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

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

* Corresponding author. Tel.: þ52 998 8807432x115; fax: þ52 998 8807433.
E-mail addresses: [email protected], [email protected] (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 12641

have already been demonstrated to have a high efficiency

in terms of Pt particles dispersion as well as stability, 2. Materials and methods
leading them in highly active electrocatalysts [2e4]. There
are a wide number of methodologies to obtain MWCNT. 2.1. Carbon nanotubes synthesis
Spray pyrolysis is one of the most commonly used; this
methodology represents advantages among others due to The multi-walled carbon nanotubes (MWCNT) were synthe-
its characteristics of using non-sophisticated equipments sized in a spray pyrolysis system (SPS) similar to the one
as well as easy of scalability. previously reported by Valenzuela et al. [18]. Toluene (J. T.
Commonly MWCNT are synthesized using precursors Baker, 98%) was used as carbon source along with two
base on iron [5] obtaining well aligned MWCNT as well as different catalytic agents, ferrocene (Fluka 98%) and nickel-
high production yields. However, it is always necessary to ocene (Sigma Aldrich, 98%). Vycor tubing (9 mm outer diam-
perform a cleaning process after the synthesis in order to eter and 45 cm in length) was used as substrates. For the
remove the residual iron particles that remain on the surface MWCNT obtained using nickelocene (MWCNT-Ni) was
which could weaken the stability of the catalyst. On the other necessary to use a thin film (manganese oxide) as substrate
hand, other type of precursors or nucleation agents based on previously deposited in the inner walls of the Vycor tubing.
different metals as cobalt [6] or nickel [7], have been used in The temperatures of MWCNT syntheses were 900  C and
order to avoid the presence of iron. Nevertheless, these 800  C for ferrocene and nickelocene, respectively. The
precursors in most of the cases exhibited low production synthesis parameters were optimized previously, finding the
yields. However, the utilization of a second metal allows the mentioned temperatures as the most favorable temperatures
use of the residual particles from the synthesis as active for each catalytic agent. After the process, once the substrate
materials along with precious metals [2,8]. On its way, the was completely cold, the MWCNT were removed (scratched)
methodology of deposition of the Pt particles over the CNT, as from the Vycor tubing and used in the next step.
well as the reduction step to get the Pt in metallic form are of
great importance to ensure a good Pt distribution, in addition 2.2. Electrocatalysts synthesis
to a small particle size.
It had been demonstrated that the structure of the MWCNT The deposition of the Pt particles over the MWCNT was per-
allows a good deposition of nanoparticles over its surface; this formed using an ultrasound assisted method and two
characteristic allows a better dispersion of the particles and different reduction methodologies. The precursor of the
hence is possible to decrease the loading of the active metal platinum particles, ammonium hexachloroplatinate
(that is normally expensive). MWCNT are then, in many ((NH4)2PtCl6), Alfa Aesar 43.78%) was mixed with the MWCNT
different ways a suitable support for metallic particles and and dispersed in alcohol during 30 min using an ultrasonic
hence an attractive material to use in fuel cells. bath. In order to evaluate the effect of the reduction step in the
As it is well known, Pt/C materials are by excellence good Pt particle size and dispersion, two methodologies were used.
electrocatalysts [9e11]. Moreover, Pt/CNT materials have The first one was a thermal reduction (method A), already
demonstrated to be very stable optimizing the Pt loading [3]. reported by Verde et al. [10]. It was performed in a tubular
Additionally, the presence of a second metal (i.e. Ru, Pd, Co, Ni, furnace under H2eN2 (10%e90%) atmosphere at 400  C. In the
etc) generates an interaction and hence a modification of the second method, the chemical reduction (method B), the elec-
electrochemical properties [4,12,13]. On its part, PtNi/C trocatalysts were dispersed with ultrapure water in an ultra-
materials have been used as electrocatalysts for alcohol fuel sonic bath, and 10 mL of NaBH4 (0.1 M) were added as reducing
cells [14] as well as for the oxygen reduction reaction in agent. Once reduced, the electrocatalysts were rinsed and
a normal PEM fuel cell, exhibiting stability and good perfor- filtered (Millipore filter 0.22 m) using a vacuum pump. It is
mance [15]. In addition, it has been demonstrated that PteNi/C important to mention that the MWCNT obtained using ferro-
materials are stable and active electrocatalysts, because the Ni cene (MWCNT-Fe) were subjected to a cleaning process in
have a synergy with Pt nanoparticles and at the same time a reflux system with nitric acid (12 h at 120  C) to remove the
allows a better exposure of the Pt surface without the neces- iron particles that remained at the surface after the synthesis.
sity of an alloy [16]. More recent studies have tested nano- Meanwhile the MWCNT synthesized with nickel were used as
structured Ni over C in the hydrogen oxidation reaction, obtained, to analyze a possible effect of the nickel particles in
demonstrating good results [17]. This research work presents the electrochemical performance.
the characterization of electrocatalysts integrated by Pt
nanoparticles deposited over MWCNT with Ni. The innovative 2.3. Characterization and electrochemical evaluation
contribution is the utilization of MWCNT synthesized using
a Ni precursor, as support of Pt particles; in this way the The morphology and the elemental composition of the
cleaning process after the MWCNT synthesis is avoided, synthesized catalysts were determined by scanning electron
allowing the possibility of take advantage over the use of the microscopy (SEM) and energy dispersive X-ray spectroscopy
Ni particles that remain on the surface. The materials were (EDS) respectively in a JEOL JSM-6390 microscope. In addition,
evaluated as electrocatalyst in the hydrogen oxidation reac- high resolution transmission electron microcopy (HRTEM)
tion using H2SO4 as electrolyte and cyclic voltammetry as well analyses were performed in a JEOL JEM-2200FS in order to
as CO stripping to determine the active surface area. In addi- determine the particle size and distribution. Finally, to know
tion the CO stripping is providing information about the the crystalline phases of the obtained materials, X-ray
stability of the materials regarding poisoning. 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 Fig. 1 e X-ray diffraction patterns of the synthesized
bath for 35 min in order to assure a homogeneous dispersion. electrocatalysts: a) Pt/MWCNT-A, b) Pt/MWCNT-B, c) PtNi/
10 mL of the ink was deposited on the surface of the glassy MWCNT-A, and d) PtNi/MWCNT-B.
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- chemically (Fig. 1b and d), this could be attributed to the
grating the area under the curve of the voltammograms. The relatively high temperature (400  C) of the thermal reduction
measurements were performed following the next procedure: process which increases the particles crystallinity. On the
to guarantee an electrolyte free of oxygen, the cell was purged other hand, the peak broadening in chemical reduced samples
during 30 min with argon (Praxair 99.999%) prior to each test. can be related to the smaller Pt crystallite size. Furthermore,
The working electrode surface was cleaned by performing 20 as expected the presence of Ni is noticed in the samples where
cycles at 100 mVs
1, after this, argon was purged again during MWCNT were synthesized using nickelocene (Fig. 1c and d);
15 min. Subsequently, ten cycles were performed at scan rate due to the MWCNT growth mechanism, Ni metallic particles
of 10 mVs
1. remained in the surface.
On the other hand, the CO posses the capacity of easy The analysis of electrocatalyst size and distribution were
adsorption on the surface of the catalysts, it is even consid- performed using HRTEM. Electrocatalysts nanoparticles
ered a pollutant. Due to its adsorption characteristic to the Pt deposited on MWCNT-Fe is presented in Fig. 2. For the mate-
active sites, the CO can also be used to evaluate the electro- rial thermally reduced (Fig. 2a) a good dispersion of small Pt
chemical surface area. ECSA results from both experiments particles is observed (1e4 nm), however there are also bigger
are compared. After the oxygen was removed and the elec- particles (6e14 nm) probably generated by coalescence.
trode surface cleaned, the system was purged with CO (Praxair Material chemically reduced exhibits smaller Pt particles,
99.99%) during 7 min keeping the cell under a potential of however they are not very well distributed along the MWCNT

0.2 V where the CO is adsorbed on the surface, saturating the presenting a high degree of agglomeration, as it is shown in
Pt active sites. Afterward, the cell was purged during 10 min Fig. 2b.
(holding the potential) to remove the CO remained in the In Fig. 3 it is presented the images of the electrocatalysts
electrolyte. With the electrode surface saturated of CO, the supported on MWCNT-Ni. These materials exhibited a similar
scan was performed at 10 mVs
1 until get two complete behavior than the explained before for both reduction types.
cycles. As it was previously explained, the calculation of the The thermal reduction method is generating particles with
ECSA was based on the area under the curve of the voltam- a good dispersion over the MWCNT in the range of 1e14 nm
mograms and using the equations reported by Pozio et al. [19]. (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
3. Results and discussion possible to observe the presence of Ni inside the MWCNT as
well as forming in some cases particles clusters (encircled
Fig. 1 presents the diffraction patterns of the synthesized areas in Fig. 3a and b).
samples. The MWCNT supported electrocatalyst exhibit A representative number of particles were randomly
intensities of the graphite 2H phase, which are associated selected and measured for each sample in order to have
with the MWCNT formation. Additionally, it is possible to a better understanding of the Pt particles size distribution;
corroborate the presence of metallic Pt in all the samples. The Fig. 4 presents the histograms obtained. As it was found in the
peaks corresponding to fcc Pt are present at (111), (200), and HRTEM analysis, for the sample Pt/MWCNT-A (Fig. 4a), the
(220). The materials reduced using the thermal method (Fig. 1a majority of the Pt particles deposited were between 1 and
and c) show sharper peaks than the materials reduced 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 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
Fig. 5 e Cyclic voltammograms performed at 10 mVsL1, in
being optimized along the MWCNT.
a potential range of L0.2 to 0.8 V vs. Ag/AgCl (Sat KCl): a)
On the other hand, CO stripping can be used not only to
Pt/Vulcan (Etek), b) Pt/MWCNT-A, c) Pt/MWCNT-B, d) PtNi/
determine the Pt active sites and the ECSA but also to study
MWCNT-A, and e) PtNi/MWCNT-B. The insert is a close-up
the tolerance of the electrocatalyst to poisoning [3]. For
of the region of the H2 desorption utilized to calculate the
materials with Pt, the CO oxidation potential vs. Ag/AgCl (KCl
EAA.
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-
Where, Q represents the charge in mCcm
2, C is the charge sents an early release of the CO from the surface and hence
required to oxidize a monolayer of the gas (0.21 mCcm
2 for H2 a higher tolerance of the materials to the CO poisoning [22].
and 0.484 mCcm
2 for CO) on metallic Pt, and L is the Pt Base on this, it can be drawn that the all the proposed mate-
loading on the electrode analyzed in mgcm
2. Fig. 5 is showing rials are more tolerant than the Pt/Vulcan. The PtNi/MWCNT
the voltammograms obtained for the H2 oxidation reaction. electrocatalyst shows the higher shift, meaning a higher
Commercial material, 10%Pt/Vulcan from Etek with was tolerance; this behavior could be attributed to the interaction
analyzed for comparison at the same conditions. The of the Pt and Ni particles, however, an extensive study needs
synthesized materials exhibit activity in the hydrogen to be done in order to establish the reaction mechanism. The
underpotential desorption (UPD) region (
0.2 to 0.06 V) vs. Ag/ property above mentioned is an important and desired prop-
AgCl (KCl Sat) electrode. Most of the materials show higher erty in electrocatalysts utilized in the oxidation of alcohols.
activity than the commercial electrocatalyst, and with a lower Table 2 summarizes the ECSA values obtained using both
Pt loading (see Table 1). Furthermore, all the materials techniques, in addition the average of particle size, and Pt
exhibited a well defined peak in the region around the
0.17 V, weight percent are included. The method seems to have direct
that is been normally associated with the desorption of H2 influence on the ECSA, being the thermal reduction the one
from the Pt (111), being this crystalline plane the most elec- that allows synthesizing higher active materials. This can be
troactive [21]. The peaks shape in the voltammograms is then attributed to the effect of the temperature in creating more
in accordance with the information obtained from XRD anal- crystalline Pt particles without agglomeration. Based on the
ysis, where thermal reduction methodology allows having results, the electrocatalyst Pt/MWCNT-A exhibit an ECSA 64%
particles of higher crystallinity and oriented to the Pt (111); higher than the commercial material (with a 51% less of Pt

Table 2 e Electrochemical surface area obtained with different techniques, and the influence of the particle size.
Electrocatalyst ECSA [m2 g
1] Pt particle sizea [nm] Pt loading [weight %]

H2 adsorption CO stripping

10Pt/Vulcan ETEK 142 174 2e3b 10c

Pt/MWCNT-A 233 235 1e4, 6e14 4.9
Pt/MWCNT-B 147 144 2e8 7.9
PtNi/MWCNT-A 186 226 2e10 6.1
PtNi/MWCNT-B 142 152 2e8 7.3

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.
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 references

a 31% higher, however posses a better tolerance to the CO
poisoning and only a 6% of Pt loading.
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