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Nickel nanocatalyst supported on sulfonated

polyaniline: Potentials toward methanol
oxidation and as anode materials of...

Article in Journal of Materials Chemistry A · April 2015

DOI: 10.1039/C5TA01837D

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Nickel nanocatalysts supported on sulfonated

polyaniline: potential toward methanol oxidation
Cite this: J. Mater. Chem. A, 2015, 3,
and as anode materials for DMFCs
Published on 20 April 2015. Downloaded by Calcutta University on 20/05/2015 06:57:38.

11349

Suparna Das, Kingshuk Dutta and Patit P. Kundu*

Received 12th March 2015
Accepted 20th April 2015
DOI: 10.1039/c5ta01837d
www.rsc.org/MaterialsA
The development of potential anode catalysts and catalyst supporting matrices for application in direct
methanol fuel cells (DMFCs) has been an active area of research for the last couple of decades. The
conventionally used Pt catalyst suffers from (a) high cost, (b) limited abundance and (c) the catalyst
poisoning effect induced by the in situ generated carbon monoxide. In this work, a comparatively less
expensive and more abundant Ni metal catalyst [supported on Vulcan carbon, polyaniline (PAni) and
partially sulfonated PAni (SPAni)] has been utilized as a potential alternative to the Pt metal catalyst for
the oxidation of methanol. SPAni emerged as the best matrix for the deposited Ni catalyst nanoparticles.
This combination generated a peak current density of 306 mA cm
2 at +0.57 V. In addition, the Ni/SPAni
catalyst produced a higher IF/IB ratio compared to the commercial Pt–Ru/C catalyst. Furthermore, a
current density of 135 mA cm
2 (at +0.2 V potential) and a maximum power density of 27 mW cm
2
were obtained at 60  C upon utilizing Ni/SPAni as the anode catalyst for DMFCs. The results, thus
obtained, were better than those obtained for the commercial Pt–Ru/C, as well as, the Ni/C and Ni/PAni
catalysts.

potential of methanol coincides with the potential at which the

Introduction
Oxidation of low molecular weight alcohols, such as methanol
and ethanol, by using noble metal catalysts has been an area of
research for several decades.1–3 Particularly, in the last couple of
decades, this particular eld of research has received greater
attention owing to its importance in the operation and
commercialization aspects of direct methanol fuel cells
(DMFCs) and direct ethanol fuel cells.4–6 In this respect, a wide
variety of noble metal catalysts and their binary and ternary
combinations, such as Pt, Pt–Ru, Pt–Sn, Pt–Co, Pt–Pd, Pt–W,
Pt–Rh, Pt–Ga, Pt–Ir, Pt–Ni, Pt–Ru–Rh, Pt–Ru–Ni, Pt–Ru–Sn, and
Pt–Ru–Mo, have evolved as prospective candidates.4–6 However
the high cost and scarce availability of Pt,7 coupled with the
catalyst poisoning effect rendered by methanol oxidation
product(s) [primarily carbon monoxide (CO)] on the Pt catalyst,
have demanded a search for alternative catalyst systems.8,9
Complete replacement of the Pt catalyst by comparatively less
expensive and more stable alternatives is highly desirable in
this regard. Ni is one such prospective metal catalyst, which has
exhibited promising results in the methanol oxidation reaction
(MOR); however, when used in combination with Pt,10–13 Ni has
been found to enhance the rate of CO oxidation, via the surface
redox activity of Ni oxides toward CO.10 Moreover, the oxidation
Advanced Polymer Laboratory, Department of Polymer Science and Technology,
University of Calcutta, 92, A. P. C. Road, Kolkata-700009, India. E-mail: ppk923@
yahoo.com; Fax: +91 2352 5106; Tel: +91 2350 1397
surface of Ni is oxidized.14 However, the prospect of using Ni
alone as a catalyst under acidic conditions for methanol
oxidation has been hindered by its relatively low stability in
acidic medium.
Exploitation of new catalyst supporting matrices, to replace
the conventionally used carbon black support, has also been an
important research eld for the last couple of decades.15–22
Among the potential materials that have been investigated over
the years, aromatic conducting polymer (ACP)-based matrices
have been found to be prospective candidates.6,7,23 A combina-
tion of certain critical advantages, such as (a) low cost, (b) an
easy synthetic route, (c) high electronic conductivity, (d) high
surface area, (e) better interaction possibility with the catalyst
particles due to the presence of heteroatoms, (f) low weight, (g)
thermal stability and (h) environmental stability, is enjoyed by
ACPs;24–29 which makes them extremely suitable as catalyst
supporting materials for DMFCs. The choice of suitable
dopants for ACPs is very important, since the presence of
dopants is critical in modulating the electronic conductivities of
ACPs. Dopants, especially sulfonic acid (–SO3H) dopants, have
also been found to interact positively with catalyst particles and
assist in producing better dispersion, distribution and utiliza-
tion of costly metal catalyst particles.30,31
Based on the above observations and potentialities, it was
intuited that the use of a Ni metal catalyst supported on
partially sulfonated ACPs can serve as a unique catalyst–support
combination for the MOR. Herein, partially sulfonated

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Fig. 1 Schematic illustration of the SPAni matrix preparation and the
catalyst deposition process.
polyaniline (SPAni) was utilized as the ACP. Complete replace-
ment of expensive Pt by low-cost Ni shall result in effective
reduction of the overall cost of the DMFC operation. In addi-
tion, the chemical incorporation of –SO3H groups into the ACP
structure, in place of using –SO3H dopants, shall produce better
interaction between the catalyst particles and the support
matrix (Fig. 1); thereby providing stability to the overall system.
In this work, we demonstrate (a) preparation of the SPAni
matrix by partial sulfonation of polyaniline (PAni) with chlor-
osulfonic acid (CSA), (b) deposition of Ni catalyst nanoparticles
on support matrices from their precursor salt, (c) determination
of the electrochemical properties of the synthesized catalyst
systems and (d) analysis of the prospects of using Ni/PAni and
Ni/SPAni as anode catalyst systems for DMFCs.
Experimental
Materials
Nickel(II) chloride hexahydrate (NiCl2$6H2O), sodium borohy-
dride (NaBH4), aniline, ammonium peroxodisulfate (APS), CSA,
methanol, acetone, and sodium hydroxide (NaOH) were bought
from Merck Millipore India. HCl (reagent grade) was obtained
from Loba Chemie. Naon-117 membrane, 5 wt% Naon
solution and the commercial Pt–Ru/C and Pt/C catalyst systems
were purchased from M/S Anabond Synergy Fuel Cell India Ltd.
All chemicals were used as received. De-ionized (DI) water was
used for all the experiments.
Synthesis of support matrix (PAni and SPAni) and deposition
of Ni nanoparticles
The approach utilized for synthesizing PAni has been adopted
from a previously reported method.32 Similarly, sulfonation of
PAni was carried out following the procedure detailed in
previously reported studies.33,34
Deposition of Ni nanoparticles on different supporting
matrices was performed by chemically reducing the precursor
NiCl2$6H2O with NaBH4 at 80  C.35 At rst, the different sup-
porting matrices, i.e. Vulcan carbon, PAni and SPAni, were
ultrasonically dispersed in a mixture of DI water and isopropyl
alcohol (1 : 1) for 10 min. The catalyst precursor salt (NiCl2$6H2O)
was then added to the formed ink under continuous stirring
conditions. The pH of the solution was raised to 8 by the addition
11350 | J. Mater. Chem. A, 2015, 3, 11349–11357
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Paper
of NaOH. This was followed by dropwise addition of 20 mL of
0.2 mol L
1 NaBH4 solution into the precursor–ink mixture for
30 min. The resulting solution was then stirred for 1 h, followed
by cooling and washing with DI water for complete removal of
chloride ions. This was then vacuum-dried for 24 h at room
temperature to obtain the nal catalyst–support powder.
Preparation of working electrode and electrochemical
measurements
Electrochemical measurements were carried out in a three
electrode Dr Bob's cell at room temperature using a glassy
carbon electrode as the working electrode, Pt wire as the
counter electrode and saturated calomel electrode (SCE) as the
reference electrode. The catalyst powders were rst made wet
with DI water, followed by the addition of a small amount of
isopropanol and 5 wt% Naon solution. The resulting ink was
ultrasonicated for 30 min. The obtained ne slurry was loaded
onto the surface of the glassy carbon electrode. All the three
electrodes were dipped in a solution of 2 M CH3OH and 0.05 M
H2SO4 and purged with ultra-pure nitrogen gas to make the
atmosphere of the cell inert. Electrochemical experiments, i.e.
cyclic voltammetry (CV) and linear sweep voltammetry (LSV),
were performed using a Gamry Potentiostat-600, within the
potential ranges of 0 V to +0.8 V and 0 V to +2.0 V, respectively.
The scanning rate employed for this purpose was 100 mV s
1.
FT-IR and X-ray diffraction (XRD) analyses
A Bruker Alpha FT-IR spectrophotometer (Model: Alpha E) was
used to record the FT-IR spectra of PAni and SPAni. The
wavenumber window employed was 500 cm
1 to 4000 cm
1.
The XRD patterns of the catalyst powders were obtained using
a Goniometer by applying an angle of 2q, within the range
of 10–100 , and a xed scan rate of 1 min
1. The Pt (111) and
Ni (111) peaks were used to calculate the particle size of Pt and
Ni according to the Scherrer equation:36
d ¼ 0.9l/b1/2 cos q (1)
where d is the average particle size in nm, l is the wavelength of
the X-ray used (1.54060 Å), b1/2 is the width of the diffraction
peak at half height in radians and q is the angle at the position
of the peak maximum.
Scanning electron microscopic (SEM) and energy-dispersive X-
ray (EDX) spectroscopic analyses
The morphology of the synthesized catalyst–support matrices
was investigated by FE-SEM (Jeol 7600F) and their chemical
compositions were analyzed using an EDX analyzer (Oxford
Instruments, INCA PentaFET-x3) attached to the scanning
electron microscope. All the micrographs were recorded at a
magnication of 50 000.
Fabrication of membrane electrode assemblies (MEAs) and
DMFC performance test
Pt–Ru/C (80 : 20) and Ni/SPAni were used as anode catalysts,
while Pt/C was used as the cathode catalyst. A metal loading of
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Results and discussion

FT-IR and XRD analyses
Successful incorporation of –SO3H groups into PAni was
conrmed by FT-IR spectroscopy. The appearance of new peaks
at 1142 cm
1 and 1402 cm
1, representing the symmetric and
asymmetric stretching of the S]O bonds present in –SO3H
groups, respectively, and the peak appearing at 3741 cm
1, due
to the stretching of the O–H bonds of –SO3H groups, conrmed
the successful sulfonation of PAni to SPAni (Fig. 2).33,38–40
Fig. 3 represents the XRD pattern of all the catalyst–support
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combinations prepared. The rst peak for Pt–Ru/C and Ni/C in

Fig. 2 FT-IR spectra of PAni and SPAni [reprinted from [33], with
permission from Elsevier, Copyright 2013].
the XRD pattern, located at a 2q value of 25.3 and 26.1 ,
respectively, can be attributed to the carbon support. The
intensity of the abovementioned peak was found to decrease for
the rest of the samples, owing to the absence of pure carbon
within the support layer. The characteristic peak obtained at a
2q value of 41.1 represents the plane (111) of face-centred cubic
(fcc) crystalline Pt.41,42 For all the Ni-based catalyst–support
combinations, a signicant characteristic peak was recorded at
a 2q value of 11.9 , 35.6 , 53.4 and 60.9 representing the
planes (003), (100), (102) and (110), respectively, of Ni(OH)2.43,44
The peaks appearing at a 2q value of 35.6 and 60.9 also
represent the planes (111) and (220), respectively, of cubic
NiO.45–47 Again, a small peak appearing at a 2q value of 42.7
obtained for Ni/C represents the plane (111) of metallic Ni,
which was shied to a 2q value of 43.3 and 41.2 for Ni/PAni
and Ni/SPAni, respectively. Table 1 presents the lattice param-
eter, crystallite size, full width at half maximum and d-spacing
values of the different combinations.

UV-vis, SEM and EDX analyses

Fig. 3 XRD spectra of the different catalyst–support combinations.
4 mg cm
2 has been employed for the preparation of the indi-
vidual electrodes. MEAs were prepared by sandwiching two
catalyst layers with the Naon-117 membrane, followed by hot
pressing for 6 min at 135  C under a pressure of 15.9 MPa.
The DMFC performance test was done using a single cell
assembly connected to the fully automated DMFC test station
(K-PAS Electronic India Ltd.). 2 M methanol was used as the
anolyte, with a ow rate of 2 mL min
1; while untreated air
was used as the catholyte, with a ow rate of 50 mL min
1 to
60 mL min
1.37
The UV-vis spectrum of NiCl2 solution before and aer reduc-
tion by NaBH4, as presented in Fig. 4, was recorded in order to
conrm the deposition of Ni nanoparticles from the precursor
salt solution. From the gure, a decrease in the intensity of the
absorption peak at 410 nm was obtained owing to the reduction
of NiCl2 to Ni nanoparticles (Fig. 4).
The structures and properties of the support, such as func-
tional groups present at the surface, graphitized structure and
active surface area, have a large effect on the activity and
durability of the catalysts.48 ACPs, with a highly accessible
surface area and high stability, have been used to improve the
activity of the carbon support, as well as, enhance the disper-
sion of metal catalyst particles.49,50 From the SEM images, it was

Table 1 Lattice parameter, crystallite size, full width at half maximum (FWHM) and d-spacing values of the different catalyst–support
combinations

Lattice parameter Crystallite/particle d-spacing

Samples (nm) size/diameter (nm) FWHM ( 2q) (nm)

Pt–Ru/C 0.64 8.8 1.90 0.23

Ni/C 0.74 10.8 1.58 0.26
Ni/Pani 0.71 8.6 1.27 0.27
Ni/SPani 0.64 6.1 1.90 0.26

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observed that the deposited catalyst particle size decreases from (Fig. 7b). Lower deposition of Ni on carbon and its higher
Ni/C to Ni/PAni (Fig. 5a and b). Nevertheless, the overall particle size compared to Pt–Ru may be the possible reasons
distribution of the catalyst particles on the PAni matrix was behind this observation.
found to be non-uniform. Upon employing SPAni as the matrix
material, the catalyst particle size got further reduced, with
better dispersion and distribution, compared to that obtained
for Ni/PAni (Fig. 5c). In effect, the reduction of catalyst particle
size, coupled with the enhancement of catalyst particle disper-
sion and distribution, on the sulfonated ACP matrices shall
increase the effective surface area of the catalyst, and thus, shall
lead to better utilization of the catalyst towards the MOR.
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Along with the catalyst particle size, dispersion and distri-

bution, the amount of catalyst deposition is also critical in
highlighting the effectiveness of a support matrix. Therefore, we
performed the EDX spectroscopic analysis of the different
catalyst–support combinations. Although the amount of
precursor metal salt used for the deposition of the Ni catalyst on
different support matrices was maintained constant, from the
EDX data it was observed that the amount of Ni nanoparticles
deposited on different matrices was different (Table 2). From
the table it is clear that the sulfonated ACP matrix, i.e., SPAni,
induced the highest catalyst deposition. The EDX data
complement the SEM observations, promoting SPAni as the
best matrix for Ni catalyst nanoparticles.

Cyclic and linear sweep voltammetries

It is well-known that higher utilization of metal catalysts has a
positive effect on the methanol electro-oxidation reaction.51
Therefore, in order to analyze the effectiveness of the different
catalyst–support combinations used in this work, we determined
the output current densities both in terms of the catalyst area
and catalyst mass (Fig. 6 and 7). While comparing the peak
current density values of the investigated catalyst (Ni) with that
of the conventional commercial catalyst (Pt–Ru), it was observed
that Ni/C exhibited a lower forward peak current density
compared to that obtained for Pt–Ru/C by about 90.1 mA cm
2
(Fig. 6b). In addition, Ni nanoparticles deposited on the carbon
support exhibited a signicant effect on the forward peak
potential by lowering the value from +0.59 V (obtained for
commercial Pt–Ru/C) to +0.55 V (Fig. 6b and 7b). However, Ni/C
showed a forward peak mass specic current density value lower
than that obtained for commercial Pt–Ru/C by 1.88 mA g
1

Fig. 4 UV-vis absorption spectra obtained before and after the Fig. 5 Scanning electron microscopic images of (a) Ni/C, (b) Ni/PAni
reduction of NiCl2 to Ni nanoparticles. and (c) Ni/SPAni.

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Paper Journal of Materials Chemistry A

Table 2 Elemental composition of the different catalyst–support combinations as obtained from EDX analysis

Atomic% Weight% Atomic% Weight% Atomic% Weight% Atomic% Weight%

Samples of metal of metal of carbon of carbon of nitrogen of nitrogen of sulfur of sulfur

Pt–Ru/C 40.7 79.8 59.3 20.2 — — — —

Ni/C 19.3 40.4 80.7 59.6 — — — —
Ni/PAni 23.3 52.8 64.4 39.3 12.3 7.9 — —
Ni/SPAni 35.0 71.9 51.6 20.5 11.7 5.0 1.7 2.6
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Fig. 6 Cyclic voltammograms representing the forward and reverse area specific peak current densities and peak potentials of the different
catalyst–support combinations.

Next, we analyzed the catalytic efficiency of Ni deposited on
ACP PAni. PAni, as a support matrix, produced decreased
forward peak area and mass specic current densities by
magnitudes of 58.2 mA cm
2 and 1.05 mA g
1, respectively,
compared to Pt–Ru/C (Fig. 6a and 7a). Relatively high deposi-
tion and uniform distribution of Ni particles on the PAni matrix
are probable reasons behind this observation (Table 2). As a
result, in LSV analysis, the maximum current density obtained
for Ni/PAni was 2.15 mA cm
2 at +0.2 V, which was lower than
the value obtained for Pt–Ru/C (i.e. 2.38 mA cm
2 at +0.2 V) but
higher than the value obtained for Ni/C (i.e. 2.04 mA cm
2 at
+0.2 V) (Fig. 8). Apart from the synergistic effect of Ni with PAni;
smaller size and higher deposition of Ni nanoparticles on the
PAni matrix compared to that on the C matrix were the main
reasons behind the observed enhancements in the area and
mass specic current densities.
In the case of the SPAni matrix, Ni deposited on it exhibited
forward peak area and mass specic current densities of 306 mA
cm
2 and 6.1 mA g
1, respectively, which were higher than the
corresponding values obtained for Pt–Ru/C by 25.6 mA cm
2 and
0.6 mA g
1, respectively; along with an observed lowering in the
peak potential (Fig. 6b and 7b). Therefore, the presence of
–SO3H groups on the PAni matrix clearly increased the effi-
ciency of the Ni catalyst and also reduced the reverse peak
current density compared to that obtained for the commercial
Pt–Ru/C. Ni/SPAni also exhibited increased forward peak area
and mass specic current densities by magnitudes of 85.2 mA
cm
2 and 1.61 mA g
1, respectively, compared to Ni/PAni (Fig. 6
and 7). From the LSV plots in Fig. 8, it can be observed that the
maximum current density obtained for Ni/SPAni was higher
than the value obtained for Ni/PAni by 0.65 mA cm
2 and that
obtained for Pt–Ru/C by 0.37 mA cm
2 at +0.2 V. Higher depo-
sition, better dispersion and distribution, smaller particle size
and higher utilization of Ni nanoparticles on the SPAni matrix,
compared to that on the other studied matrix materials (PAni
and C), resulted in the best catalytic activity of the Ni catalyst on
the SPAni matrix.
The most probable reasons behind the obtained higher
electro-catalytic activity of Ni/SPAni towards the MOR compared
to that produced by Pt–Ru/C are: (a) the presence of the SPAni
support resulted in easy adsorption of water on the surface of
the metal catalyst, and the resulting formation of Ni–(OH)ads
promoted the oxidation of the in situ formed carbonaceous
species to CO2;52,53 and (b) the presence of –SO3H groups within
the SPAni support enhanced the amount and reduced the size of
the deposited catalyst nanoparticles, and ensured their uniform
dispersion, thus resulting in an effective enhancement of the
electro-catalytically active surface area of the catalyst system.54,55
As a result of the abovementioned two reasons the accessibility
of the active Ni metal catalyst sites towards the reactant
increases signicantly, compared to the Pt–Ru metal catalyst.
Chronoamperometry
The performance of the electro-catalysts towards methanol
oxidation was evaluated by chronoamperometric analysis in 2 M
methanol and 0.05 M H2SO4 at a given anodic potential of +0.4 V

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Fig. 7 Cyclic voltammograms representing the forward and reverse
mass specific peak current densities and peak potentials of the
different catalyst–support combinations.
vs. SCE; and the obtained results are presented in Fig. 9. In all of
the obtained current vs. time curves, there was an initial current
drop in the rst 100 s (possibly due to the charging current),
followed by a slower decay. It was observed that Pt–Ru/C
exhibited an initial current density of 280 mA cm
2, which
decreased to 62 mA cm
2 aer 700 s. Ni/C exhibited a lower
Fig. 8 Linear sweep voltammetric plots of the different catalyst–
support combinations.
11354 | J. Mater. Chem. A, 2015, 3, 11349–11357
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initial current density of 250 mA cm
2, which decreased further
below Pt–Ru/C to 42 mA cm
2 aer 700 s; owing to the fact that
Ni undergoes base metal dissolution in acidic medium. On the
other hand, Ni/PAni exhibited higher stability than that showed
by Pt–Ru/C, as evidenced from the lower drop in current density
produced by Ni/PAni (i.e. from 271 mA cm
2 to 83 mA cm
2).
Furthermore, it was enticing to observe that incorporation of
–SO3H groups into the support matrix PAni further enhanced
the stability of the electro-catalyst (Fig. 9). As can be seen from
the gure, Ni/SPAni exhibited a current density of 121 mA cm
2
aer 700 s, which was almost double that obtained for
commercial Pt–Ru/C. Since –SO3H groups potentially enhance
the proton uptake capacity of the catalyst support, catalyst
poisoning decreases, resulting in enhanced stability.56
IF/IB ratio
The ratio of the forward anodic peak current density (IF) to the
reverse anodic peak current density (IB) obtained for the electro-
catalysts is presented in Fig. 10a. It can be observed from the
gure that the IF/IB ratio increases from Ni/C to Ni/PAni, which
got further enhanced to the maximum value for Ni/SPAni (i.e.
1.44). It should be noted that the commercial Pt–Ru/C exhibited
an IF/IB ratio of 1.27, which was 11.8% lower than that obtained
for Ni/SPAni. For the electro-catalysts studied in this work, the
forward peak current (IF) was found to increase linearly with an
increase in the backward peak current (IB) (Fig. 10b), indicating
that the greater the dehydrogenation effect produced in the
forward scan, the greater is the obtained oxidation of the
carbonaceous poisonous species.
DMFC test and cycle stability
DMFC performances obtained in single cell stacks, for the
commercial Pt–Ru/C and the reported Ni/SPAni, were recorded
and are presented in Fig. 11. Ni/SPAni produced a current
density value of 135 mA cm
2 (at a potential of +0.2 V), along
with a maximum power density value of 27 mW cm
2. These
values were slightly higher than that obtained for Pt–Ru/C (i.e. a
Fig. 9Chronoamperometric curves of the different catalyst–support
combinations.
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Fig. 10 (a) Variation of the forward and backward peak current ratio (IF/IB) and (b) forward peak current (IF) vs. backward peak current (IB) plots for
electro-oxidation of 2 M CH3OH + 0.05 M H2SO4 of the different catalyst–support combinations.
Fig. 11 Direct methanol fuel cell performance obtained upon
employing Pt–Ru/C and Ni/SPAni as anode catalysts at 60  C.
Fig. 12Cycle stability of the Ni/SPAni catalyst system in comparison to
the commercial Pt–Ru/C catalyst system.
current density of 119.7 mA cm
2 and a maximum power
density of 23.94 mW cm
2). It should be noted that since the IF/
IB value produced by Ni/SPAni is marginally higher than that
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Journal of Materials Chemistry A
obtained for Pt–Ru/C, the obtained current density and the
maximum power density values of the Ni/SPAni catalyst are
slightly higher than those observed for the commercial Pt–Ru/C
catalyst. In effect, the dual factor of protonic and electronic
conductivity exhibited by SPAni in the Ni/SPAni catalyst system
makes it a promising anode catalyst for DMFCs.
Next, we compared the cycle stabilities of the commercial Pt–
Ru/C and the synthesized Ni/SPAni catalyst systems, and the
obtained results are presented in Fig. 12. For this purpose we
subjected the two catalyst systems to repeated charge–discharge
cycles in DMFC, and measured the current density output at
+0.2 V cell potential produced by the catalyst systems in each
cycle. It was observed that while Pt–Ru/C showed a stable
current density value up to the analyzed 10 charge–discharge
cycles, Ni/SPAni exhibited progressively decreasing current
density values for subsequent charge–discharge cycles.
However, the current density values exhibited by the Ni/SPAni
catalyst system were found to be higher than those exhibited by
the Pt–Ru/C catalyst system up to the 7th cycle, and were equal to
that of the commercial catalyst for the 8th and the 9th cycle.
Although, a higher stability is required for the new catalyst
system in order to effectively compete with the commercial
catalyst; the obtained results in this preliminary work are
promising enough to further exploit this new catalyst system for
DMFCs.
Conclusions
The novel catalyst–support combinations utilized in this work
have shown promising results for further exploitation towards
the MOR. SPAni emerged as the best support matrix for Ni
catalyst deposition, dispersion, distribution and utilization,
resulting in the highest output area and mass specic current
densities. The obtained forward peak current densities were
higher than those of the commercial Pt–Ru/C catalyst system,
while the reverse peak current densities were found to be lower
than those of the commercial catalyst. Moreover, both the
forward and reverse peak potentials obtained for the Ni/SPAni
catalyst system were lower compared to Pt–Ru/C. Furthermore,
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a current density of 135 mA cm
2 (at +0.2 V potential) and a
maximum power density of 27 mW cm
2 were obtained at 60  C
upon utilizing Ni/SPAni as the anode catalyst for DMFCs. In
addition, in the cycle stability analysis, the current density
values exhibited by the Ni/SPAni catalyst system were found to
be higher than those exhibited by the Pt–Ru/C catalyst system
up to the 7th charge–discharge cycle in DMFCs, and were equal
to those of the commercial catalyst for the 8th and the 9th cycle.
These results present new possibilities in exploiting Ni as a
possible alternative to Pt–Ru and sulfonated ACPs as effective
catalyst support matrices for the oxidation of methanol and as
Published on 20 April 2015. Downloaded by Calcutta University on 20/05/2015 06:57:38.
an anode catalyst system for DMFCs.
Acknowledgements
KD would like to thank the Council of Scientic and Industrial
Research (CSIR), India, for a Senior Research Fellowship (Award
no. 09/028 (0901)/2012-EMR-I). PPK is thankful to the Ministry
of New and Renewable Energy (MNRE), Govt. of India, for a
grant-in-aid (Grant no. 102/56/2009-NT).
Notes and references
1 Y. Zhao, X. Yang, J. Tian, F. Wang and L. Zhan, J. Power
Sources, 2010, 195, 4634.
2 T. Kessler and A. M. C. Luna, J. Appl. Electrochem., 2002, 32,
825.
3 A. M. C. Luna, J. Appl. Electrochem., 2000, 30, 1137.
4 H. Liu, C. Song, L. Zhang, J. Zhang, H. Wang and
D. P. Wilkinson, J. Power Sources, 2006, 155, 95.
5 E. Antolini, J. Power Sources, 2007, 170, 1.
6 K. Dutta, S. Das, D. Rana and P. P. Kundu, Polym. Rev., 2015,
55, 1.
7 K. Dutta and P. P. Kundu, Polym. Rev., 2014, 54, 401.
8 C. Bianchini and P. K. Shen, Chem. Rev., 2009, 109, 4183.
9 P. Kumar, K. Dutta, S. Das and P. P. Kundu, Int. J. Energy Res.,
2014, 38, 1367.
10 K.-W. Park, J.-H. Choi, B.-K. Kwon, S.-A. Lee, Y.-E. Sung,
H.-Y. Ha, S.-A. Hong, H. Kim and A. Wieckowski, J. Phys.
Chem. B, 2002, 106, 1869.
11 E. Antolini, J. R. C. Salgado and E. R. Gonzalez, Appl. Catal.,
B, 2006, 63, 137.
12 J.-H. Choi, K.-W. Park, B.-K. Kwon and Y.-E. Sung, J.
Electrochem. Soc., 2003, 150, A973.
13 F. Liu, J. Y. Lee and W. J. Zhou, Small, 2006, 2, 121.
14 M. A. A. Rahim, R. M. A. Hameed and M. W. Khalil, J. Power
Sources, 2004, 134, 160.
15 Y.-J. Yang, D. P. Wilkinson and J. Zhang, Chem. Rev., 2011,
111, 7625.
16 S. Sharma and B. G. Pollet, J. Power Sources, 2012, 208, 96.
17 S. Biallozor, A. Kupniewska and V. Jasulaitene, Fuel Cells,
2003, 3, 8.
18 Z. Chen, L. Xu, W. Li, M. Waje and Y. Yan, Nanotechnology,
2006, 17, 5254.
19 C. Arbizzani, M. Biso, E. Manferrari and M. Mastragostino, J.
Power Sources, 2008, 178, 584.
11356 | J. Mater. Chem. A, 2015, 3, 11349–11357
View Article Online
Paper
20 H. Gharibi, M. Amani, H. Pahlavanzadeh and M. Kazemeini,
Electrochim. Acta, 2013, 97, 216.
21 M. Zhiani, B. Rezaei and J. Jalili, Int. J. Hydrogen Energy, 2010,
35, 9298.
22 S. Patra and N. Munichandraiah, Langmuir, 2009, 25, 1732.
23 E. Antolini and E. R. Gonzalez, Appl. Catal., A, 2009, 365, 1.
24 K. Dutta, P. Kumar, S. Das and P. P. Kundu, Polym. Rev.,
2014, 54, 1.
25 R. Y. Mahale, A. Arulkashmir, K. Dutta and
K. Krishnamoorthy, Phys. Chem. Chem. Phys., 2012, 14, 4577.
26 K. Dutta and P. P. Kundu, J. Colloid Interface Sci., 2013, 397,
192.
27 K. Dutta and P. P. Kundu, J. Colloid Interface Sci., 2013, 407,
516.
28 K. Dutta and P. P. Kundu, J. Phys. Chem. B, 2013, 117, 7797.
29 K. Dutta, P. Kumar, S. Das and P. P. Kundu, Colloids Surf., A,
2013, 436, 830.
30 M. Zhiani, H. Gharibi and K. Kakaei, J. Power Sources, 2012,
210, 42.
31 F.-J. Liu, L.-M. Huang, T.-C. Wen, C.-F. Li, S.-L. Huang and
A. Gopalan, Synth. Met., 2008, 158, 767.
32 K. Dutta, R. Y. Mahale, A. Arulkashmir and
K. Krishnamoorthy, Langmuir, 2012, 28, 10097.
33 K. Dutta, S. Das, P. Kumar and P. P. Kundu, Appl. Energy,
2014, 118, 183.
34 K. Dutta, S. Das and P. P. Kundu, J. Membr. Sci., 2015, 473,
94.
35 Z. B. Wang, G. P. Yin, J. Zhang, Y. C. Sun and P. F. Shi,
Electrochim. Acta, 2006, 51, 5691.
36 F. Gu, S. F. Wang, M. K. Lü, G. J. Zhou, D. Xu and D. R. Yuan,
J. Phys. Chem. B, 2004, 108, 8119.
37 P. Kumar, K. Dutta and P. P. Kundu, Int. J. Energy Res., 2014,
38, 41.
38 K. Dutta, S. Das and P. P. Kundu, J. Membr. Sci., 2014, 468,
42.
39 S. Das, P. Kumar, K. Dutta and P. P. Kundu, Appl. Energy,
2014, 113, 169.
40 P. Kumar, K. Dutta, S. Das and P. P. Kundu, Appl. Energy,
2014, 123, 66.
41 A. Dutta, S. S. Mahapatra and J. Datta, Int. J. Hydrogen Energy,
2011, 36, 14898.
42 J. Datta, A. Dutta and S. Mukherjee, J. Phys. Chem. C, 2011,
115, 15324.
43 Z.-A. Hu, Y.-L. Xie, Y.-X. Wang, H.-Y. Wu, Y.-Y. Yang and
Z.-Y. Zhang, Electrochim. Acta, 2009, 54, 2737.
44 M. R. Sturgeon, M. H. O'Brien, P. N. Ciesielski, R. Katahira,
J. S. Kruger, S. C. Chmely, J. Hamlin, K. Lawrence,
G. B. Hunsinger, T. D. Foust, R. M. Baldwin, M. J. Biddy
and G. T. Beckham, Green Chem., 2014, 16, 824.
45 D.-I. Jang and S.-J. Park, Fuel, 2012, 102, 439.
46 P. S. Patil and L. D. Kadam, Appl. Surf. Sci., 2002, 199, 211.
47 M. Alagiri, S. Ponnusamy and C. Muthamizhchelvan, J.
Mater. Sci.: Mater. Electron., 2012, 23, 728.
48 Y. Zhao, L. Zhan, J. Tian, S. Nie and Z. Ning, Electrochim.
Acta, 2011, 56, 1967.
49 H. Zhao, L. Li, J. Yang, Y. Zhang and H. Li, Electrochem.
Commun., 2008, 10, 876.
This journal is © The Royal Society of Chemistry 2015

Paper
50 H. Zhao, L. Li, J. Yang and Y. Zhang, J. Power Sources, 2008,
184, 375.
51 H.-Y. Lee, W. Vogel and P. P.-J. Chu, Langmuir, 2011, 27,
14654.
52 Y. Xu, X. Peng, H. Zeng, L. Dai and H. Wu, C. R. Chim., 2008,
11, 147.
53 M. Zhiani, B. Rezaei and J. Jalili, Int. J. Hydrogen Energy, 2010,
35, 9298.
Published on 20 April 2015. Downloaded by Calcutta University on 20/05/2015 06:57:38.
This journal is © The Royal Society of Chemistry 2015
View publication stats
View Article Online
Journal of Materials Chemistry A
54 H. J. Wang, H. Yu, F. Peng and P. Lv, Electrochem. Commun.,
2006, 8, 499.
55 C. Y. Du, T. S. Zhao and Z. X. Liang, J. Power Sources, 2008,
176, 9.
56 D. W. Hatchett, N. M. Millick, J. M. Kinyanjui,
S. Pookpanratana, M. Bar, T. Hofmann, A. Luinetti and
C. Heske, Electrochim. Acta, 2011, 56, 6060.
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