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 Keywords Galvanostatic electrodeposition  Platinum 
morphology, average size, and the electrochemical be- Vulcan XC-72  Electrocatalyst  ORR
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- 1 Introduction
trode coated with Vulcan XC-72 carbon powder. Cyclic
voltammetry and linear sweep voltammetry were used to The morphology of coated metal on a support is a sig-
determine the electrochemically active surface area (ESA) nificant factor that affects the activity and efficiency of the
and oxygen reduction reaction (ORR) activity of the pre- material prepared. The possibilities of controlling the
pared Pt/C materials, respectively. XRD and scanning morphology of metallic deposits have been previously
electron microscopy were used to study the influence of the studied with the aim of providing high-quality metallic
electrodeposition methods applied on the morphology of coatings (or continuous films). For the application of such
platinum particles deposited in water and mixed water– coatings, the supports used were usually metallic and non-
ethylene glycol solutions. The average size of Pt crystal- metallic materials which are characterized by very high
lites was in the range of ca. 6–10 nm, and the average size degree of adhesion for the coating of the metallic deposits
of deposited Pt particles was in the range of ca. [1]. Recently, significant interest has been raised in utiliz-
30–150 nm. It was found that the presence of ethylene ing electrodeposition for the formation of an array of metal
glycol in the electrolyte solution increased the overpoten- nanoparticles on the surface of different carbon supports [2,
tial of electrodeposition and it also strongly affected the 3]. The reason for this particular interest is to obtain M/C
morphology of Pt deposits when constant current elec- materials with maximum electrochemically active surface
trodeposition was employed. Moreover, it was shown that area, which requires formation of the electrodeposits not
pulse current electrodeposition is a more effective method only on the surface but also in the pores of the carbon
compared to constant current electrodeposition method for support.
the preparation of the Pt/Vulcan electrode with high ESA Nano- and micro-structured metal–carbon materials are
of Pt and enhanced catalytic activity toward ORR. The used as catalysts in various chemical and electrochemical
results obtained concerning the morphology and the spatial reactions [4–6]. In particular, Pt/C nano-structured mate-
distribution of platinum particles electrodeposited on the rials, due to their superior catalysis for low-temperature
surface of carbon support at different conditions demon- hydrogen and methanol fuel cell reactions, have attracted
strate new possibilities to improve synthesis of Pt/C by much interest worldwide to researchers and manufacturers
electrodeposition methods. [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-
& V. E. Guterman
alyzes the oxygen reduction reaction at the cathode and
[email protected]
fuel (e.g., hydrogen, methanol, ethanol, etc.) oxidation at
1
Southern Federal University, Rostov-on-Don, Russia the anode. However, due to high cost and shortage of the

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metal, significant efforts have been made to lower down current, potential, time, and the use of organic molecules
the content of platinum through increasing the catalytic [23, 27–29]. Different organic molecules can be used to
efficiency of Pt catalysts. One of the effective ways to control the qualities of particles prepared. For instance, in
decrease the amount of Pt catalysts but still keep their high previous works [30, 31], it was shown that dimethyl sul-
catalytic activities is to enlarge the effective surface area of foxide (DMSO) in the wet chemical synthesis of platinum
Pt by diminishing the size of the catalyst particles [10–14]. nanoparticles on carbon support strongly affects their mi-
It is known [2, 9, 15] that the support material can crostructure. When the content of DMSO concentration
significantly influence the properties of prepared electro- increases in the solution, the average size of platinum
catalysts, for instance, the size of metal particles, their particles decreases and their size distribution also becomes
stability, size distribution of the particles, etc. It has been narrower.
found that the optimal dispersion pattern and Pt particle The influence of organic molecules such as citric acid,
size can be obtained using an appropriate preparative tartrate, poly(vinyl pyrrolidone), etc. has been also inves-
procedure on an ideal supporting material. The support tigated in the electrodeposition of different metals such as
should have the following structure and properties: (1) high Ag [32], Co [33], Pt and Pt–Ru [10, 34], Cu and Sn [35–
surface area and good electronic conductivity, (2) low 37], Zn [38]. According to the reports [32–38], the use of
combustive reactivity under both dry and humid air con- the organic molecules can enhance control of crystalliza-
ditions at low temperatures (100 °C or less), (3) good re- tion of the metal, kinetics of the metal deposition, surface
actant gas access to the platinum nanoparticles, (4) have morphology, electrochemically active surface area, size
adequate water handling capability, particularly at the and shape, the structural characteristics and dispersion of
cathode where water is generated, show good corrosion the deposits by limiting and preventing the formation of
resistance under fuel cell operating conditions (5) and also agglomerates of the metals.
easy-to-recover Pt in the used catalyst [15–17]. Platinum It should be noted that it is undesirable to use conven-
deposition on various types of carbon and carbon-based tionally used surface-active organic molecules in the
supports has been reported, such as glassy carbon [18, 19], electrodeposition of metals since it is difficult to remove
carbon nanotubes [20, 21], conducting polymers [18], them from the Pt/C materials and in addition, the organic
carbon black [22, 23], etc. Vulcan XC-72 carbon black is molecules can poison the catalyst and this may lead to a
the most widely used carbon support because of its good loss of effective catalytic active sites or a loss of electronic
compromise between electronic conductivity, durability, conductivity, resulting in performance loss during fuel cell
and high surface area [6, 24]. The anchoring of the Pt operation. Ethylene glycol (EG) is among the most at-
particles at the carbon microparticles not only increases the tractive organic solvents, which demonstrates some posi-
stability of the particles but also provides free electron tive effects during wet chemical synthesis of Pt/C materials
access to the particles. [39–42]. The obtained catalyst is usually easily cleaned
The simplest and traditional method to prepare carbon- from the EG by rinsing it thoroughly with pure water. But
supported Pt electrocatalyst is to impregnate the support even when this has not happened, EG can be readily re-
with a platinum precursor; followed by reduction in hy- moved from the Pt/C materials by electrochemical oxida-
drogen at high temperature. However, this method requires tion or by oxidative heat treatment at low temperatures
a high amount of Pt to achieve good results. Besides, the without changing the properties of the prepared materials.
control of particle size and size distribution by this simplest Nanoparticles demonstrate inherent tendency to agglom-
method is rather limited [2, 7, 25]. Chemical reduction erate into bigger particles to reduce their high surface en-
method using reducing agents at lower temperature is also ergy. Based on Ming-Chi Tsai et al. [43], EG can be used
commonly used for preparation of the metallic supported to inhibit significant agglomeration of platinum nanopar-
catalysts [8, 9, 26]. However, the impurities are easily in- ticles during the process of electrodeposition. However,
corporated from the bath solutions and this may deteriorate there are limited works which have studied the effects of
the catalytic activity of platinum catalysts. Furthermore, ethylene glycol solvent on the electrochemically active
chemical reduction method is a complex process consisting surface area, size and surface morphology in the elec-
of several subsequent stages which can substantially affect trodeposition of Pt nanoparticles, and the performance of
the ultimate outcome. the prepared materials toward oxygen reduction reactions
Recently, the preparation of nano-structured catalyst by [34, 43].
electrochemical reduction technique has attracted consid- In the present study, the electrochemical techniques
erable attention due to advantages such as a simple pro- such as galvanostatic electrodeposition at constant current
cedure for deposition, enhanced thermal stability, low-cost and multiple cycles of galvanostatic pulsed current were
operation which allows high purity of deposits, and easy applied to prepare carbon-supported platinum catalyst from
control of the nanoparticle formation by the selection of a dilute solution of 5 mM H2PtCl6 ? 1MH2SO4 in the

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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

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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.

Fig. 1 Schematic representation of the parameters of pulse 2.3.2 Electrochemical measurements

electrodeposition
After the electrodeposition process, the catalyzed electrode
was rinsed thoroughly with bi-distilled water and the ob-
30 mA, the 2h range of 30°–90° for a representative sample tained catalyst electrode was examined in a freshly pre-
(Fig. 2a) and the 2h narrow range of 37–50° (Fig. 2b) for pared 100 mL of 0.1 M HClO4 solution. Prior to each CV
routine calculations, step size—0.02°, scan rate—0.5°/s. experiment, pure bubbling argon was passed through the
Peltier-cooled Si(Li) solid-state detector tuned for high electrolyte solution for 30 min to remove oxygen dissolved
count rate removes K-b and fluorescence radiation. Thermo in the solution. This atmosphere was maintained by a flow
ScientificTM WinXRDTM software running under Windows of argon gas in the solution during the experiment. Then,
XPTM was used for data collection. the electrode surface was scanned voltammetrically with
A zero-background holder and polymer tissues were 100 cycles in the range between -0.04 and 1.2 V versus
used in order to mount the samples. The catalyst layer SHE at a scan rate of 200 mV s-1 in order to clean the
prepared by electrodeposition was scratched down from the electrode from residues hidden in the porous electrode and
surface of glassy carbon RDE and transferred onto a obtain stable measurements of cyclic voltammograms.
polymer tissue; afterwards it was fixed at the zero-back- Then, cyclic voltammograms (2 cycles) with a scan rate of
ground (Si wafer) holder. A number of measurements for 20 mV s-1 were used to determine the ESA of the Pt
the polymer tissue samples, the carbon substrates (on the catalysts. The ESA was estimated by measuring the charge
polymer tissue) had been performed in order to determine associated with the hydrogen adsorption/desorption at the
their contribution to the main Pt reflections. Two calibra- potential region about -0.03 to 0.3 V.
tion standards (polycrystalline SiO2, a-quartz and corun- The measurement of the ESA of the Pt catalyst is an
dum, Al2O3) were measured as well for more accurate important parameter for the assessment of possible activity
calculations of (FWHM) during the data analysis. The of catalysts by comparing the ESA value. The charge in-
crystallite size for all the prepared catalysts is calculated tegration feature in the pine software plots of I versus t can
from the width of (111) diffraction peak using Scherer be integrated to calculate the charge under the curve after
equation (Eq. 1). double-layer correction. Thus, the ESA is calculated using

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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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.
Fig. 3 Chronopotentiometric curves for electrodeposition of Pt on
Vulcan XC-72 electrode by a constant current b multiple pulse Q ¼ Ip ttot ðton =ðton þ toff ÞÞ: ð3Þ
current galvanostatic electrodeposition methods from electrolyte
solution of 5 mM H2PtCl6, H2SO4 in water–EG and water media Figure 2 shows the XRD patterns of electrodeposited Pt
by constant current and multiple cycles of galvanostatic
Eq. 2 from the mean charge required for both hydrogen pulsed current from water and mixed water–EG solutions.
adsorption/desorption for the platinum electrocatalyst The prepared Pt/C materials showed five different charac-
measured by cyclic voltammetry [30] and is presented in teristic diffraction peaks at 2h values about 40°, 46°, 68°,
Tables 1 and 2. 81, and 87° corresponding to the planes (111), (200), (220),
(311), and (222), respectively (Fig. 2a). The broad
Q
ESA ¼ ; ð2Þ diffraction peaks of Pt in the prepared Pt/C materials are
m  210 indicative of the nanosized Pt. The average crystallite size
where Q is the average of charges exchanged during hy- of Vulcan-supported Pt was calculated from the broadening
drogen adsorption and desorption (lC) which is obtained of the (111) diffraction peak using Scherrer equation
after double-layer correction; m is the mass of platinum (Table 2). As shown in table, the average crystallite size of
loading (lg); and the numerical value 210 (lC cm-2) Pt obtained by the pulse method is smaller compared to that
represents the charge required to oxidize a monolayer of obtained by constant current electrodeposition. This can
hydrogen on Pt surface. also be observed from Fig. 2b, there is an increase of the
Linear sweep voltammograms (LSVs) at a rotating disk full width at half maximum (FWHM) when the method of
electrode (RDE) were recorded to evaluate the electrocat- electrodeposition is changed from constant current to pulse
alytic activity of the prepared Pt/C electrocatalysts for method, indicating the decrease of Pt crystallite size.
oxygen reduction reactions (ORR). In this case, after the Using EG in both methods resulted in a decrease in the
ESA measurements, a 0.1 M HClO4 electrolyte solution average size of the crystallites. The smallest size of Pt
was saturated with oxygen at atmospheric pressure for crystals is 6.4 nm obtained by pulse method in mixed
50 min. Then, while continuing to purge oxygen gas, the water–EG solution followed by 7.5, 8.5, and 9.9 nm by
potential of the working electrode was changed from 1.196 pulse method in water, constant current in water–EG, and
to 0.020 V with a sweep rate of 20 mVs-1 at different disk water solutions of the electrolyte, respectively.
electrode rotation rates (400, 600, 1000, 1400, 1800, and As stated previously, the ESA values were determined
2400 rpm). To compare the activity of the catalysts, mea- by measuring the average quantity of electricity consumed
sured currents were normalized by the mass of platinum by the adsorption and desorption of hydrogen. The ex-
(Ag-1 of Pt) and/or by the ESA of the catalyst (mA cm-2 perimental data from Table 2 indicate that there is no
of Pt). considerable difference in the ESAs of Pt deposits obtained

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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. Chen et al. [46] observed similar effects.
electrodeposition is employed. As can be seen from The authors used glycerol as an organic additive in the
Table 1, the electrochemically active surface areas appear electrodeposition of Pt on carbon nanotubes directly grown
to be more or less equal (ca. 20 m2 g-1) except in the case on carbon cloth and proposed that increasing the viscosity
of pulse method in water medium by which the highest of the electrolyte solution as a method for controlling the
ESA of Pt particles (ca. 37 m2 g-1) was obtained. This can size of the Pt deposits.
be rationalized by considering the corresponding results of The curves obtained in water–EG medium (Fig. 3) are at
SEM micrographs (Figs. 4c, 5c) of platinum particles. That lower negative overpotential compared to that in water
is, the smallest Pt particle size, highest coverage, and en- medium under both constant current and pulse electrode-
hanced dispersion of the particles were obtained in this position methods (compare dashed and solid lines in
case thereby resulting in the highest ESA value. Fig. 3). Once ethylene glycol in the electrolyte solution is
Figure 3a, b exhibits the electrodeposition of Pt onto adsorbed on the electrode surface, it may block the elec-
Vulcan XC-72 electrode by constant and pulsed current trode surface and prevent charge transfer between Pt ions
galvanostatic electrodeposition method, respectively. The and the electrode thus hindering electrodeposition of Pt
decaying part and the minimum point of the curves in particles. This may be the reason for the observed slight
Fig. 3a show that the process of nucleation takes place at a shift toward more negative overpotential in the solution
faster rate in water than in EG solution. The addition of EG containing EG compared to that in the water solution of the
into the electrolyte solution may result in a chemical in- electrolyte as shown in Fig. 3a, b. Moreover, the shift in
teraction of the active ions with EG and/or increased vis- the overpotential may be caused by different factors such
cosity of the solution which thereby resulting in a slow as a change in the structure of solvation shell of ions, in-
diffusion rate of Pt-containing ions. This in turn may lead creased viscosity of the solution, a contribution from an
to minimize the rate of growth of Pt clusters during increased ohmic potential drop, as a result of an increase in

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Fig. 5 High-resolution SEM micrographs. The same materials as in Fig. 4

the resistance of the electrolyte solution upon using the two (4) Showed a transition of morphology from spherical to
component (EG–water) solution, etc. petal-shaped Pt deposits. The morphology of the
SEM as shown in Figs. 4 and 5 with different magnifi- electrodeposited particles went through a change
cations is used to characterize the morphology and struc- from spherical to petal-like shape merely for the
ture of the obtained Pt deposits. Figure 4a, b exhibits the presence of EG in the electrolyte solution, keeping
SEM micrographs of Pt particles deposited by constant all other parameters the same.
current galvanostatic electrodeposition in water and in
Thus, the addition of EG into the electrolyte solution is
water–EG media, respectively. Well dispersed, higher
promising from the point of view of controlling the particle
coverage, 2–3 times smaller size, and highly developed
size and morphology of Pt particles using constant current
petal-shaped Pt particles were observed on the carbon
electrodeposition. Unfortunately, change in shape, de-
support when the water–EG medium is used in contrast to
creasing the size, and improving the uniformity of the
those in water medium. In water medium (Fig. 4a), the
distribution of platinum particles in the case of the water–
particles are generally spherical in shape with rather large
ethylene glycol solution did not lead to a considerable in-
diameter of 120–180 nm.
crease in ESA. Apparently, spherical particles in the case
Thus, the presence of EG in the electrolyte solution
of the aqueous electrolyte (Fig. 5a), composed of platinum
during the electrodeposition process resulted in the fol-
nanosized particles of 6–10 nm are characterized by high
lowing effects under constant current electrodeposition:
surface roughness and hence have ESA value comparable
(1) Enhanced dispersion of the Pt deposits on Vulcan with that of Pt particles obtained from water–EG solution
XC-72 carbon support; (compare the ESA values in water and water–EG media
(2) Reduction in the size of Pt crystallites; and their corresponding SEM micrographs in Fig. 5a, b
(3) Prevented the particles from significant agglom- under constant current electrodeposition).
eration as was also noted by Tsai Ming-Chi et al. Figure 5c, d presents SEM micrographs of Pt deposits
[43]; by galvanostatic pulse electrodeposition from the water and

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

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

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morphology of Pt particles and in improving particle dis- 6. Paulus UA, Schmidt TJ, Gasteiger HA, Behm RJ (2001) Oxygen
persion under constant current electrodeposition. SEM reduction on a high-surface area Pt/Vulcan carbon catalyst: a
thin-film rotating ring-disk electrode study. J Electroanal Chem
analysis of Pt particles obtained by constant current elec- 495:134–145. doi:10.1016/S0022-0728(00)00407-1
trodeposition revealed that the EG strongly affects the 7. Shen PK, Tian Z (2004) Performance of highly dispersed Pt/C
morphology of the particles, which can possibly be at- catalysts for low temperature fuel cells. Electrochim Acta
tributed to the adsorption of EG on the electrode surface. 49:3107–3111. doi:10.1016/j.electacta.2004.02.024
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smaller particles. However, the presence of EG molecules cells. J Phys Chem 107:6292–6299. doi:10.1021/jp022505c
in the electrolyte solution did not considerably affect the 9. Liang Y, Zhang H, Yi B, Zhang Z, Tan Z (2005) Preparation and
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ESA of Pt particles. The particles have nearly the same Ru catalysts for proton exchange membrane fuel cells. Carbon
ESA either in water or water–EG solutions in the case of 43:3144–3152
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was obtained when pulse electrodeposition method was trocatalytic activity of Pt-nanostructures prepared by electrode-
position using poly(vinyl pyrrolidone) as a shape-control agent.
used in water solution of the electrolyte. Nevertheless, the Electrochim Acta 83:383–386
materials obtained in the presence of EG (materials CE and 11. Ho VTT, Nguyen NG, Pan C, Cheng J, Rick J, Su W, Lee J, Sheu
PE) have higher mass activity and significantly increased H, Hwang B (2012) Advanced nanoelectrocatalyst for methanol
specific activity when we compare these catalysts with that oxidation and oxygen reduction reaction, fabricated as one-di-
mensional Pt nanowires on nanostructured robust Ti0.7Ru0.3O2
obtained in water solution of the electrolyte. This can be support. Nano Energy 1:687–695. doi:10.1016/j.nanoen.2012.07.
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This work will need to be further optimized to gain a of carbon-supported platinum catalysts for the electrooxidation of
methanol. J Electroanal Chem 382:65–72. doi:10.1016/0022-
better insight into the mechanisms of ethylene glycol effect 0728(94)03648-M
in the electrodeposition process of Pt nanoparticles. Be- 13. Gasteiger HA, Kocha SS, Bhaskar S, Wagner FT (2005) Activity
sides, it will be necessary to develop methods of benchmarks and requirements for Pt, Pt-alloy, a reduction cata-
nanoparticles deposition on the surface and deeper in the lysts for PEMFCs. Appl Catal B Environ. doi:10.1016/j.apcatb.
2004.06.021
carbon layer for the preparation of Pt/C materials that can 14. Guo S, Wang E (2011) Noble metal nanomaterials controllable
possibly be applied as electrocatalysts in low-temperature synthesis and application in fuel cells and analytical sensors.
hydrogen and methanol fuel cells. Our next study will be Nano Today 6:240–264. doi:10.1016/j.nantod.2011.04.007
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Acknowledgments This work was financially supported by the 16. Ralph TR, Hogarth MP (2002) Catalysis for low temperature fuel
Grant of Southern Federal University: No 213.01-2014/005VG. cells, vol 46. Johnson Matthey Public Limited Company, Hatton
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