Applied Surface Science 265 (2013) 214–221

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Applied Surface Science

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Fabrication and electrocatalytic application of functionalized nanoporous carbon

material with different transition metal oxides
L. Samiee a,∗ , F. Shoghi a , A. Vinu b,∗∗
a
Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran, Iran
b
Australian Institute for Bioengineering and Nanotechnology(AIBN), The University of Queensland, Corner College and Cooper Roads (Bld75), Brisbane, Qld 4072, Australia

a r t i c l e i n f o a b s t r a c t

Article history: In the work presented here, an attempt is made to study the effect of functionalization with different tran-
Received 7 April 2012 sition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous
Received in revised form 29 October 2012 carbon supports.
Accepted 29 October 2012
In this respect, the functionalized samples have been synthesized by using CMK-3 and metal-
locene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional
Keywords:
wet impregnation method. All the materials have been characterized by XRD (low and high), N2
Rotating disk electrode
adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution
PEMFC
Nanoporous carbon
field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk
Functionalization electrode (RDE) techniques.
Transition metal oxides The results showed that the mesostructural order has been destroyed by functionalization of CMK-
3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image
mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in
the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes
in NiO and CuO functionalized samples in relative to other functionalized supports.
Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed
an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-
Fe2 O3 -Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.

© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Porous materials with three-dimensionally (3D) interconnected
ordered structures are technologically important for a variety of
applications including the use as catalysts, supports, separation
systems, sensors, adsorbents, electronic materials, double-layer
capacitors, and hydrogen storage materials [1].
Recently, ordered mesoporous carbons (OMC) have attracted
considerable attention as catalyst supports because of their high
surface areas and their regular structure, which might be useful to
disperse metal particles.
The OMC structure is based on periodic arrays of carbon
nanorods connected by carbon spacers with uniform mesopores
among them [2].
∗ Corresponding author. Tel.: +98 21 48255244; fax: +98 21 44739590.
∗∗ Corresponding author. Tel.: +61 7 3346 4122; fax: +61 7 3346 3973.
E-mail addresses: Leila.Samiee83@gmail.com, Samieel@ripi.ir (L. Samiee),
a.vinu@uq.edu.au (A. Vinu).
The selection of the nanoporous silica template is crucial for the
successful preparation of nanoporous carbons with regular struc-
tures.
The pore size in nanoporous carbon materials can be tuned
by controlling the structure of the silica replica [3]. Among the
different types of nanoporous silica templates like MCM-41 and
MCM-48, SBA-15 have a 2D porous structure comprised of hexag-
onal arrays of cylindrical pores which are finely interconnected
by micropores through the walls [4]. As the nanoporous chan-
nels in SBA-15-type materials are interconnected by micropores,
an ordered nanoporous carbon structure is maintained even after
silica removal. Using this concept, a nanoporous carbon with hexag-
onal symmetry, CMK-3, is obtained from a SBA-15 template [5,6].
It is expected that the traditional systems for energy generation
would be replaced by fuel cells in a medium long term [7].
High expectations of the commercialization of fuel cells and the
accompanied environmental benefits has led to intensified studies
on various fundamental and applied fronts [8].
Among the various types of fuel cells, low temperature systems
are particularly promising because they are free from the techni-
cal complications due to high temperature management. On the

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.10.173
 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221 215

Table 1
Textural parameters such as specific surface area, specific pore volume, pore size distribution and crystallite size of Pt in catalysts.

Catalysts Transition metals (%) dspacing (nm) Pore size (nm) Pore volume BET (m2 /g) Crystallite size EAS (m2 /g)b
(cm3 /g)a of Pt (nm)

Pure CMK3-Pt 0 8.9 4.6 1.23 1260 7.2 8.23

CMK-3-NiO-Pt 1 7.95 3.99 1.17(0.51) 1175 7.6 47.02
CMK-3-Fe2 O3 -Pt 1 7.62 3.84 1.1(0.54) 1124 10.9 10.41
CMK-3-CoO-Pt 1 – 2.57 0.75(0.65) 1172 11.8 37.74
CMK-3-CuO-Pt 1 8.65 4.5 0.86(0.49) 783 7.9 45.44
a
Total pore volume calculated at p/p0 = 0.88. Values in parentheses are micropore volumes (pore size < 1.4 nm).
b
ESA = QH /0.21[Pt] where [Pt] represents the platinum loading, QH is the charge for hydrogen desorption and 0.21 shows the charge required for oxidation of a monolayer
of H2 on bright Pt (mC cm−2 ).

other hand, low temperature fuel cells (PEMFCs) need good water However, there is not such a study, to the best of our knowledge,
management and an efficient catalyst. for a complex system containing carbon and transition metal oxides
A large amount of platinum is generally used as a cathode cat- for an cathodic performance in fuel cells, therefore, we were stim-
alyst in the present PEMFCs. But, the durability and the cost of the ulated to study of the structural and electrochemical properties of
PEMFC are the two core issues which need to be considered for the functionalized nanoporous carbon supports by different types of
successful commercialization of PEMFC. PEMFCs require a platinum transition metal oxides. This paper suggests a possibility of prepa-
catalyst as an active material for the electrodes, which makes the ration of the periodic structures of OMC which has high surface
cost of the whole device high and limits their commercialization [9]. activity and well electrochemical property.
In addition, dissolution of highly Pt catalysts during long-term
operation is another matter that should be regarded. 2. Experimental
Thus, it is highly necessary to find out the way to reduce the
amount of platinum catalyst in the PEMFC. One of the best ways to 2.1. Materials
reduce the platinum catalyst but keeping the same performance is
to utilize new carbon materials with excellent textural characteris- Tetraethyl orthosilicate, sucrose, and tri-block copolymer
tics as catalysts supports. In the last few years ordered nanoporous poly(ethylene glycol)-block-poly(propylene glycol)-block-poly
like carbons have been proposed as catalyst supports for PEMFC (ethylene glycol) (Pluronic P123, molecular weight = 5800,
[10,11]. Ordered nanoporous carbon supports have several char- EO20 PO70 EO20 ) were obtained from Aldrich. H2 PtCl6 ·6H2 O and
acteristics, which include high surface area for finely dispersing
catalytic metal particles, high electrical conductivity for providing
electrical pathways, mesoporosity for facile diffusion of reactants
and by-products, and water handling capability for removing water
generated at the electrode [12].
But regarding to nanoporous carbon supports, the relatively
poor electrical conductivity is an important factor that should be
improved. From the past years, much effort has been aimed at
searching for alternative electrode materials (nickel oxide, cobalt
oxide, iron oxide, copper oxide and manganese oxide), which
are inexpensive and exhibit pseudocapacitive associated with
electrosorption and surface redox behavior similar to that of Pt, Ru
and Ir [13].
So, as a result, functionalization by transition metal oxides can
be a way for improvement of overall properties of nanoporous car-
bon supports for using in PEMFCs.

Fig. 2. The N2 adsorption–desorption isotherms (a) and BJH pore size distribution
Fig. 1. SAXRD patterns of electrocatalysts. (b) of functionalized-catalysts.
216 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221
Fig. 3. SEM micrographs of CMK-3-NiO-Pt (a), CMK-3-CuO-Pt (b), CMK-3-Fe2 O3 -Pt (c) and CMK-3-CoO-Pt (d) of functionalized-catalysts, respectively.
metallocene (metal: Ni, Co, Fe and Cu) was also purchased from
Aldrich.
2.2. Preparation of mesoporous carbon supports
Functionalized mesoporous carbons with different transition
metal oxides (CMK-3-X) (X denotes the different types of transi-
tion metal oxides) were prepared by using SBA-15 [24] materials
as templates, sucrose as the carbon source and metallocene as the
transition metal source.
In a typical synthesis of mesoporous carbon, 1 g of SBA-15 was
added to a solution obtained by dissolving 1.25 g of sucrose and
0.14 g of H2 SO4 in 5 g of water, and keeping the mixture in an
oven for 6 h at 100 ◦ C. Subsequently, the oven temperature was
raised to 160 ◦ C for another 6 h. In order to obtain fully polyme-
rized and carbonized sucrose inside the pores of the silica template,
0.8 g of sucrose, 0.09 g of H2 SO4 and 5 g of water were again added
to the pre-treated sample and the mixture was again subjected
to the thermal treatment described above. The template–polymer
composites were then pyrolyzed in a nitrogen flow at 877 ◦ C and
kept under these conditions for 6 h to carbonize the polymer. The
mesoporous carbon was recovered after dissolution of the silica
framework in 5 wt% hydrofluoric acid, by filtration, washed several
times with ethanol, and dried at 120 ◦ C.
Functionalization of nanoporous carbon by (1 wt%) transition
metal oxides was done by an impregnation method. A solution of
metallocene source (MeC10 H10 , Me = Ni, Co, Fe, Cu) in ethanol was
mixed to carbon solution and the slurry was then dried at 60–70 ◦ C
for 5–6 h with continuous stirring. Finally, the samples were treated
under N2 flow, at 400 ◦ C.
2.3. Preparation of cathodic electrode materials using
functionalized mesoporous carbons
Platinum supported mesoporous carbon electrodes were syn-
thesized using impregnation method. Platinum (5 wt%) and
CMK-3-X were dispersed into ethanol solution and the mixture was
stirred for about 6 h, followed by drying at room temperature in N2
flow.
The dried powder was reduced at 400 ◦ C for 2 h in mixed gas H2
(10%) and N2 (90%) flow. For comparison, pure-CMK-3 with 5 wt%
of platinum was also prepared using the impregnation method.
2.4. Characterization of the mesoporous carbon supports
The X-ray powder diffraction (XRD) pattern of material was
collected on a Rigaku diffractometer using Cu K␣ (k = 0.154 nm)
radiation. The diffractogram was recorded in the 2 range of
0.7–10◦ for low angle and 10–90◦ for high angle with a 2 step size
of 0.01◦ and a step time of 1 s. Nitrogen adsorption and desorption
isotherm was measured at −196 ◦ C on a Quantochrome Autosorb
1 sorption analyzer. All samples were outgassed at 500 ◦ C for 3 h
prior to the nitrogen adsorption measurements. The specific sur-
face area was calculated using the Brunauer–Emmett–Teller (BET)
method. The pore size was obtained from the adsorption branch of
the nitrogen isotherm by Barret Joyner and Halenda (BJH) method.
The morphology of the materials was observed on a Hitachi S-
4800 field emission scanning electron microscope (HR-FESEM) and
EDS mapping using and accelerating voltage of 5.0 kV.
Finally, the HRTEM images were obtained with TEM JEOL JEM-
2000EX2. The preparation of samples for HRTEM analysis involved
 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221
Fig. 4. EDX image mapping of Ni element in CMK-3-NiO-Pt (a), Cu element in CMK-3-CuO-Pt (b), Fe element in CMK-3-Fe2 O3 -Pt (c) and Co element in CMK-3-CoO-Pt (d),
respectively.
sonication in ethanol for 2–5 min and deposition on a copper grid.
The accelerating voltage of the electron beam was 200 kV.
2.5. Cathodic electrode performance of the nanoporous carbons
impregnated with platinum catalyst
The performance of platinum loaded nanoporous carbon elec-
trode was compared with that of pure-CMK-3 with 5 wt% of
platinum. The cathodic properties of platinum loaded CMK-3 were
examined by cyclic voltammetry (CV) and rotating disk electrode
(RDE) using CH 760C electrochemical analyzer. The measurement
was carried out in a 0.5 M H2 SO4 aqueous solution. Platinum foil
and calomel were used as counter and reference electrodes, respec-
tively. The electrode materials (3 mg/mL) were suspended into
CH3 OH aqueous solution. The suspension (10 ␮L) was spread onto
0.071 C m2 Au electrode using a micropipette.
After the solvent evaporated, the electrode surface was covered
with 5 ␮L of Nafion solution (diluted to 1% solution with CH3 OH)
and the electrode was dried at 60 ◦ C for 1 h to evaporate the solvent.
3. Results and discussion
3.1. Structural properties of the catalysts
Fig. 1 shows the SAXRD powder patterns of the functionalized
nanoporous carbon supports by different types of transition metal
oxides. The textural parameters of the materials including the spe-
cific surface area, the specific pore volume and the pore diameter
are given in Table 1.
217
As can be seen in Fig. 1, except the CMK-3-CoO-Pt, the other sam-
ples exhibit a sharp peak at lower angle and several higher order
peaks (for CMK-3-NiO-Pt and CMK-3-CuO-Pt catalysts), indicating
that the materials possess well-ordered mesoporous structure with
uniform mesopores.
The shape of the SAXRD pattern of the nanoporous carbon
supports is almost similar to that of the template, confirming
that the replicating process was successfully carried out and the
structure of the template was successfully transformed from the
template to the nanoporous carbon samples. The d spacing of the
nanoporous carbon synthesized using SBA-15 materials decreases
in the following order: CMK-3-CuO-Pt > CMK-3-NiO-Pt > CMK-3-
Fe2 O3 -Pt > CMK-3-CoO-Pt.
The shift of (1 0 0) peak to higher angle and reduction of its
intensity could be interpreted as a formation of transition metal
oxides nanoparticles inside the linear arrays of pore channels of
CMK-3 support. The peak broadening in XRD patterns could be
also attributed to loss of long range order and collapsing of the
mesochannels.
It has been concluded that CMK-3-NiO-Pt and CMK-3-CuO-
Pt, support materials are highly stable even after the platinum
impregnation and reduction procedure and the significant change
in their textural parameters is not observed even after the
modification.
The textural parameter of the platinum loaded nanoporous car-
bon materials were also obtained by the nitrogen adsorption. Fig. 2a
shows the nitrogen adsorption isotherms at 77 K of CMK3-X-Pt
along with the BJH-PSD (Fig. 2b). Except to CMK-3-CoO-Pt sam-
ple which has a H4 hysteresis loop, other isotherms are of type IV,
218 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221
Fig. 5. EDX image mapping of Pt element in CMK-3-NiO-Pt (a), CMK-3-CuO-Pt (b), CMK-3-Fe2 O3 -Pt (c) and CMK-3-CoO-Pt (d), respectively.
according to the IUPAC classification, and exhibit a H2 hysteresis
loop.
As the relative pressure increases (p/p0 > 0.35), isotherms
exhibit a sharp step characteristic of capillary condensation of
nitrogen within uniform mesopores, where the p/p0 position of the
inflection point is correlated to the diameter of the mesopore. The
adsorption pore size distribution of functionalized samples is given
in Fig. 3b. They show uniform pore size distribution.
The specific surface area, the specific pore volume of the CMK-
3-NiO-Pt are 1175 cm2 g−1 , 1.17 cm3 /g respectively, which are very
close to pure-CMK-3 and higher than those of other functionalized
samples. But the pore diameter and pore volume of the cobalt oxide
functionalized sample have been drastically decreased from 4.6 to
2.57 nm and from 1.23 cm3 /g to 0.75 cm3 /g, respectively, revealing
that the structural order of material was affected by the function-
alization.
This reduced stability is probably a consequence of the changes
in the number of micropores that are drastically increased in the
case of CMK-3-CoO-Pt.
The carbon materials should possess a high mesoporosity allow-
ing the adsorption of molecules and ions that are too large to enter
micropores.
Moreover, the adsorption capacity of CMK-3-CoO-Pt is lower as
compared to other samples, which are probably a consequence of
its disordered structure (see XRD) and/or the presence of micropo-
res.
The surface morphology of the obtained carbon materials was
observed by high resolution field emission scanning electron
microscope (HR-FESEM) (Fig. 3).
All the carbon samples show rod like morphology [14–16] which
is almost similar to their original silica template. It is interesting
to note that the morphological order of the mesoporous carbon
materials decreases with functionalization by CoO and Fe2 O3 .
Figs. 4 and 5 show the EDX image mapping of functionalizing
elements (Ni, Cu, Fe and Co), Pt and the micro-region element distri-
bution exhibited the good and uniform dispersion of these elements
in the carbon support.
The results are very much consistent with the results obtained
from the HR-TEM (Fig. 6). Whereas the formation of well ordered
hexagonal (p6mm) arrays of mesopores can be clearly noticed, but
for the nanoporous carbon supports functionalized by CoO, the level
of order was noticed to decrease evidenced by the appearance of
some areas of partly disordered structure in their corresponding
HRTEM micrographs.
The average particle size of the nanoparticles (d) was estimated
by using Scherrer equation (1) after background subtraction from
(1 1 1) peak at 2 of ∼40◦ , also [17]:
k
d= (1)
ˇ cos 
where k is the coefficient, generally taken as 0.9,  is wavelength of
X-ray radiation equal to 1.54051 Å, ˇ is full width at half-maximum
(FWHM) measured in radians, and  is the angle measured at the
position of platinum peaks. Table 1 shows the crystalline size of the
Pt.
Table 1 shows that the platinum crystallite sizes in CMK-3-NiO-
Pt and CMK-3-CuO-Pt samples are smaller than the other samples.
 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221 219

Fig. 6. TEM micrographs of CMK-3-NiO (a and b) and CMK-3-CoO (c and d), supports.

This can be explained by considering that fully periodic
mesostructures demands higher nucleation and growth energies
than disordered nanoparticles [18]. The difference could be possi-
bly attributed to the different constraints present in the periodic
carbon mesoporous compared to a partially disordered structure
in CMK-3-Fe2 O3 -Pt and CMK-3-CoO-Pt [19]. In fact, for an ordered
system higher energies are required to create a critical nucleus of
crystallized Pt due to the constraints of the nanoscale periodicity.
These well-dispersed platinum particles (Fig. 5) with small
size and uniform shape are highly critical to obtain excellent
cathodic performance in the PEMFCs. In addition, the well-
dispersed uniform platinum nanoparticles on the mesochannels of
the nanoporous carbon supports are also easily accessible for the
hydrogen or methanol [20].
in the cyclic voltammograms. Hydrogen adsorption and desorption
peaks can be clearly seen.
It was observed that the double-layer thickness and the charge
of H2 desorption increase in order to CMK-3-NiO-Pt > CMK-3-CuO-
Pt > CMK-3-CoO-Pt > CMK-3-Fe2 O3 -Pt. The current obtained by the
CMK-3-NiO-Pt and CMK-3-CuO-Pt catalysts is much higher than
that of the others and hydrogen peaks are more pronounced for
these samples and among two, CMK-3-NiO-Pt showed the highest
performance.

3.2. Cathodic electrode performance of platinum loaded of

functionalized mesoporous carbon material with different
transition metal oxides

Furthermore, we evaluated the transport characteristics of sam-

ples by conducting cyclic voltammetry (CV) experiments in N2
saturated 0.5 M H2 SO4 . Fig. 7 shows the cyclic voltammograms
of the functionalized mesoporous carbon with different transition
metal oxides loaded with 5 wt% of platinum.
CV was employed to obtain the amount of the charge of H2
desorption for samples functionalized with different transition
metal oxides.
The cyclic votammograms of all the platinum supported sam- Fig. 7. Cyclic voltammograms of catalysts in N2 saturated 0.5 H2 SO4 ; scan rate
ples exhibit well-defined hydrogen adsorption–desorption peaks 10 mV/s.
220 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221

Fig. 8. ORR Polarization curves for different electrocatalysts at different rotation rates, in an oxygen saturated 0.5 M H2 SO4 electrolyte; scan rate 1 mV/s. Insets show
Koutecky–Levitch plots at various electrodes potentials.

The good performance of platinum supported CMK-3-CuO-Pt is It has been reported that the relationship between the O2 reduc-
also due to the fact that the large pore diameter allows the easy tion current at a thin catalyst layer on RDE and its rotation rate is
diffusion of platinum nanoparticles inside the channels and limits given by:
the agglomeration of the particles both in the pore entrance and
1 1 1 1 1
on the porous surface of the support. On the other hand, smaller = + = + (2)
j jk jd jk Bω1/2
Pt crystallites in these samples can be resulted to higher available
active surface area and catalytic activity. In a film-coated electrode surface, the overall measured current j,
On the other hand, the lower performance of the CMK-3-Fe2 O3 - is related to the kinetic current, jk , the boundary-layer diffusion-
Pt and CMK-3-CoO-Pt is mainly due to its smaller pore diameter limited current jd , The boundary-layer diffusion-limited current
which might be blocked by the bigger platinum nanoparticles and can be expressed as:
there by the reduction in the performance in the PEMFC can be
2/3
expected. jd = 0.62ne FCO DO −1/6 ω1/2 = Bω1/2 (3)
The oxygen reduction reaction depends strongly on the hydro-
dynamic conditions. To study the kinetics of the oxygen reduction where 0.62 is a constant used, when ω is expressed in revo-
on a catalyst ink-type electrodes, a rotating disk electrode, RDE lution per minute, ne the number of electrons transferred per
was used, immersed in oxygen saturated 0.5 M H2 SO4 , saturation molecule of O2 in the overall reaction, F the Faraday constant, CO the
being achieved by bubbling oxygen for 30 min. Prior to the electro- concentration of oxygen dissolved (1.1 × 10−6 mol cm−3 ), DO the
chemical measurements, the electrode was activated by scanning diffusion coefficient of oxygen in the solution (1.4 × 10−5 cm2 s−1 ),
the potential between 0.1 and 0.4 V for 20 min in the outgassed  is the cinematic viscosity of the sulfuric acid (1.0 × 10−2 cm−2 s−1 )
acid electrolyte. Throughout the current–potential measure- [21] and B is the Levich constant which was calculated From
ments, an oxygen atmosphere was maintained on the electrolyte Koutecky–Levich plots (Table 2).
surface.
Fig. 8 shows the current–potential curves for the different cat- Table 2
alysts for oxygen reduction obtained at various rotation rates, Kinetic parameters of different catalysts.
scanning the potential from 1 to 0 V at 1 mV/s. Catalysts B (mA cm−2 rpm−1/2 ) Jd experimental (mA cm−2 )
The ORR currents at the disk electrode start between 0.4 and @ 3500 rpm
0.6 V and reach a limiting current around 0.1 V. It is evident that CMK-3-NiO-Pt 0.204 −8.69
the limiting current increases in order to CMK-3-NiO-Pt > CMK-3- CMK-3-Fe2 O3 -Pt 0.160 −4.95
CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe2 O3 -Pt. CMK-3-CoO-Pt 0.159 −6.09
CMK-3-CuO-Pt 0.194 −7.77
 L. Samiee et al. / Applied Surface Science 265 (2013) 214–221
Fig. 9. Mass transfer-corrected Tafel plots for different electrocatalysts.
Here the goal is not to provide extensive kinetic analysis, but
to point to certain trends. Fig. 9 shows the mass transfer corrected
Tafel plot, deduced from data of Fig. 8, corrected for diffusion to
give the kinetic currents using the following equation [22–24]:
jd
jk = j
jd − j
Fig. 9 also compares the kinetic currents of different catalysts. The
Tafel plots show a linear behavior in the mixed activation–diffusion
region. According to the Tafel plots, it is observed that the
overpotential decreases in the order of CMK-3-NiO-Pt > CMK-
3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe2 O3 -Pt. In these cases, the
general shape of Tafel slopes seems to be the same, and it looks
like as if one Tafel curve was shifted parallel with respect to cur-
rent density axes. This suggests that the rate-determining step and
reaction mechanism are similar in all the samples.
With comparison of the electrochemical results, it can be clearly
concluded that textural parameters of the nanoporous carbon
support materials and Pt crystallite size are not the only effec-
tive parameters, but also surface reactivity is an important factor
to control the cathodic performance of the electrode catalyst
in the PEMFCs. For example, in spite of higher surface area of
CMK-3-Fe2 O3 -Pt, CMK-3-CoO-Pt, these two samples have lower
electrochemical active surface area in relation to CMK3-CuO-Pt
sample.
Transition metal oxides can favor transfer of OH− ions to the
surface and as a result the functionalized structure possibly pro-
vides OH− accessible pores and a very high surface area for charge
storage [25–28] according to following equation (5):
charge
Transition metal oxides (TMO) + OH−  TMOOH + e−
discharge
4. Conclusions
The effect of functionalization with different transition metal
oxides on structural properties and electrochemical behavior of
Pt/carbon supports have been summarized to followings:
1. SAXRD, FESEM and HRTEM results showed the mesostructural
structure has been destroyed by functionalization with CoO
whereas it is not that much affected in NiO and CuO functional-
ized samples.
2. EDX image mapping of functionalizing elements (Ni, Cu, Fe and
Co), Pt and the micro-region element distribution exhibited the
221
good and uniform dispersion of these elements in the carbon
support.
3. Among the materials prepared and due to the lower stability,
CMK-3-CoO-Pt has registered the lowest pore volume and pore
diameter.
4. WAXRD results shows that the platinum crystallite sizes in
nanoporous-carbon functionalized by NiO and CuO are smaller
than the other samples which are related to higher energies
requirement to create a critical nucleus of crystallized Pt due
to the constraints of the nanoscale periodicity.
5. Kinetic analysis proved that NiO and CuO functionalized sam-
ples have the highest electrochemical activity relative to other
samples.
6. Electrochemical evaluations are determined by two factors:
namely, surface area and surface reactivity (redox potential).
Taking these two factors into consideration, CMK3-NiO-Pt gives
the highest performance and electrochemical activity.
Acknowledgements
We would like to acknowledge, the support of Japan Science
and Technology (JST) Agency, Iran Renewable Energy Organiza-
tion (SUNA) and Fuel Cell Steering Committee. Further, we would
like also to appreciate the kind support of National Institute for
Materials Science, 1-1, Tsukuba, Ibaraki 305-0044, Japan during the
sabbatical leave of one of the authors (L.S.) during her PhD program.
(4)
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