, no systematic investigation of electrochemical
z Corresponding author, e-mail: atech@muctr.edu.ru
was performed. Besides, the electrocatalytic activity of
a êt-åÓéx electrode was estimated only with respect to
the reaction of the methanol oxidation. The obtaining of
some additional information about the properties of this
composite material was the aim of the present work.
EXPERIMENTAL PROCEDURE
The solutions were prepared from reactants of qual-
ification “ultra-high purity” and twice distilled water.
The polarization measurements were conducted with
the aid of a PI-50-1.1 potentiostat coupled with a PR-8
programmer. To perform experiments, we used a three-
electrode cell with a reversible hydrogen electrode in
the same solution as the reference electrode. All the
potentials in the paper are referred to this reference
electrode. In the role of an auxiliary electrode we used
platinum wire. All the experiments were conducted in
an atmosphere of nitrogen. An electrode of glassy car-
bon was polished to mirror finish, degreased in a solu-
tion of KOH at a temperature of 60°ë for the duration
of 3–5 min, and washed with warm (t ≈ 50°C) distilled
water. To purify a surface from possible contaminants,
a specimen would be placed in a 2 M solution of sulfu-
ric acid and subjected to potentiodynamic polarization
in the interval of potentials 0.05–1.1 V for the duration
of 20 min at the potential scan rate 100 mV s–1. There-
after the specimen was washed with twice distilled
water and positioned in a working cell.
The deposition of a Pt-MoOx coating was conducted
out of acid solutions containing 0.008 M of hexachlo-

776
 ELECTROCHEMICAL PROPERTIES OF COMPOSITE MATERIALS
roplatinic acid hydrate, 0.2 M of sodium molybdate,
and 2 M of sulfuric acid in potentiodynamic conditions
while cycling the electrode in the interval 0.05–0.8 V at
the potential scan rate 50 mV s–1 for the duration of
20 min (the overall number of cycles was equal to 40).
Cyclic voltammograms were registered in the course of
the deposition process. In order to compare properties
of the obtained electrode materials to properties of pure
platinum and to unravel the role played by molybde-
num compounds in electrode processes, there were
conducted blank experiments that involved the deposi-
tion of metallic platinum in similar conditions out of an
electrolyte that contained all the required components
with the exception of sodium molybdate. The weight of
the obtained deposits amounted to about 1 mg (the elec-
trode’s area was equal to 6.8 cm2).
In order to examine the electrochemical properties
of the obtained deposits, cyclic voltammograms for the
deposits were obtained in a 2 M solution of sulfuric
acid (at various rates of the potential scan). The electro-
catalytic properties of electrode materials were esti-
mated with the aid of quasi-stationary polarization
curves for the oxygen reduction reaction, which were
obtained in reproducible potentiodynamic conditions in
a 2 M solution of sulfuric acid, through which air was
bubbled prior to performing experiments. The stirring
of the electrolyte was performed with the aid of a rig-
idly mounted magnetic stirrer, while monitoring the
rotation rate of the stirrer.
The investigation of the morphology of the surface
of the obtained deposits as well as the determination of
their chemical composition was conducted with the aid
of a scanning electron microscope JSM-5300LV manu-
factured by the firm JEOL with an adapter for x-ray dif-
fraction microanalysis Link (Oxford), with dispersion
by energies. The determination of the chemical compo-
sition of the surface of the obtained electrode materials
was conducted from the secondary-electron emission
spectra to within an accuracy of 1%. The scanning
depth was equal to ~0.1 µm.
EXPERIMENTAL PART
When cycling potentials of a glassy-carbon elec-
trode in the interval 0.05–0.8 V in a solution that con-
tained hexachloroplatinic acid hydrate and sodium
molybdate (Fig. 1), we visually fixed the formation of a
deposit on the electrode surface. It was established
from the secondary-electron emission spectra (Fig. 2a)
that the substances that entered the composition of the
film that formed at the surface of the electrode included
platinum, molybdenum (its average content in the
deposit was equal to ~8 wt %), and oxygen. It should be
noted that the obtained spectrum exhibited peaks of
carbon, which probably correspond to the substrate. We
cannot rule out that carbon may form also in the course
of transformations experienced by extrinsic organic
substances. However, during the deposition of a similar
deposit onto the surface of highly porous titanium,
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 43
777
I, mA
40
0
0.1 0.3 0.5 0.7 0.9
E, V
–40 1
2
–80
Fig. 1. Cyclic voltammograms obtained for the synthesis of
composite coating Pt-MoOx on the surface of glassy carbon:
(1) 2nd cycle and (2) 40th cycle; potential scan rate v =
50 mV s–1.
there were discovered no peaks of carbon, but instead
there were clearly distinguishable peaks of titanium [7].
Therefore, more plausible seems to be the assumption
that the appearance of peaks corresponding to carbon is
connected with the porosity of the obtained deposit,
which agrees with the data concerning the morphology
of the surface of the obtained deposit (Fig. 2b).
In the cyclic voltammograms that were registered in
the course of the process of deposition one can distin-
guish a pair of peaks at the potentials equal to 0.46 V
(anodic run) and 0.26 V (cathodic run). The peaks in
question may correspond to assorted redox transitions
experienced by molybdenum compounds. The area
under the cathodic peak for each cycle exceeds the area
under the peak during an anodic run. Such asymmetry
of the peaks testifies to predominance of the cathodic
process during the deposition of the Pt-MoOx film, in so
doing there also may occur both the insertion of molyb-
denum compounds into the composition of the deposit
and the accumulation of products that form during the
irreversible reduction of molybdate ions in the bulk
electrolyte. The insertion of molybdenum compounds
in the composition of the film that forms on the elec-
trode leads to the appearance of a peak at a potential of
0.46 V during the anodic run of a cyclic voltammogram
(the height of this peak increases with increasing time
of cycling, thus pointing out to the continuation of the
growth of the deposit in the course of the cycling).
In the cyclic voltammograms for composite material
Pt-åÓéx (Fig. 3) that were obtained in a 2 M solution
of sulfuric acid one can observe broad reversible peaks
in the region of potentials Ö = 0.05–0.29 V, which cor-
responds to the adsorption and desorption of hydrogen
on platinum, as well as some responses that are charac-
teristic of the formation of a layer of chemisorbed oxy-
gen (Ö = 0.85–1.1 V) and the process of its desorption
No. 7 2007
778 KUZNETSOV et al.

cps
Pt
(a)
15

Mo
10

C
Mo
5 Pt
Mo Pt Pt
Pt
Pt Pt
O Mo Pt Pt Mo
0
0 5 10 15 Energy, keV

(b)

~5 µm

Fig. 2. (a) Local x-ray diffraction spectrum for the surface of a Pt-MoOx electrode at point 1 and (b) morphology of the surface of
a Pt-MoOx electrode under 500x magnification.

(Ö = 1.1–0.7 V). In contradistinction to a cyclic volta-
mmogram for platinum, one can notice also the appear-
ance of pairs of peaks at a potential of 0.44–0.46 V in
the anodic run and at a potential of 0.3 V in the cathodic
run, which are apparently connected with processes of
reversible recharging of molybdenum compounds. The
maximum of the anodic peak shifts into the region of
more positive potentials following an increase in the
potential scan rate. A similar property was observed in
the case of a film of molybdenum oxide as well [8]. It
seems that the peak that is observed in the anodic run of
a cyclic voltammogram at a potential of 0.44–0.46 V is
identical to a similar peak that is observed in the curves
that were obtained for the process of deposition of the
film under investigation (Fig. 1).
To estimate the degree of reversibility of redox
transformations with the participation of molybdenum-
containing species, we estimated the charge that was
spent for these reactions at different values of the poten-
tial scan rate. The estimation was conducted on the
basis of the area under a curve, with a correction made
for the current at a potential of 0.7–0.8 V (the minimum
value of the current in the anodic run, which is weakly
dependent on the electrode potential and which is prob-
ably close to the current of the “double-layer” region on
pure platinum). It was discovered that the charge that
corresponds to the oxidation of molybdenum com-
pounds in the anodic run depends on the potential scan
rate and decreases somewhat, specifically, from
0.033 C at the potential scan rate equal to 20 mV s–1 to

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 43 No. 7 2007

 ELECTROCHEMICAL PROPERTIES OF COMPOSITE MATERIALS 779

I, mA
20 (a)

I
10 3
2

0 1
0.3 0.6 0.9 1.2
E, V

–10
Q, C
0.04

0.02
–20
0 40 80 120
v, mV s–1
I, mA
(b)
8 3
2

4 1

0
0.7 0.9 1.1
E, V
–4

Fig. 3. Cyclic voltammograms for a Pt-MoOx electrode obtained in a 2 M solution of sulfuric acid (a) at the following values of the
potential scan rate: (1) 20, (2) 50, and (3) 100 mV s–1 and (b) area I, enlarged; the insert presents the dependence of the area under
the peak corresponding to the reduction of molybdenum compounds on the potential scan rate.

0.025 C at the potential scan rate of 100 mV s–1 (Fig. 3,
insert). This effect may be explained by the oxidation of
some molybdenum-containing species with a relatively
low rate and, correspondingly, by the incompleteness of
the transformation of the film at larger values of the
potential scan rate. On the basis of the gravimetry data
and the determination of the chemical composition of
the deposit and the charge, there was given an estimate
of the number of electrons that correspond to a redox
transformation of a single molybdenum atom. It
amounted to 0.27 at the potential scan rate equal to
20 mV s–1.
The aggregate of peaks in the cathodic run of a
cyclic voltammogram that occur at potentials of 0.05–
0.6 V correspond to the process of formation of
adsorbed hydrogen atoms Hads at the surface of plati-
num and also to redox transformations experienced by
molybdenum-containing species. The peaks that corre-
spond to the hydrogen desorption and the oxidation of
molybdenum compounds are separated in the anodic
run. It is of interest to mention that the sum of areas cor-
responding to the hydrogen region (Ö = 0.05–0.29 V)
and the process of oxidation of molybdenum-contain-
ing species (Ö = 0.29–0.57 V) is smaller than the
summed area of peaks in the cathodic run of a cyclic
voltammogram at Ö = 0.05–0.6 V. A possible reason for
this phenomenon is the irreversible reduction of molyb-
denum-containing species, which is observed in that
potential region.
The hydrogen region for the êt-åÓOx electrode is
pronounced less clearly than for pure platinum. A sim-
ilar change in the run of a cyclic voltammogram was
also observed for platinum that was co-deposited with
isopolytungstate [9]. The said circumstance may be
connected with that, in the region of potentials corre-
sponding to the hydrogen region, there occur transfor-
mations of molybdenum compounds that lead to its
deeper reduction. Nor can we rule out that the presence

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 43 No. 7 2007

780 KUZNETSOV et al.

I, mA
6
(a)

2 I
3 1

0
0.3 0.6 0.9 1.2
E, V

–3

–6 I, mA
3
(b)

2
1 2
1

0
0.7 0.9 1.1
E, V
–1

–2

Fig. 4. Cyclic voltammograms (a) obtained in a 2 M solution of sulfuric acid as follows: (1) on disperse platinum deposited onto
the surface of glassy carbon (normalized) and (2) on composite material Pt-MoOx deposited onto the surface of glassy carbon and
(b) area I, enlarged; v = 20 mV s–1.

of a molybdenum-containing phase on the surface of a
platinum deposit may diminish the amount of adsorbed
hydrogen atoms that is obtained in the hydrogen region.
A correct estimation of the share of the contribution,
which redox transformations experienced by molybde-
num make into the charge measured in the hydrogen
region, may be performed when comparing cyclic vol-
tammograms for deposits of platinum and Pt-MoOx that
possess an identical area of the true surface. In order to
perform a comparison of experimental voltammograms
as calculated per true surface of a deposit, there was
performed their normalization. In so doing, it was pre-
sumed at this stage that the current of the charging of
the electric double layer, which is fixed in the double-
layer segment of a cyclic voltammogram, is propor-
tional to the true surface area of an electrode. The
assumption we used is not too rough, at the very least
for the materials under investigation, in the composi-
tion of which platinum is predominant, and the contri-
bution of oxy molybdates to the current that flows out-
side the region of their recharging is unlikely to be
great. Indeed, the charge that corresponds to the hydro-
gen region for a composite coating in the anodic run of
a cyclic voltammogram is commensurate with the
charge for a deposit of pure platinum (Fig. 4).
The hydrogen region and the peak corresponding to
the reduction of molybdenum compounds are practi-
cally not separated in the cathodic run of a voltammo-
gram, and the obtained charge is affected by the reduc-
tion of molybdenum-containing species.
On the basis of the data concerning the charge that
is fixed in the hydrogen region of a cyclic voltammo-
gram for Pt-MoOx (anodic run) and the data of gravim-

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 43 No. 7 2007

 ELECTROCHEMICAL PROPERTIES OF COMPOSITE MATERIALS
i, mA cm–2
1.0
0.5
2 of [10].
1
1.0 0.5 0 CONCLUSIONS
E, V
Fig. 5. Quasi-stationary cathodic polarization curves
obtained for the oxygen reduction reaction in a 2 M solution
of sulfuric acid as follows: (1) on disperse platinum and (2)
composite material Pt-MoOx.
etry there was estimated the average size of platinum
particles in a deposit. The assessment, which was per-
formed under the assumption about a spherical shape of
particles, led to the size of particles of platinum equal
to 15.8 nm, which is quite realistic. Thus, the hydrogen
region (anodic run of a cyclic voltammogram) may to a
first approximation be used for evaluating the area of a
platinum deposit to within an accuracy of an order of
magnitude.
It should be noted that the peak that corresponds to
the reduction of chemisorbed oxygen is displaced by
0.07 V in the direction of more positive potentials as
compared with the peak that corresponds to pure plati-
num, which allows us to draw the conclusion about a
certain alleviation of the oxygen desorption from the
surface of an electrode material. Besides, the area of the
oxygen region is somewhat smaller than for pure plati-
num, which coincides with the data that were obtained
for Pt-WOx in [9].
In order to capable of comparing electrocatalytic
properties of electrode materials, we obtained cathodic
quasi-stationary polarization curves in a potentiostatic
regime (Fig. 5). Both the oxygen reduction reaction and
the slow reduction of molybdenum-containing species
that enter the composition of an electrode deposit may
make contributions to the measured value of the
cathodic current. However, as follows from cyclic vol-
tammograms, the redox transition of molybdenum
compounds begins at a potential of 0.55 V. Conse-
quently, values of cathodic currents that are fixed at
more positive values of potential are connected solely
with the process of reduction of molecular oxygen. Fol-
lowing the inclusion of molybdenum compounds into a
deposit, there is observed a shift of the wave that corre-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 43
781
sponds to the oxygen reduction in the direction of more
positive potentials (Fig. 5, curve 2; the potential that
corresponds to the beginning of the oxygen reduction
for platinum is equal to 0.76 V and that for Pt-MoOx is
equal to 0.91 V). This result points to catalytic proper-
ties of the composite material Pt-MoOx and cannot be
related to the difference in the true surface areas of
deposits, which are commensurate with to within an
order of magnitude. The limiting current that is fixed in
a quasi-stationary polarization curve depends on stir-
ring, i.e. it has a diffusion nature. The data we obtained
on the catalytic activity of synthesized electrode mate-
rials correlate with the results reported by the authors
(1) A deposit of Pt-MoOx was obtained on the sur-
face of a glassy-carbon electrode by an electrochemical
technique. The inclusion of molybdenum into the
deposit was judged upon from the secondary-electron
emission spectra.
(2) In a cyclic voltammogram for the deposit
obtained in a 2 M solution of sulfuric acid one can dis-
tinguish a pair of peaks that are connected with redox
transitions of molybdenum compounds. The number of
electrons that correspond to a redox transformation of a
molybdenum atom was calculated. It amounted to
0.27 electrons per molybdenum atom.
(3) It was demonstrated that the composite coating
Pt-MoOx possesses catalytic activity in the oxygen
reduction reaction. One can manage to observe the oxy-
gen reduction reaction on the composite material
Pt-åÓOx under study as early as at the potential of
0.91 V.
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