J Appl Electrochem
DOI 10.1007/s10800-015-0820-5
RESEARCH ARTICLE
Effect of ethylene glycol on electrochemical and morphological
features of platinum electrodeposits from chloroplatinic acid
Weldegebriel Yohannes1 • S. V. Belenov1 • V. E. Guterman1 • L. M. Skibina1
V. A. Volotchaev1 • N. V. Lyanguzov1
Received: 20 December 2014 / Accepted: 16 March 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract The aim of this work was to investigate the
morphology, average size, and the electrochemical be-
havior of platinum nanoparticles electrodeposited from
water and mixed water–ethylene glycol solutions of the
electrolyte of H2PtCl6 and H2SO4 at a rotating disk elec-
trode coated with Vulcan XC-72 carbon powder. Cyclic
voltammetry and linear sweep voltammetry were used to
determine the electrochemically active surface area (ESA)
and oxygen reduction reaction (ORR) activity of the pre-
pared Pt/C materials, respectively. XRD and scanning
electron microscopy were used to study the influence of the
electrodeposition methods applied on the morphology of
platinum particles deposited in water and mixed water–
ethylene glycol solutions. The average size of Pt crystal-
lites was in the range of ca. 6–10 nm, and the average size
of deposited Pt particles was in the range of ca.
30–150 nm. It was found that the presence of ethylene
glycol in the electrolyte solution increased the overpoten-
tial of electrodeposition and it also strongly affected the
morphology of Pt deposits when constant current elec-
trodeposition was employed. Moreover, it was shown that
pulse current electrodeposition is a more effective method
compared to constant current electrodeposition method for
the preparation of the Pt/Vulcan electrode with high ESA
of Pt and enhanced catalytic activity toward ORR. The
results obtained concerning the morphology and the spatial
distribution of platinum particles electrodeposited on the
surface of carbon support at different conditions demon-
strate new possibilities to improve synthesis of Pt/C by
electrodeposition methods.
& V. E. Guterman
gut57@mail.ru
1
Southern Federal University, Rostov-on-Don, Russia
•
Keywords Galvanostatic electrodeposition  Platinum 
Vulcan XC-72  Electrocatalyst  ORR
1 Introduction
The morphology of coated metal on a support is a sig-
nificant factor that affects the activity and efficiency of the
material prepared. The possibilities of controlling the
morphology of metallic deposits have been previously
studied with the aim of providing high-quality metallic
coatings (or continuous films). For the application of such
coatings, the supports used were usually metallic and non-
metallic materials which are characterized by very high
degree of adhesion for the coating of the metallic deposits
[1]. Recently, significant interest has been raised in utiliz-
ing electrodeposition for the formation of an array of metal
nanoparticles on the surface of different carbon supports [2,
3]. The reason for this particular interest is to obtain M/C
materials with maximum electrochemically active surface
area, which requires formation of the electrodeposits not
only on the surface but also in the pores of the carbon
support.
Nano- and micro-structured metal–carbon materials are
used as catalysts in various chemical and electrochemical
reactions [4–6]. In particular, Pt/C nano-structured mate-
rials, due to their superior catalysis for low-temperature
hydrogen and methanol fuel cell reactions, have attracted
much interest worldwide to researchers and manufacturers
[7–9]. Among metals, Pt is so far the best and most
preferable chemically stable and active electrocatalyst in
fuel cells. During operations of fuel cells, platinum cat-
alyzes the oxygen reduction reaction at the cathode and
fuel (e.g., hydrogen, methanol, ethanol, etc.) oxidation at
the anode. However, due to high cost and shortage of the
123

metal, significant efforts have been made to lower down
the content of platinum through increasing the catalytic
efficiency of Pt catalysts. One of the effective ways to
decrease the amount of Pt catalysts but still keep their high
catalytic activities is to enlarge the effective surface area of
Pt by diminishing the size of the catalyst particles [10–14].
It is known [2, 9, 15] that the support material can
significantly influence the properties of prepared electro-
catalysts, for instance, the size of metal particles, their
stability, size distribution of the particles, etc. It has been
found that the optimal dispersion pattern and Pt particle
size can be obtained using an appropriate preparative
procedure on an ideal supporting material. The support
should have the following structure and properties: (1) high
surface area and good electronic conductivity, (2) low
combustive reactivity under both dry and humid air con-
ditions at low temperatures (100 °C or less), (3) good re-
actant gas access to the platinum nanoparticles, (4) have
adequate water handling capability, particularly at the
cathode where water is generated, show good corrosion
resistance under fuel cell operating conditions (5) and also
easy-to-recover Pt in the used catalyst [15–17]. Platinum
deposition on various types of carbon and carbon-based
supports has been reported, such as glassy carbon [18, 19],
carbon nanotubes [20, 21], conducting polymers [18],
carbon black [22, 23], etc. Vulcan XC-72 carbon black is
the most widely used carbon support because of its good
compromise between electronic conductivity, durability,
and high surface area [6, 24]. The anchoring of the Pt
particles at the carbon microparticles not only increases the
stability of the particles but also provides free electron
access to the particles.
The simplest and traditional method to prepare carbon-
supported Pt electrocatalyst is to impregnate the support
with a platinum precursor; followed by reduction in hy-
drogen at high temperature. However, this method requires
a high amount of Pt to achieve good results. Besides, the
control of particle size and size distribution by this simplest
method is rather limited [2, 7, 25]. Chemical reduction
method using reducing agents at lower temperature is also
commonly used for preparation of the metallic supported
catalysts [8, 9, 26]. However, the impurities are easily in-
corporated from the bath solutions and this may deteriorate
the catalytic activity of platinum catalysts. Furthermore,
chemical reduction method is a complex process consisting
of several subsequent stages which can substantially affect
the ultimate outcome.
Recently, the preparation of nano-structured catalyst by
electrochemical reduction technique has attracted consid-
erable attention due to advantages such as a simple pro-
cedure for deposition, enhanced thermal stability, low-cost
operation which allows high purity of deposits, and easy
control of the nanoparticle formation by the selection of
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J Appl Electrochem
current, potential, time, and the use of organic molecules
[23, 27–29]. Different organic molecules can be used to
control the qualities of particles prepared. For instance, in
previous works [30, 31], it was shown that dimethyl sul-
foxide (DMSO) in the wet chemical synthesis of platinum
nanoparticles on carbon support strongly affects their mi-
crostructure. When the content of DMSO concentration
increases in the solution, the average size of platinum
particles decreases and their size distribution also becomes
narrower.
The influence of organic molecules such as citric acid,
tartrate, poly(vinyl pyrrolidone), etc. has been also inves-
tigated in the electrodeposition of different metals such as
Ag [32], Co [33], Pt and Pt–Ru [10, 34], Cu and Sn [35–
37], Zn [38]. According to the reports [32–38], the use of
the organic molecules can enhance control of crystalliza-
tion of the metal, kinetics of the metal deposition, surface
morphology, electrochemically active surface area, size
and shape, the structural characteristics and dispersion of
the deposits by limiting and preventing the formation of
agglomerates of the metals.
It should be noted that it is undesirable to use conven-
tionally used surface-active organic molecules in the
electrodeposition of metals since it is difficult to remove
them from the Pt/C materials and in addition, the organic
molecules can poison the catalyst and this may lead to a
loss of effective catalytic active sites or a loss of electronic
conductivity, resulting in performance loss during fuel cell
operation. Ethylene glycol (EG) is among the most at-
tractive organic solvents, which demonstrates some posi-
tive effects during wet chemical synthesis of Pt/C materials
[39–42]. The obtained catalyst is usually easily cleaned
from the EG by rinsing it thoroughly with pure water. But
even when this has not happened, EG can be readily re-
moved from the Pt/C materials by electrochemical oxida-
tion or by oxidative heat treatment at low temperatures
without changing the properties of the prepared materials.
Nanoparticles demonstrate inherent tendency to agglom-
erate into bigger particles to reduce their high surface en-
ergy. Based on Ming-Chi Tsai et al. [43], EG can be used
to inhibit significant agglomeration of platinum nanopar-
ticles during the process of electrodeposition. However,
there are limited works which have studied the effects of
ethylene glycol solvent on the electrochemically active
surface area, size and surface morphology in the elec-
trodeposition of Pt nanoparticles, and the performance of
the prepared materials toward oxygen reduction reactions
[34, 43].
In the present study, the electrochemical techniques
such as galvanostatic electrodeposition at constant current
and multiple cycles of galvanostatic pulsed current were
applied to prepare carbon-supported platinum catalyst from
a dilute solution of 5 mM H2PtCl6 ? 1MH2SO4 in the
J Appl Electrochem

Table 1 Summary for deposition time (t), applied cathodic current 2.2 Electrochemical deposition of Pt
(I), Pt content in the catalyst (% wt), ESA of Pt particles. The quantity
of electricity is constant (ca. 21 mC) Electrochemical experiments were carried out in a three-
t (s) I (mA) x (Pt) (% wt) ESA (m2 g-1) electrode cell configuration at room temperature with a
Vulcan XC-72 carbon-Nafion-coated glassy carbon as
5 4.27 24 17.1
working electrode, a platinum wire and a saturated potas-
7.5 2.84 26 16.7
sium chloride silver chloride electrode as counter elec-
15 1.42 24 19.3
trode, and as reference electrode, respectively. All
20 1.07 29 14.2
potentials in this study, however, are reported with respect
30 0.71 23 8.2
to the potential of the standard hydrogen electrode (SHE).
75 0.28 22 4.4
Electrochemical measurements were performed with
AFCBP1 potentiostat and AFMSRE rotator (Pine Research
Instrumentation, Inc., USA). Electrodeposition was con-
presence and absence of ethylene glycol in the electrolyte ducted in 1 M H2SO4, 5 mM chloroplatinic acid (H2PtCl6)
solution. The average size of the particles, the ESA, and aqueous solution in the presence and absence of ethylene
morphology of the deposits in water and mixed water– glycol. Pt was electrodeposited by two different tech-
ethylene glycol media is compared by employing electro- niques: by a constant current and multiple cycles of pulsed
chemical, X-ray diffraction (XRD), and scanning electron galvanostatic electrodeposition techniques.
microscopy (SEM) techniques. Too large of a deposition current is not helpful to in-
crease platinum deposition because most of the current can
be consumed on hydrogen evolution. Thus, current values
2 Experimental were selected in such a way that the evolution of hydrogen
was less dominant. Prior to each electrodeposition ex-
2.1 Preparation of electrode periment, the electrode was immersed into the electrolyte
and waited for 20 min. Then, electrodeposition was con-
Carbon black Vulcan XC-72 (Cabot Corporation, with ducted using a rotating disk electrode at a speed of
surface area of 270 m2 g-1) was used as carbon support. A 1000 rpm in order to compensate the loss in mass transfer
homogeneous suspension was prepared by mixing 6 mg of due to the use of dilute solution of H2PtCl6 [44].
Vulcan XC-72 carbon, 900 lL of isopropanol, and 100 lL
0.5 % of Nafion and dispersing using an ultrasonicator for 2.3 Characterization of Pt/C
10 min. After dispersion, the mixture was mechanically
stirred for additional 10 min. Glassy carbon electrodes 2.3.1 Characterization of structure
(with geometric surface areas of 0.196 cm2) were polished
with emery paper and alumina slurry. The electrodes were The morphology and average size of the electrodeposited
cleaned with bi-distilled water and dried at room tem- Pt particles were studied using scanning electron mi-
perature. Then, 6 lL of the resulting suspension was croscopy (Zeiss Supra 25, acceleration voltage of 20 keV).
dropped onto a previously polished and cleaned surface of In order to analyze size, morphology, and distribution of
glassy carbon disk electrode by micropipette and dried at carbon-supported Pt particles on the surface of the elec-
room temperature. Then, in order to attach the Vulcan XC- trodes, the micrographs obtained were processed by com-
72 carbon particles to the surface of glassy carbon elec- puter, using image analysis software called ImageJ.
trode, 7 lL of Nafion solution (0.05 %) was pippeted onto The X-ray powder diffraction data were collected using
the electrode and dried at room temperature. This electrode ARL X’TRA instrument: Bragg–Brentano geometry, a
is henceforth called as Vulcan XC-72 electrode which will vertical theta-theta goniometer of 260 mm radius, CuKa
be subsequently used as a substrate for the catalyst. radiation (k1 = 1.54056Å); typical settings: 40 kV,

Table 2 The ESA, average size Electrodeposition method Solvent Sample ESA (m2 g-1) d (nm) SEM D (nm) XRD
of Pt deposits (d), average size
of Pt crystallites (D) with Constant current Water CW 19.3 150 9.9
deposition time of 15 s, and
Water–EG CE 20.2 50a 8.5
applied current of 1.42 mA
Pulse current Water PW 36.8 30 7.5
Water–EG PE 16.9 130 6.4
a
The particles are not spherical but petal-like particles with an average length of 50 nm and width of
20 nm

123

Fig. 1 Schematic representation of the parameters of pulse
electrodeposition
30 mA, the 2h range of 30°–90° for a representative sample
(Fig. 2a) and the 2h narrow range of 37–50° (Fig. 2b) for
routine calculations, step size—0.02°, scan rate—0.5°/s.
Peltier-cooled Si(Li) solid-state detector tuned for high
count rate removes K-b and fluorescence radiation. Thermo
ScientificTM WinXRDTM software running under Windows
XPTM was used for data collection.
A zero-background holder and polymer tissues were
used in order to mount the samples. The catalyst layer
prepared by electrodeposition was scratched down from the
surface of glassy carbon RDE and transferred onto a
polymer tissue; afterwards it was fixed at the zero-back-
ground (Si wafer) holder. A number of measurements for
the polymer tissue samples, the carbon substrates (on the
polymer tissue) had been performed in order to determine
their contribution to the main Pt reflections. Two calibra-
tion standards (polycrystalline SiO2, a-quartz and corun-
dum, Al2O3) were measured as well for more accurate
calculations of (FWHM) during the data analysis. The
crystallite size for all the prepared catalysts is calculated
from the width of (111) diffraction peak using Scherer
equation (Eq. 1).
Fig. 2 XRD patterns for Pt/
Vulcan XC 72 materials a over
a wide range of 2h (30–90°),
CW sample; b over a narrow
range of 2h (37–50°). Asterisk
indicates carbon substrate
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J Appl Electrochem
0:95xk
D¼ ; ð1Þ
b2h cos h
where D is the average crystallite size in (nm), k is the
wave length, b2h and h are the full width at half maximum
(FWHM) and a diffraction angle of (111) reflection in ra-
dians, respectively.
2.3.2 Electrochemical measurements
After the electrodeposition process, the catalyzed electrode
was rinsed thoroughly with bi-distilled water and the ob-
tained catalyst electrode was examined in a freshly pre-
pared 100 mL of 0.1 M HClO4 solution. Prior to each CV
experiment, pure bubbling argon was passed through the
electrolyte solution for 30 min to remove oxygen dissolved
in the solution. This atmosphere was maintained by a flow
of argon gas in the solution during the experiment. Then,
the electrode surface was scanned voltammetrically with
100 cycles in the range between -0.04 and 1.2 V versus
SHE at a scan rate of 200 mV s-1 in order to clean the
electrode from residues hidden in the porous electrode and
obtain stable measurements of cyclic voltammograms.
Then, cyclic voltammograms (2 cycles) with a scan rate of
20 mV s-1 were used to determine the ESA of the Pt
catalysts. The ESA was estimated by measuring the charge
associated with the hydrogen adsorption/desorption at the
potential region about -0.03 to 0.3 V.
The measurement of the ESA of the Pt catalyst is an
important parameter for the assessment of possible activity
of catalysts by comparing the ESA value. The charge in-
tegration feature in the pine software plots of I versus t can
be integrated to calculate the charge under the curve after
double-layer correction. Thus, the ESA is calculated using
J Appl Electrochem
Fig. 3 Chronopotentiometric curves for electrodeposition of Pt on
Vulcan XC-72 electrode by a constant current b multiple pulse
current galvanostatic electrodeposition methods from electrolyte
solution of 5 mM H2PtCl6, H2SO4 in water–EG and water media
Eq. 2 from the mean charge required for both hydrogen
adsorption/desorption for the platinum electrocatalyst
measured by cyclic voltammetry [30] and is presented in
Tables 1 and 2.
Q
ESA ¼ ; ð2Þ
m  210
where Q is the average of charges exchanged during hy-
drogen adsorption and desorption (lC) which is obtained
after double-layer correction; m is the mass of platinum
loading (lg); and the numerical value 210 (lC cm-2)
represents the charge required to oxidize a monolayer of
hydrogen on Pt surface.
Linear sweep voltammograms (LSVs) at a rotating disk
electrode (RDE) were recorded to evaluate the electrocat-
alytic activity of the prepared Pt/C electrocatalysts for
oxygen reduction reactions (ORR). In this case, after the
ESA measurements, a 0.1 M HClO4 electrolyte solution
was saturated with oxygen at atmospheric pressure for
50 min. Then, while continuing to purge oxygen gas, the
potential of the working electrode was changed from 1.196
to 0.020 V with a sweep rate of 20 mVs-1 at different disk
electrode rotation rates (400, 600, 1000, 1400, 1800, and
2400 rpm). To compare the activity of the catalysts, mea-
sured currents were normalized by the mass of platinum
(Ag-1 of Pt) and/or by the ESA of the catalyst (mA cm-2
of Pt).
3 Results and discussion
In our previous work [45], the current used for Pt elec-
trodeposition on the porous Vulcan XC72 electrode was
optimized to obtain improved ESA of deposited Pt in water
solution of the electrolyte and the current employed to
reach this optimum condition was found to be about
1.42 mA as shown in Table 1.
In the present work, Pt was electrodeposited by constant
current and by multiple cycles of galvanostatic pulse
electrodeposition. In each case, the total consumption of
electrical charge corresponds to about 21 mC. The results
for the electrodeposition of Pt are summarized in Table 2.
The parameters, Ip = 1.42 mA, ton = 0.5 s, toff = 1.0 s
and ttot = 45 s, and 30 pulses were applied during pulse
electrodeposition.
For pulse method, the average applied pulse current Ip
and the average electrodeposition charge Q can be related
by Eq. 3 [2], where ton is the pulse length and toff is the
time between two pulses and ttot is the total deposition
time. The scheme for pulse electrodeposition is shown in
Fig. 1.
Q ¼ Ip ttot ðton =ðton þ toff ÞÞ: ð3Þ
Figure 2 shows the XRD patterns of electrodeposited Pt
by constant current and multiple cycles of galvanostatic
pulsed current from water and mixed water–EG solutions.
The prepared Pt/C materials showed five different charac-
teristic diffraction peaks at 2h values about 40°, 46°, 68°,
81, and 87° corresponding to the planes (111), (200), (220),
(311), and (222), respectively (Fig. 2a). The broad
diffraction peaks of Pt in the prepared Pt/C materials are
indicative of the nanosized Pt. The average crystallite size
of Vulcan-supported Pt was calculated from the broadening
of the (111) diffraction peak using Scherrer equation
(Table 2). As shown in table, the average crystallite size of
Pt obtained by the pulse method is smaller compared to that
obtained by constant current electrodeposition. This can
also be observed from Fig. 2b, there is an increase of the
full width at half maximum (FWHM) when the method of
electrodeposition is changed from constant current to pulse
method, indicating the decrease of Pt crystallite size.
Using EG in both methods resulted in a decrease in the
average size of the crystallites. The smallest size of Pt
crystals is 6.4 nm obtained by pulse method in mixed
water–EG solution followed by 7.5, 8.5, and 9.9 nm by
pulse method in water, constant current in water–EG, and
water solutions of the electrolyte, respectively.
As stated previously, the ESA values were determined
by measuring the average quantity of electricity consumed
by the adsorption and desorption of hydrogen. The ex-
perimental data from Table 2 indicate that there is no
considerable difference in the ESAs of Pt deposits obtained
123

Fig. 4 SEM images of Pt particles obtained by galvanostatic electrodeposition using the techniques constant current: a water, b water–EG
media, and pulse current: c water d water–EG media, respectively
in water and water–EG media when constant current
electrodeposition is employed. As can be seen from
Table 1, the electrochemically active surface areas appear
to be more or less equal (ca. 20 m2 g-1) except in the case
of pulse method in water medium by which the highest
ESA of Pt particles (ca. 37 m2 g-1) was obtained. This can
be rationalized by considering the corresponding results of
SEM micrographs (Figs. 4c, 5c) of platinum particles. That
is, the smallest Pt particle size, highest coverage, and en-
hanced dispersion of the particles were obtained in this
case thereby resulting in the highest ESA value.
Figure 3a, b exhibits the electrodeposition of Pt onto
Vulcan XC-72 electrode by constant and pulsed current
galvanostatic electrodeposition method, respectively. The
decaying part and the minimum point of the curves in
Fig. 3a show that the process of nucleation takes place at a
faster rate in water than in EG solution. The addition of EG
into the electrolyte solution may result in a chemical in-
teraction of the active ions with EG and/or increased vis-
cosity of the solution which thereby resulting in a slow
diffusion rate of Pt-containing ions. This in turn may lead
to minimize the rate of growth of Pt clusters during
123
J Appl Electrochem
electrodeposition. Chen et al. [46] observed similar effects.
The authors used glycerol as an organic additive in the
electrodeposition of Pt on carbon nanotubes directly grown
on carbon cloth and proposed that increasing the viscosity
of the electrolyte solution as a method for controlling the
size of the Pt deposits.
The curves obtained in water–EG medium (Fig. 3) are at
lower negative overpotential compared to that in water
medium under both constant current and pulse electrode-
position methods (compare dashed and solid lines in
Fig. 3). Once ethylene glycol in the electrolyte solution is
adsorbed on the electrode surface, it may block the elec-
trode surface and prevent charge transfer between Pt ions
and the electrode thus hindering electrodeposition of Pt
particles. This may be the reason for the observed slight
shift toward more negative overpotential in the solution
containing EG compared to that in the water solution of the
electrolyte as shown in Fig. 3a, b. Moreover, the shift in
the overpotential may be caused by different factors such
as a change in the structure of solvation shell of ions, in-
creased viscosity of the solution, a contribution from an
increased ohmic potential drop, as a result of an increase in
J Appl Electrochem
Fig. 5 High-resolution SEM micrographs. The same materials as in Fig. 4
the resistance of the electrolyte solution upon using the two
component (EG–water) solution, etc.
SEM as shown in Figs. 4 and 5 with different magnifi-
cations is used to characterize the morphology and struc-
ture of the obtained Pt deposits. Figure 4a, b exhibits the
SEM micrographs of Pt particles deposited by constant
current galvanostatic electrodeposition in water and in
water–EG media, respectively. Well dispersed, higher
coverage, 2–3 times smaller size, and highly developed
petal-shaped Pt particles were observed on the carbon
support when the water–EG medium is used in contrast to
those in water medium. In water medium (Fig. 4a), the
particles are generally spherical in shape with rather large
diameter of 120–180 nm.
Thus, the presence of EG in the electrolyte solution
during the electrodeposition process resulted in the fol-
lowing effects under constant current electrodeposition:
(1) Enhanced dispersion of the Pt deposits on Vulcan
XC-72 carbon support;
(2) Reduction in the size of Pt crystallites;
(3) Prevented the particles from significant agglom-
eration as was also noted by Tsai Ming-Chi et al.
[43];
(4) Showed a transition of morphology from spherical to
petal-shaped Pt deposits. The morphology of the
electrodeposited particles went through a change
from spherical to petal-like shape merely for the
presence of EG in the electrolyte solution, keeping
all other parameters the same.
Thus, the addition of EG into the electrolyte solution is
promising from the point of view of controlling the particle
size and morphology of Pt particles using constant current
electrodeposition. Unfortunately, change in shape, de-
creasing the size, and improving the uniformity of the
distribution of platinum particles in the case of the water–
ethylene glycol solution did not lead to a considerable in-
crease in ESA. Apparently, spherical particles in the case
of the aqueous electrolyte (Fig. 5a), composed of platinum
nanosized particles of 6–10 nm are characterized by high
surface roughness and hence have ESA value comparable
with that of Pt particles obtained from water–EG solution
(compare the ESA values in water and water–EG media
and their corresponding SEM micrographs in Fig. 5a, b
under constant current electrodeposition).
Figure 5c, d presents SEM micrographs of Pt deposits
by galvanostatic pulse electrodeposition from the water and
123
 J Appl Electrochem

Fig. 6 SEM images of Pt particles deposited on the surface of Vulcan XC-72 support; a, a0 constant current in water solution b, b0 constant
current in water–EG solution c, c0 pulse method in water solution d, d0 pulse method in water–EG solution

water–EG solutions, respectively. Under this method, the
SEM revealed generally spherical, more uniformly dis-
tributed, and much higher coverage of Pt particles in
comparison with the particles obtained using constant
current electrodeposition. The use of either the water or
water–EG solution of the electrolyte under pulse elec-
trodeposition method and altering the method of elec-
trodeposition from constant current to pulse method in the
water solution did not change the shape of the particles.
That is, the shape remained more or less spherical (Fig. 5a,
c, d) but generally a decrease in particle size, a homoge-
nous particle distribution and enhanced nuclei density
(higher coverage) of Pt particles was observed on the
carbon support using pulse electrodeposition method
(Fig. 5c, d). In this method, the particles shown in Fig. 5c
obtained from water solution of the electrolyte are even

123
J Appl Electrochem

0 It is important to note that despite the highest ESA was

obtained for the material deposited from water solution by
pulse method (material PW), the linear sweep voltammetry
-10
measurements showed that the highest mass activity and
specific activity for oxygen reduction reaction (ORR) were
-20 characteristic for the material obtained in water–EG by
CW
I, A/g(Pt)

pulse method (PE) (Fig. 7; Table 3). The catalysts obtained

-30 using constant current in water–EG (CE) exhibit somewhat
CE lower activity compared to the material PE, but a little
higher activity compared to the catalyst PW. Moreover, it
-40
PW can be seen that significantly higher [from 3-fold (PW) up
to a 10-fold (PE)] enhancement in specific activity when
-50 PE compared to the material obtained by constant current in an
aqueous medium (CW) (Table 3). Thus, the highest
-60 specific activity is characteristic for the materials PE and
0.6 0.7 0.8 0.9 CE obtained in water–EG solutions. Consequently, the
addition of ethylene glycol affects positively to the elec-
E, V trochemical activity of Pt/C materials in the ORR, and the
Fig. 7 LSV curves for Pt/C catalysts. Electrolyte—0.1 M HClO4 preferred method of electrodeposition is pulse method.
saturated with O2 at room temperature, scan rate -20 mV s-1,
rotating speed—1000 rpm
4 Conclusions

Pt particles supported on a dispersed Vulcan XC-72 surface

smaller, well developed, more uniformly distributed, and in
higher quantity than that in water–EG medium. This indi-
cates that the EG may not have played a role in the inhi-
bition of nuclei formation and growth of platinum
nanoparticles in this case.
The images in Fig. 6a0 , b0 , c0 , d0 are obtained in the
BSE mode by which the contrast between Pt and carbon
can be significantly enhanced, enabling to see the Pt
particles clearly on surface of the carbon Vulcan XC-72
layer (compare Fig. 6 a, b, c, d with a0 , b0 , c0 , d0 ). It must
be emphasized that for all materials studied, the platinum
particles are located only on the surface of carbon sup-
port layer Vulcan XC-72 (Fig. 6), but not in the depth of
the porous carbon layer. This phenomenon may decrease
the efficiency of the electrodeposited Pt to be used as
electrocatalyst for low-temperature fuel cells and there-
fore requires further studies of conditions that allow
deeper deposition of Pt nanoparticles into the carbon
layers.
were successfully prepared by constant and pulsed current
galvanostatic electrodeposition techniques from dilute so-
lution of 5 mM H2PtCl6, 1MH2SO4 in water, and mixed
water–EG solvents. The developed surface area of Pt par-
ticles was from 17 to 37 m2 g-1. The average size of de-
posited particles was from 30 nm (water solution, pulse
current) to 150 nm (water solution, constant current).
Analysis of the obtained Pt/C by XRD leads to the con-
clusion that Pt particles consisted of small crystallites with
an average size from 6 to 10 nm. The SEM micrographs
revealed that the Pt deposits went through a transition from
spherical to a petal-like shape in the water–EG solution
when constant current galvanostatic electrodeposition was
used. In addition, the average particle size was consider-
ably decreased in water–EG. However, no change was
observed regarding the shape when a galvanostatic pulse
method was employed regardless of the type of media used.
This study shows that the addition of EG into the elec-
trolyte solution is helpful in controlling the size and

Table 3 Characteristics of Pt/C Sample ESA, m2 g-1 Pt Mass activity, jmass (Ag-1 of Pt) Specific activity, Jspec (Am-2 of Pt)
catalysts obtained by
electrodeposition Potential value, V Potential value, V

0.75 0.78 0.8 0.75 0.78 0.8

SW 19.3 1.7 1.2 1.0 0.09 0.06 0.05
SE 20.2 11.5 6.5 4.1 0.57 0.32 0.20
PW 36.8 10.0 6.0 3.9 0.27 0.16 0.10
PE 16.9 13.9 8.7 5.6 0.82 0.52 0.33

123

morphology of Pt particles and in improving particle dis-
persion under constant current electrodeposition. SEM
analysis of Pt particles obtained by constant current elec-
trodeposition revealed that the EG strongly affects the
morphology of the particles, which can possibly be at-
tributed to the adsorption of EG on the electrode surface.
The adsorption of EG may contribute to the effective in-
hibition of growth of Pt particles and hence forming
smaller particles. However, the presence of EG molecules
in the electrolyte solution did not considerably affect the
ESA of Pt particles. The particles have nearly the same
ESA either in water or water–EG solutions in the case of
constant current electrodeposition. The highest ESA of Pt
was obtained when pulse electrodeposition method was
used in water solution of the electrolyte. Nevertheless, the
materials obtained in the presence of EG (materials CE and
PE) have higher mass activity and significantly increased
specific activity when we compare these catalysts with that
obtained in water solution of the electrolyte. This can be
attributed to higher concentration of active sites on the
surfaces of the CE and PE catalysts.
This work will need to be further optimized to gain a
better insight into the mechanisms of ethylene glycol effect
in the electrodeposition process of Pt nanoparticles. Be-
sides, it will be necessary to develop methods of
nanoparticles deposition on the surface and deeper in the
carbon layer for the preparation of Pt/C materials that can
possibly be applied as electrocatalysts in low-temperature
hydrogen and methanol fuel cells. Our next study will be
devoted to the development of such methods.
Acknowledgments This work was financially supported by the
Grant of Southern Federal University: No 213.01-2014/005VG.
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