i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7

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High electroactivity performance in Pt/MWCNT

and PtNi/MWCNT electrocatalysts

Ana M. Valenzuela-Muñiz a,c, Gabriel Alonso-Nuñez b,

Mario Miki-Yoshida a, Gerardine G. Botte c, Ysmael Verde-Gómez d,*
a
Centro de Investigación en Materiales Avanzados S.C. and Laboratorio Nacional de Nanotecnologı́a,
Miguel de Cervantes 120, Chihuahua, Chih. 31109, Mexico
b
Universidad Nacional Autónoma de México, Centro de Nanociencias y Nanotecnologı́a, Ensenada,
B.C. 22860, Mexico
c
Center for Electrochemical Engineering Research, Chemical and Biomolecular Engineering Department,
Ohio University, 166 Stocker Center, Athens, OH 45701, USA
d
Instituto Tecnológico de Cancún, Av. Kabah Km 3, Cancún, Quintana Roo 77500, Mexico

article info abstract

Article history: This work presents the synthesis, characterization and electrochemical evaluation of
Received 15 September 2012 electrocatalysts for PEM fuel cells base on Pt and PteNi nanoparticles over multi-walled
Received in revised form carbon nanotubes (MWCNT). The MWCNT were synthesized by spray pyrolysis of
24 November 2012 toluene, using ferrocene and nickelocene as catalytic agents. The Pt nanoparticles were
Accepted 27 November 2012 deposited using the ultrasound assisted aqueous deposition method, followed by either
Available online 27 December 2012 thermal or chemical reduction. The materials were characterized by scanning and trans-
mission electron microscopy, as well as X-ray diffraction. The MWCNT exhibit lengths of
Keywords: 200 mm (using ferrocene) and 30 mm (using nickelocene) and diameters around 50e70 nm. Pt
Carbon nanotubes nanoparticles showed sizes between 4 and 8 nm. The electrochemical active area toward
PtNi/MWCNT the hydrogen oxidation reaction was evaluated by cyclic voltammetry (CV) in a standard
Electrocatalyst three electrodes cell. In addition to corroborate the electrochemical active area, CO strip-
Electrochemical surface area ping tests were done. From both, the CV and CO stripping analyses, it was found that the
CO stripping synthesized electrocatalysts exhibited an electrochemical activity higher (140e230 m2gr
1)
Fuel cells than 10%Pt/Vulcan (Etek).
Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction supports for electrocatalysts. Additionally, the MWCNT

The outstanding properties that multi-walled carbon nano-
tubes (MWCNT) possess, such as electron conduction, chem-
ical and thermal stability, corrosion tolerant, nanostructured
morphology, among others [1], allow them to have advantages
over other carbonaceous materials commonly used as
present the ability to allow metallic nanoparticles to be
homogeneously dispersed over the external walls, making
possible to decrease the metal loading.
The design of electrocatalysts for PEM fuel cells using
low loadings of Pt has been widely studied due to the direct
impact that the metal has on the fuel cell cost. MWCNT

* Corresponding author. Tel.: þ52 998 8807432x115; fax: þ52 998 8807433.
E-mail addresses: yverde@itcancun.edu.mx, ysmaelverde@yahoo.com (Y. Verde-Gómez).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.11.134
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7
have already been demonstrated to have a high efficiency
in terms of Pt particles dispersion as well as stability,
leading them in highly active electrocatalysts [2e4]. There
are a wide number of methodologies to obtain MWCNT.
Spray pyrolysis is one of the most commonly used; this
methodology represents advantages among others due to
its characteristics of using non-sophisticated equipments
as well as easy of scalability.
Commonly MWCNT are synthesized using precursors
base on iron [5] obtaining well aligned MWCNT as well as
high production yields. However, it is always necessary to
perform a cleaning process after the synthesis in order to
remove the residual iron particles that remain on the surface
which could weaken the stability of the catalyst. On the other
hand, other type of precursors or nucleation agents based on
different metals as cobalt [6] or nickel [7], have been used in
order to avoid the presence of iron. Nevertheless, these
precursors in most of the cases exhibited low production
yields. However, the utilization of a second metal allows the
use of the residual particles from the synthesis as active
materials along with precious metals [2,8]. On its way, the
methodology of deposition of the Pt particles over the CNT, as
well as the reduction step to get the Pt in metallic form are of
great importance to ensure a good Pt distribution, in addition
to a small particle size.
It had been demonstrated that the structure of the MWCNT
allows a good deposition of nanoparticles over its surface; this
characteristic allows a better dispersion of the particles and
hence is possible to decrease the loading of the active metal
(that is normally expensive). MWCNT are then, in many
different ways a suitable support for metallic particles and
hence an attractive material to use in fuel cells.
As it is well known, Pt/C materials are by excellence good
electrocatalysts [9e11]. Moreover, Pt/CNT materials have
demonstrated to be very stable optimizing the Pt loading [3].
Additionally, the presence of a second metal (i.e. Ru, Pd, Co, Ni,
etc) generates an interaction and hence a modification of the
electrochemical properties [4,12,13]. On its part, PtNi/C
materials have been used as electrocatalysts for alcohol fuel
cells [14] as well as for the oxygen reduction reaction in
a normal PEM fuel cell, exhibiting stability and good perfor-
mance [15]. In addition, it has been demonstrated that PteNi/C
materials are stable and active electrocatalysts, because the Ni
have a synergy with Pt nanoparticles and at the same time
allows a better exposure of the Pt surface without the neces-
sity of an alloy [16]. More recent studies have tested nano-
structured Ni over C in the hydrogen oxidation reaction,
demonstrating good results [17]. This research work presents
the characterization of electrocatalysts integrated by Pt
nanoparticles deposited over MWCNT with Ni. The innovative
contribution is the utilization of MWCNT synthesized using
a Ni precursor, as support of Pt particles; in this way the
cleaning process after the MWCNT synthesis is avoided,
allowing the possibility of take advantage over the use of the
Ni particles that remain on the surface. The materials were
evaluated as electrocatalyst in the hydrogen oxidation reac-
tion using H2SO4 as electrolyte and cyclic voltammetry as well
as CO stripping to determine the active surface area. In addi-
tion the CO stripping is providing information about the
stability of the materials regarding poisoning.
12641
2. Materials and methods
2.1. Carbon nanotubes synthesis
The multi-walled carbon nanotubes (MWCNT) were synthe-
sized in a spray pyrolysis system (SPS) similar to the one
previously reported by Valenzuela et al. [18]. Toluene (J. T.
Baker, 98%) was used as carbon source along with two
different catalytic agents, ferrocene (Fluka 98%) and nickel-
ocene (Sigma Aldrich, 98%). Vycor tubing (9 mm outer diam-
eter and 45 cm in length) was used as substrates. For the
MWCNT obtained using nickelocene (MWCNT-Ni) was
necessary to use a thin film (manganese oxide) as substrate
previously deposited in the inner walls of the Vycor tubing.
The temperatures of MWCNT syntheses were 900  C and
800  C for ferrocene and nickelocene, respectively. The
synthesis parameters were optimized previously, finding the
mentioned temperatures as the most favorable temperatures
for each catalytic agent. After the process, once the substrate
was completely cold, the MWCNT were removed (scratched)
from the Vycor tubing and used in the next step.
2.2. Electrocatalysts synthesis
The deposition of the Pt particles over the MWCNT was per-
formed using an ultrasound assisted method and two
different reduction methodologies. The precursor of the
platinum particles, ammonium hexachloroplatinate
((NH4)2PtCl6), Alfa Aesar 43.78%) was mixed with the MWCNT
and dispersed in alcohol during 30 min using an ultrasonic
bath. In order to evaluate the effect of the reduction step in the
Pt particle size and dispersion, two methodologies were used.
The first one was a thermal reduction (method A), already
reported by Verde et al. [10]. It was performed in a tubular
furnace under H2eN2 (10%e90%) atmosphere at 400  C. In the
second method, the chemical reduction (method B), the elec-
trocatalysts were dispersed with ultrapure water in an ultra-
sonic bath, and 10 mL of NaBH4 (0.1 M) were added as reducing
agent. Once reduced, the electrocatalysts were rinsed and
filtered (Millipore filter 0.22 m) using a vacuum pump. It is
important to mention that the MWCNT obtained using ferro-
cene (MWCNT-Fe) were subjected to a cleaning process in
a reflux system with nitric acid (12 h at 120  C) to remove the
iron particles that remained at the surface after the synthesis.
Meanwhile the MWCNT synthesized with nickel were used as
obtained, to analyze a possible effect of the nickel particles in
the electrochemical performance.
2.3. Characterization and electrochemical evaluation
The morphology and the elemental composition of the
synthesized catalysts were determined by scanning electron
microscopy (SEM) and energy dispersive X-ray spectroscopy
(EDS) respectively in a JEOL JSM-6390 microscope. In addition,
high resolution transmission electron microcopy (HRTEM)
analyses were performed in a JEOL JEM-2200FS in order to
determine the particle size and distribution. Finally, to know
the crystalline phases of the obtained materials, X-ray
diffraction studies (XRD) were performed in a Phillips X Pert
12642 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7
MPD diffractometer (l ¼ 1.54056  A) operated at 43 kV and
30 mA. The electrochemical surface area (ECSA) was evalu-
ated by two electrochemical techniques, cyclic voltammetry
(CV) and CO stripping. The electrochemical experiments were
performed in a standard three-electrode cell at room
temperature and atmospheric pressure. The working elec-
trode was a glassy carbon rod (0.9163 cm2); platinum foil
(2 cm2) and Ag/AgCl [Sat KCl] were used as counter and
reference electrodes respectively. 0.5 M of H2SO4 (Fisher
Scientific 98%) was used as electrolyte. The electrochemical
interface used was a Solartron SI 1287 potentiostat.
In order to have a baseline and to do a comparison, an
electrode using commercial material (10%Pt on Vulcan, Etek)
was evaluated along with the synthesized materials. The
deposition of material over the working electrode was per-
formed base on the procedure described by Pozio et al. [19]. An
ink was created by adding 9 mg of electrocatalyst, 60 mL of
a solution 3:1 of Nafion 5% in aliphatic alcohols in ultrapure
water, and 1 mL of ethanol. The ink was place in an ultrasonic
bath for 35 min in order to assure a homogeneous dispersion.
10 mL of the ink was deposited on the surface of the glassy
carbon and allowed to dry during 15 min inside a desiccator.
It is well known that the CV is a technique commonly used
to determine the Electrochemical Surface Area (ECSA), inte-
grating the area under the curve of the voltammograms. The
measurements were performed following the next procedure:
to guarantee an electrolyte free of oxygen, the cell was purged
during 30 min with argon (Praxair 99.999%) prior to each test.
The working electrode surface was cleaned by performing 20
cycles at 100 mVs
1, after this, argon was purged again during
15 min. Subsequently, ten cycles were performed at scan rate
of 10 mVs
1.
On the other hand, the CO posses the capacity of easy
adsorption on the surface of the catalysts, it is even consid-
ered a pollutant. Due to its adsorption characteristic to the Pt
active sites, the CO can also be used to evaluate the electro-
chemical surface area. ECSA results from both experiments
are compared. After the oxygen was removed and the elec-
trode surface cleaned, the system was purged with CO (Praxair
99.99%) during 7 min keeping the cell under a potential of

0.2 V where the CO is adsorbed on the surface, saturating the
Pt active sites. Afterward, the cell was purged during 10 min
(holding the potential) to remove the CO remained in the
electrolyte. With the electrode surface saturated of CO, the
scan was performed at 10 mVs
1 until get two complete
cycles. As it was previously explained, the calculation of the
ECSA was based on the area under the curve of the voltam-
mograms and using the equations reported by Pozio et al. [19].
3. Results and discussion
Fig. 1 presents the diffraction patterns of the synthesized
samples. The MWCNT supported electrocatalyst exhibit
intensities of the graphite 2H phase, which are associated
with the MWCNT formation. Additionally, it is possible to
corroborate the presence of metallic Pt in all the samples. The
peaks corresponding to fcc Pt are present at (111), (200), and
(220). The materials reduced using the thermal method (Fig. 1a
and c) show sharper peaks than the materials reduced
Fig. 1 e X-ray diffraction patterns of the synthesized
electrocatalysts: a) Pt/MWCNT-A, b) Pt/MWCNT-B, c) PtNi/
MWCNT-A, and d) PtNi/MWCNT-B.
chemically (Fig. 1b and d), this could be attributed to the
relatively high temperature (400  C) of the thermal reduction
process which increases the particles crystallinity. On the
other hand, the peak broadening in chemical reduced samples
can be related to the smaller Pt crystallite size. Furthermore,
as expected the presence of Ni is noticed in the samples where
MWCNT were synthesized using nickelocene (Fig. 1c and d);
due to the MWCNT growth mechanism, Ni metallic particles
remained in the surface.
The analysis of electrocatalyst size and distribution were
performed using HRTEM. Electrocatalysts nanoparticles
deposited on MWCNT-Fe is presented in Fig. 2. For the mate-
rial thermally reduced (Fig. 2a) a good dispersion of small Pt
particles is observed (1e4 nm), however there are also bigger
particles (6e14 nm) probably generated by coalescence.
Material chemically reduced exhibits smaller Pt particles,
however they are not very well distributed along the MWCNT
presenting a high degree of agglomeration, as it is shown in
Fig. 2b.
In Fig. 3 it is presented the images of the electrocatalysts
supported on MWCNT-Ni. These materials exhibited a similar
behavior than the explained before for both reduction types.
The thermal reduction method is generating particles with
a good dispersion over the MWCNT in the range of 1e14 nm
(Fig. 3a) while during the chemical reduction (Fig. 3b) the Pt
particles are getting agglomerated, which could influence the
electrochemical behavior. In addition, for both samples it is
possible to observe the presence of Ni inside the MWCNT as
well as forming in some cases particles clusters (encircled
areas in Fig. 3a and b).
A representative number of particles were randomly
selected and measured for each sample in order to have
a better understanding of the Pt particles size distribution;
Fig. 4 presents the histograms obtained. As it was found in the
HRTEM analysis, for the sample Pt/MWCNT-A (Fig. 4a), the
majority of the Pt particles deposited were between 1 and
4 nm. However, a bimodal distribution of the particle size can
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7 12643

Fig. 2 e High resolution TEM images of the electrocatalysts synthesized using clean MWCNT: a) Pt/MWCNT-A, and b) Pt/
MWCNT-B.

be observed with a second concentration of particles in the around 4e6 nm; the nanoparticles were measured from the
range of 6e14 nm. For the material chemically reduced (Pt/ agglomerates. On the other hand the thermally reduced
MWCNT-B, Fig. 4b) the particle size distribution is localized electrocatalysts obtained using MWCNT-Ni as a support, show
around the 2e8 nm with the highest percentage of particles particle sizes in the region of the 2e10 nm (Fig. 4c), and from 2

Fig. 3 e High resolution TEM images of the electrocatalysts synthesized using MWCNT with Ni: a) PtNi/MWCNT-A, and b)
PtNi/MWCNT-B.
12644 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7

Fig. 4 e Particle size distribution histograms: a) Pt/MWCNT-A, b) Pt/MWCNT-B, c) PtNi/MWCNT-A, and d) PtNi/MWCNT-B.

to 8 nm for the chemically reduced one (Fig. 4d). It is important chemical process the particles are reduced fast and getting
to notice the presence of big particles (20e22 nm) being attached to the surface of the MWCNT, while during the
attributed to the residual Ni during the MWCNT synthesis. thermal process the metallic precursors are first deposited
The use of MWCNT has allowed the decrement of the Pt over the MWCNT and then reduced, allowing the chance for
loading, keeping and even increasing the ECSA. Table 1 pres- some Pt to be lost during the process.
ents the elemental analysis performed by EDS in SEM. The From Table 1 is also important to notice that, in the case of
synthesis was calculated to accomplish a Pt weight the electrocatalysts obtained using MWCNT-Ni, the chemical
percentage of 10; however the achieved loadings were lower. reduction affected the Ni content decreasing it from an initial
It was found that using the method of thermal reduction the 18% (analysis not presented here) to a 2%. This means that the
deposition efficiency was inferior than using the chemical NaBH4 is strong enough not only to reduce the Pt but also to
reduction. This could be attributed to the fact that during the leach some of the Ni out of the MWCNT surface, being later
removed in the rinse step.
A cyclic voltammogram shows the current generated when
the gasses molecules (H2 or CO) are desorbed from the surface
Table 1 e Elemental analysis obtained by EDS in a SEM. of the Pt active sites. By integrating the area under the curve it
is possible to obtain an electric charge, and calculate the
Electrocatalyst Weight %
electrochemical surface area. Different authors as Pozio [19],
C O Pt Fe Ni Verde [10] and Grigoriev [20], among others have used varia-
Pt/MWCNT-A 92.1 1.3 4.9 1.6 e tions of Equation (1) to calculate the electrochemical surface
Pt/MWCNT-B 88.9 1.4 7.9 1.7 e area.
PtNi/MWCNT-A 85.8 0.72 6.1 e 7.3
PtNi/MWCNT-B 90.5 0 7.3 e 2
ECSA ¼ Q=C L (1)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7
Fig. 5 e Cyclic voltammograms performed at 10 mVsL1, in
a potential range of L0.2 to 0.8 V vs. Ag/AgCl (Sat KCl): a)
Pt/Vulcan (Etek), b) Pt/MWCNT-A, c) Pt/MWCNT-B, d) PtNi/
MWCNT-A, and e) PtNi/MWCNT-B. The insert is a close-up
of the region of the H2 desorption utilized to calculate the
EAA.
Where, Q represents the charge in mCcm
2, C is the charge
required to oxidize a monolayer of the gas (0.21 mCcm
2 for H2
and 0.484 mCcm
2 for CO) on metallic Pt, and L is the Pt
loading on the electrode analyzed in mgcm
2. Fig. 5 is showing
the voltammograms obtained for the H2 oxidation reaction.
Commercial material, 10%Pt/Vulcan from Etek with was
analyzed for comparison at the same conditions. The
synthesized materials exhibit activity in the hydrogen
underpotential desorption (UPD) region (
0.2 to 0.06 V) vs. Ag/
AgCl (KCl Sat) electrode. Most of the materials show higher
activity than the commercial electrocatalyst, and with a lower
Pt loading (see Table 1). Furthermore, all the materials
exhibited a well defined peak in the region around the
0.17 V,
that is been normally associated with the desorption of H2
from the Pt (111), being this crystalline plane the most elec-
troactive [21]. The peaks shape in the voltammograms is then
in accordance with the information obtained from XRD anal-
ysis, where thermal reduction methodology allows having
particles of higher crystallinity and oriented to the Pt (111);
Table 2 e Electrochemical surface area obtained with different techniques, and the influence of the particle size.
Electrocatalyst ECSA [m2 g
1]
H2 adsorption CO stripping
10Pt/Vulcan ETEK 142
Pt/MWCNT-A 233
Pt/MWCNT-B 147
PtNi/MWCNT-A 186
PtNi/MWCNT-B 142
a Range of particle size with major frequency in the particle size distribution histograms, based on HRTEM images.
b From reference [18].
c Company specifications.
12645
this characteristic enhance the electroactivity as shown in
Table 2.
The CO stripping tests performed are presented in Fig. 6.
The ECSA was calculated using the area under the curve and
Equation (1). The majority of the active areas calculated using
CO stripping are higher than the calculated by H2 adsorption
(normal CV), however, the tendency is almost the same in
both methodologies. The materials reduced with the thermal
method (Pt/MWCNT and PtNi/MWCNT) exhibit ECSA higher
than the Pt/Vulcan. This can be attributed to a better distri-
bution of the metallic particles over the surface of the
MWCNT. On the other hand, the electrocatalysts reduced
chemically show ECSA close to the commercial material, this
is due to the agglomeration and poor particle distribution that
was achieved with this methodology. However, is important
to notice that the content of Pt of those materials is lower that
the commercial one, indicating that the utilization of the Pt is
being optimized along the MWCNT.
On the other hand, CO stripping can be used not only to
determine the Pt active sites and the ECSA but also to study
the tolerance of the electrocatalyst to poisoning [3]. For
materials with Pt, the CO oxidation potential vs. Ag/AgCl (KCl
Sat) can be observed normally at 0.62 V. In Fig. 6 is possible to
see that all the synthesized materials present a small shift to
the negative potential for the CO oxidation peak. This repre-
sents an early release of the CO from the surface and hence
a higher tolerance of the materials to the CO poisoning [22].
Base on this, it can be drawn that the all the proposed mate-
rials are more tolerant than the Pt/Vulcan. The PtNi/MWCNT
electrocatalyst shows the higher shift, meaning a higher
tolerance; this behavior could be attributed to the interaction
of the Pt and Ni particles, however, an extensive study needs
to be done in order to establish the reaction mechanism. The
property above mentioned is an important and desired prop-
erty in electrocatalysts utilized in the oxidation of alcohols.
Table 2 summarizes the ECSA values obtained using both
techniques, in addition the average of particle size, and Pt
weight percent are included. The method seems to have direct
influence on the ECSA, being the thermal reduction the one
that allows synthesizing higher active materials. This can be
attributed to the effect of the temperature in creating more
crystalline Pt particles without agglomeration. Based on the
results, the electrocatalyst Pt/MWCNT-A exhibit an ECSA 64%
higher than the commercial material (with a 51% less of Pt
Pt particle sizea [nm] Pt loading [weight %]
174 2e3b 10c
235 1e4, 6e14 4.9
144 2e8 7.9
226 2e10 6.1
152 2e8 7.3
12646 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 2 6 4 0 e1 2 6 4 7
Fig. 6 e CO stripping cyclic voltammograms performed at 10 mVsL1, in a potential range of L0.2 to 1.2 V vs. Ag/AgCl (Sat
KCl).
content). On its hand, the PtNi/MWCNT-A shows an ECSA only
a 31% higher, however posses a better tolerance to the CO
poisoning and only a 6% of Pt loading.
4. Conclusions
High performance electrocatalysts based on Pt and Pt-Ni
nanoparticles were obtained by two synthesis methods using
MWCNT as support. The reduction method has a positive
influence in the particle crystallinity, and hence in the electro-
chemical activity. Since the chemical reduction methodology is
generating materials with similar ECSA than the commercial
electrocatalyst, it can be considered as a good alternative of
synthesis due to the advantageous conditions used (room
temperature and atmospheric pressure). MWCNT were proved
to be suitable support for electrocatalysts with low Pt content
(less than 8%), achieving electrochemical activities 30e60%
higher than commercial materials. Finally electrochemical
results suggest that Ni inclusion generate materials more
tolerant to CO poisoning and suitable for alcohol fuel cells
electrodes. The feasibility of using the synthesized materials in
fuel cells could be tested by fabricating electrode assemblies,
and will be performed in future work.
Acknowledgments
This work was supported by FORDECYTeCONACYT under
project No. 116157. Also authors recognized the technical
support of Carlos Elı́as Ornelas Gutierrez and Enrique Torres
Moye. The authors would also like to acknowledge the support
of the Center for Electrochemical Engineering Research at
Ohio University for the resources used during the electro-
chemical testing and for partial financial support.
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