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 6 ( 2 0 1 1 ) 1 3 3 2 5 e1 3 3 3 4

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Optimization of the amount of Nafion in multi-walled carbon

nanotube/Nafion composites as Pt supports in gas diffusion
electrodes for proton exchange membrane fuel cells
Hussein Gharibi a,*, Masoumeh Javaheri a, Mehdi Kheirmand b, Rasol Abdullah Mirzaie c
a

Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175 Tehran, Iran
Department of Chemistry, Faculty of Science, Yasouj University, Yasouj, Iran
c
Department of Chemistry, Faculty of Science, Shahid Rajaee University, Tehran, Iran
b

article info

abstract

Article history:

The Nafion loading in multi-walled carbon nanotube (MWCNT) composites with Nafion

Received 20 June 2010

used as Pt support in the oxygen reduction reaction (ORR) has been studied. We varied the

Received in revised form

amount of Nafion in these composites and added a Pt loading of 0.3 mg cm
2 to the catalyst

11 August 2010

layer. The performance of these electrodes in the ORR was measured with linear sweep

Accepted 2 September 2010

voltammetry (LSV), electrochemical impedance spectroscopy (EIS), chronoamperometry,

Available online 8 October 2010

inductive coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy
(TEM), and scanning electron microscopy (SEM). In addition, we compared the performance

Keywords:

of the MWCNTs as Pt supports with those of the composites. Our results indicate that the

Catalyst layer (CL)

composites are better Pt supports in comparison with MWCNT.

Gas diffusion electrode (GDE)

Copyright 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights

Oxygen reduction reaction (ORR)

reserved.

Proton exchange membrane fuel cell

(PEMFC)
Pt support

1.

Introduction

Carbon nanotubes possess a wide variety of remarkable

properties, most notably high electrical and thermal conductivities, mechanical strength, and large catalytic surface areas,
and thus have potential uses in a variety of power generation
and storage devices, including proton exchange membrane
fuel cells (PEMFCs) [1].
Composite electrodes consisting of Pt nanoparticles supported on multi-walled carbon nanotubes grown directly on
carbon paper (Pt/MWCNTs/carbon paper) have previously
been synthesized by using glacial acetic acid as a reducing
agent [2]. Lee and Hu have successfully developed a simple but

effective method for grafting various chemical reagents onto

the opposite tube-ends of individual carbon nanotubes, as
confirmed with X-ray photoelectron spectroscopy measurements. This approach could be used in the site-selective selfassembly of both MWCNTs and single-walled carbon nanotubes (SWCNTs) into a large variety of novel functional
systems with highly controllable structures and various
applications [3,4]. Tang and Wu presented a detailed
comparison of MWCNTs and SWCNTs in an effort to identify
the better supporting carbon material for electrocatalysts in
direct methanol fuel cells (DMFCs) [5,6]. Salvetat et al. found
that the mechanical properties of nanotubes are strongly
dependent on their structures; various types of nanotubes

* Corresponding author.
E-mail addresses: h.gharibi@gmail.com, gharibi@modares.ac.ir (H. Gharibi).
0360-3199/$ e see front matter Copyright 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.09.008

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Table 1 e Gas diffusion electrodes (GDEs) with various

Nafion loadings.
GDE
1
2
3
4
5

Pt loading
mg cm
2

Nafion loading
mg cm
2

Pt/MWCNT
composite

Pt/
MWCNT

0.3
0.3
0.3
0.3
0.3

0.5
0.75
1
1.25
1





e

e
e
e
e


including SWCNTs and arc-grown multi-walled nanotubes

were considered [7]. Carbon nanotubes were selectively grown
directly on carbon paper by performing chemical vapor
deposition catalyzed with electrodeposited cobalt. The
prepared carbon nanotubes were employed as the supports
for platinum catalysts, which were electrodeposited onto the
nanotubes [8].
For comparison, similar loadings of the Pt catalyst supported on carbon nanotubes were prepared with two
approaches: the borohydride reduction method and the ion
exchange technique. It was found that the Pt/SWCNTs catalyst prepared with the ion exchange method exhibits higher Pt
utilization than the Pt/SWCNTs prepared with the borohydride reduction method. Furthermore, in comparison to an
E-TEK 20 wt.% Pt/C catalyst with the support of carbon black,
electrochemical measurements were used to show that the
Pt/SWCNTs prepared with the ion exchange method exhibit
a higher catalytic activity in methanol oxidation [9e11]. Wang
et al. tested a hydrothermal catalyst preparation process that
utilizes CNTs as a base with the aim of reducing the amount of
Pt; Pt/CNTs with 40% Pt weight were prepared. The catalyst
was characterized with IR spectroscopy, XRD, TEM, and
Proven Solution Analyzer software. Their results show that by
using the HNO3eH2O2 redox system the ports of the CNTs are
opened and that large quantities of impurities are removed.
The effects of varying the reaction temperature and time on Pt
granule size have been determined [12,13]. Pt nanoparticles of
around 1.5 nm in size that are well-dispersed on CNTs were
obtained when ethylenediaminetetraacetic acid disodium salt
(EDTAe2Na/Pt) was utilized [14].
Hu et al. have suggested that CNTs can promote electron
transfer reactions when used as electrodes. However, chemical reactions can occur that result in changes in nanotube

structure and that generate active functional groups, such as

hydroxyl and carboxyl. Hu et al. have compared the structure,
stability, and electrode kinetics of carboxyl-modified CNT
electrodes prepared by soaking in concentrated nitric acid
with those of non-modified CNT electrodes [15].
Pt and PteRu particles deposited on polypyrroleecarbon
nanotube composite polymer films exhibit excellent catalytic
activity and stability in methanol oxidation, which indicates
that composite films are promising support materials for fuel
cell applications [16,17]. The electrocatalytic properties of Pd/
MWCNT electrodes in the oxidation of hydrazine have been
investigated with cyclic voltammetry (CV); excellent electrocatalytic activity was observed, which might be due to the
small particle size and high dispersion of palladium particles
[18]. Guo et al. reported a matrix of composite films consisting
of carbon nanotubes and Nafion for the immobilization of
on glassy carbon (GC) electrode surfaces. A
Ru(bpy)2
3
composite film-modified electrode was found to exhibit better
long-term electrochemical and electrogenerated chemiluminescence (ECL) stability than a pure Nafion film-modified
electrode [19].
Ambrosio et al. were investigated the Platinum catalyst
supported on mesoporous carbon for PEMFC [20].
The effects of varying the Nafion loading in the catalyst
layer on cell performance, pore size distribution, and Pt
surface area were investigated [21,22]. The presence of Nafion

Fig. 1 e ICP curve for the platinum concentrations on the

supports.

Fig. 3 e Nyquist plots of the impedance responses from

10 kHz to 100 mHz for the GDEs including the Nafion
membrane (Nafion 112) at OCV vs. Ag/AgCl, at 25  C.

Fig. 2 e Nyquist plots of the impedance responses from

10 kHz to 100 mHz for the GDEs at 400 mV vs. Ag/AgCl, at
25  C.

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Fig. 4 e XRD patterns of GDE1, GDE2, GDE3, GDE4, and GDE5.

ionomer increases the size of the three-dimensional zone of

catalytic activity and the platinum utilization in the electrode,
and also helps to retain moisture and prevent membrane
dehydration, especially at high current densities. The Nafion
content in the electrode must be optimized to achieve high
performance. As the platinum loading increases, the electrode
thickness and the Nafion thickness increase, and hence the
optimum Nafion content can depend on the platinum loading
[23e27]. Electrodes with Pt/CNT catalysts sulfonated through
the in situ radical polymerization of 4-styrenesulfonate have
been found to exhibit better performance than their unsulfonated counterparts, mainly because of the easier access for
protons and the well-dispersed distribution of the sulfonated
Pt/CNT catalysts; thus sulfonation improves performance and
reduces the cost of Pt/CNT-based PEMFCs. A half-MEA with an
active area of 1.0 cm  1.0 cm was fabricated by employing
a Nafion 115 membrane and an in-house CNT-based gas
diffusion electrode (GDE) with a platinum loading of approx.
0.05 mg cm
2; Nafion electrolytes were not used [28]. In
a previous study [29,30], we prepared a catalyst layer containing a PANIeNafion composite.
In this paper, we introduce a new method for the preparation of MWCNT/Nafion composites, and our results with
this method are compared with those of other methods. The
main distinguishing feature of this method is in the timing of
the addition of the Nafion solution to the MWCNTs. The

effects of varying the Nafion loading in the catalyst layer on

the electrode performance and the Pt surface area were
investigated; for this purpose we fabricated four electrodes
with different amounts of Nafion (0.5, 0.75, 1, and
1.25 mg cm
2). The performance of these electrodes in the ORR
was compared with that of an electrode with MWCNTs as a Pt
support and a Nafion loading of 1 mg cm
2. Furthermore, the
electrodes were characterized with cyclic voltammetry (CV),
linear sweep voltammetry (LSV), electrochemical impedance
spectroscopy (EIS), chronoamperometry, scanning electron
microscopy (SEM), transmission electron microscopy (TEM),
and X-ray diffraction (XRD). The new method was found to
result in better performance and lower resistance.

Fig. 5 e Cyclic voltammetry curves for the GDEs for a scan

rate of 50 mV sL1.

Fig. 6 e IeV curves of the GDEs in the ORR for a scan rate of
1 mV sL1 at 25  C.

2.

Experimental

2.1.

Composite preparation

In this research, we fabricated four composites with various

amounts of Nafion. Since MWCNTs are chemically inert, the
MWCNTs (20e30 nm Aldrich) were functionalized by pretreatment with 70% nitric acid in order to introduce surface
oxides before preparation of the composites [3,4,15,18]. In our

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study, the MWCNTs were refluxed under constant agitation at

120  C in concentrated nitric acid for 12 h. The solid phase was
removed by filtration and washed with distilled water, and the
recovered functionalized MWCNTs were then dried at 80  C
for 12 h.
The composites were prepared from the dried samples and
Nafion solution (5% from Aldrich). Mixtures of functionalized
MWCNTs and various amounts of Nafion solution in 2-propanol (Merck), water, and glycerol (Merck) were sonicated for
20 min with a sonicator (Misonix model S-3000) to prepare
homogeneous suspensions; these suspensions were dried at
70  C.
Four MWCN/Nafion composites were prepared, each containing a different amount of Nafion. The resulting electrodes
contained 0.5, 0.75, 1, and 1.25 mg cm
2 of Nafion in the
catalyst layer and were named GDE1, GDE2, GDE3, and GDE4,
respectively.

2.2.
Preparation of Pt/MWCNT and Pt/composite
(NafioneMWCNT)
In this step, Pt was deposited on the MWCNT/Nafion
composites. One additional electrode named GDE5 in which Pt
was deposited on functionalized MWCNTs was prepared.
The MWCNT/Nafion composites for GDE1eGDE4 and the
functionalized MWCNTs for GDE5 were vigorously mixed with
H2PtCl6 solution in a 2-propanol (Merck) and water (1:3 v/v)
solvent mixture at 50  C for 6 h. These suspensions were then
heated to 80  C, and the pH of each suspension was adjusted

to 8.5 with a 0.5 M Na2CO3 solution. An abundant amount of

sodium formate (HCOONa) [Merck] was added to perform
a chemical reduction for 2 h. Each suspension was then
filtered, washed, and dried at 90  C for 4 h. Our ICP results
indicated that the samples contained 6.7 wt.% Pt, and so GDEs
could be prepared from the Pt/functionalized MWCNTs and
the Pt/MWCNT/Nafion composites.

2.3.

Fabrication of the GDEs

For the diffusion layer, a mixture of 30 wt.% PTFE and 70 wt.%

Vulcan in 2-propanol (Merck), water, and glycerol (Merck) was
sonicated for 20 min with a sonicator (Misonix model S-3000)
to produce a homogeneous suspension. The suspension was
rolled onto the carbon paper (TGPH-0120T) (Toray), and the
electrode was dried in air at 120  C for 1 h and then finally
sintered at 340  C for 30 min. The loading of Nafion in the
diffusion layer was fixed at 1 mg cm
2 [31,32].
To prepare the catalyst layers in GDE1eGDE4, a homogeneous suspension containing the desired amounts of the
Pt-MWCNT/Nafion composite (6.7 wt.%), glycerol (Merck),
2-propanol (Merck), and water was sonicated for 20 min. This
suspension was rolled onto the diffusion layer; the electrode
was then dried at 40  C for 30 min and then at 80  C for 30 min.
The Pt loading was 0.3 mg cm
2.
To prepare the catalyst layer of GDE5, a homogeneous
suspension containing the desired amounts of Pt/MWCNT
(6.7 wt.%), Nafion solution (5% from Aldrich) in glycerol,
2-propanol, water, and glycerol was sonicated for 20 min. This
suspension was rolled onto the diffusion layer; the electrode
was dried at 40  C for 30 min and then at 80  C for 30 min. The
Pt loading was 0.3 mg cm
2.

2.4.

Electrochemical measurements

An EG&G Princeton Applied Research Model 273A instrument

was used to determine the electrochemical properties of the
electrodes. The performances of the porous GDEs (geometric
exposed area 1 cm2) in the reduction of oxygen were investigated in 2 M H2SO4. All measurements were performed at 25  C
in a conventional three-electrode cell, with O2 flowing at
50 mL min
1. The GDEs were mounted into a Teflon holder
that contains a pyrolytic graphite disk as a current collector
and has provision for feeding oxygen from the back of the

Fig. 7 e Graphical representation of the Nafion ionomer

position in catalyst layer.

Fig. 8 e Chronoamperograms of the GDEs in the presence

of O2, E [ 0.4 V vs. Ag/AgCl, at 25  C, not stirred the
solution.

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electrode. A large area platinum flat electrode was used as

the counter electrode. An Ag/AgCl reference electrode was
placed close to the working electrode surface. A rotating disk
electrode immersed in 2 M H2SO4 with a rotation rate of
1500 rpm was used to perform cyclic voltammetry. The electrochemical cell was connected to a potentiostategalvanostat
(EG&G Model 273A) for IeV polarization measurements and
chronoamperometry, and to a frequency response detector
(model 1025) for electrochemical impedance spectroscopy. In
order to perform a quantitative evaluation of resistance
against the ORR, the AC impedance method was used. In the
Nyquist plot of the semicircle diameter, Rp is the polarization
resistance and the sum of the electrode and electrolyte
resistance that was subtracted for these GDEs. The polarization resistance is the sum of two terms: the charge transfer
and diffusion resistances. Impedance measurement was
investigated in 0.4 V vs. Ag/AgCl potential for obtaining Rp.
This potential is in ohmic resistance region. The AC potential
amplitude was 5 mV, and the frequency range was
10 kHze0.1 Hz. We used impedance measurements to characterize the ionic resistances of the electrodes. At low
frequencies, a Warburg-like response (45 slope) is observed,
which indicates the occurrence of ion migration through the
Nafion membrane and catalyst layer. The ionic resistance Rion
can be obtained from the length of the Warburg-like region
projected onto the real impedance (Zreal) axis [33,34,35]. For
obtaining Rion, the impedance measurement has been investigated in OCV potential and experimental complex-plane
impedance plots (10 kHze0.1 Hz) for Argon-bathed are shown
in Fig. 3.

2.5.
Measurements of the physical properties of the
electrodes
A scanning electron microscope (Model XL30, Philips co.) was
used after coating the electrodes surfaces with gold, a transmission electron microscope (TEM/STEM CM Philips 200) was
used to produce the TEM images, and XRD analysis was
carried out for the catalysts by using an XPERT MPD Philips
diffractometer with a Cu X-ray source operating at 40 kV and

Fig. 9 e SEM image of the catalyst layer of GDE1

(0.5 mg cmL2 Nafion in a MWCNT/Nafion composite) at
a magnification of 15,0003.

13329

40 mA. The XRD patterns were obtained at a scanning rate of

1 /min with a step size in the 2q scan of 0.02 in the range
20e100 .
The amount of Pt reduced on each support was determined
by using the inductive coupled plasma (ICP) technique (ICPOES, Varian Vista-PRO, Australia); for these measurements we
dissolved 5 mg of each sample (synthesized Pt on the
supports) and standard samples (Pt/C 10% and 20% wt) in
a mixture of hydrochloric acid and nitric acid (3/1). These
solutions were refluxed at 70  C and then used in the ICP
measurements.

3.

Results and discussion

The GDEs (1e5) were prepared with different amounts of

Nafion, as explained in Experimental section and Table 1. The
results are shown in Figs. 1e16 and in Table 2.
The ICP results indicate that the Pt loading in these GDEs is
0.3 mg cm
2 (Fig. 1).
As mentioned above, there are three participants in electrochemical reactions: gases, electrons, and protons. The
reactions can only take place on portions of the catalyst
surface to which all three participants have access. The electrons travel through the electrically conductive solids,
including the catalyst itself, so it is important that the catalyst
particles are electrically connected in some way to the
substrate. Protons travel through the ionomer, so the catalyst
must also be in intimate contact with the ionomer. Finally, the
reactant gases travel only through voids, so the electrode
must be sufficiently porous to allow gases to travel to the
reaction sites. At the same time, product water must be
effectively removed or the electrode will flood and prevent
oxygen access. The reactions take place at a three-phase
boundary between ionomer, solid, and empty space [32].

3.1.

AC impedance spectroscopy

To gain more information about the GDEs (GDE1eGDE5), the

a.c. impedance spectrum of each electrode was obtained. The

Fig. 10 e SEM image of the catalyst layer of GDE2

(0.75 mg cmL2 Nafion in a MWCNT/Nafion composite) at
a magnification of 15,0003.

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resulting data were obtained at 400 mV vs. Ag/AgCl saturated

with KCl, and were plotted in the Nyquist representation. The
polarization resistance Rp was found to be lower for GDE3,
which contains 1 mg cm
2 Nafion in the catalyst layer, than
for the other GDEs. Although the impedance spectra have
similar semi-circular shapes, the diameters of the semi-circles
differ significantly. As shown in Fig. 2, the resistances of GDE1,
GDE2, and GDE4 are too high in comparison with those of the
other electrodes. When the amount of Nafion in the GDEs is
increased from 0.5 to 0.75, the resistance of the electrode
decreases. However, upon an additional increase in the
amount of Nafion, a high resistance is observed, i.e., in GDE4.
The high resistance of this electrode is due to an excess of
Nafion in the catalyst layer. Therefore, we should optimize the
amount of Nafion in the GDEs. One approach is to suggest that
the optimum value of the amount of Nafion arises for the GDE
with the lowest resistance, so GDE3 is then the best electrode.
In the case of GDE5, the ionomer blocks the catalyst sites, so
the resistance of electrode GDE5 is higher than that of GDE3.
The ionic resistance or proton transport of each GDE was
determined by using a half-cell assembly in a conventional
three-electrode system; the working electrode contained
carbon paper, MPL, catalyst layer, and a Nafion 112
membrane. The results are shown in Fig. 3 and Table 2: GDE3
has the lowest ionic resistance, which is attributed to its
optimum three-phase zone.

3.2.

XRD pattern of platinum

0:9l
B2q cosq

(1)

where d is the average particle size, l is the wavelength of the

X-ray (1.54056 
A), q is the angle at the maximum of the peak,
and B2q is the width of the peak at half-height. This variation
in the crystal size of Pt arises because the support of Pt in each
sample is different.
These results show that Nafion plays an important role
during the synthesis and that varying the concentration of
Nafion has some influence on the formation of the Pt particles,
i.e., the concentration of Nafion influences the reduction of
platinum on the surface of the MWCNTs. In the preparation of
GDE5, the Pt nuclei grew as soon as the reducing agents,
sodium formate (HCOONa), was added to the mixture, i.e.,
before they were covered with Nafion. This growth resulted in
the inferior performance of GDE5 in comparison with those of
GDE2 and GDE3 since some of its Pt particles were masked by
Nafion, which was added to this mixture after the coating of
Pt onto the MWCNT support. Since the Pt particles are covered
with Nafion, the concentration of exposed Pt on the surface
of the MWCNT support is reduced; therefore, the performance
of GDE5 decreases. This conclusion is verified by the XRD
pattern for GDE3 (see Fig. 4).

3.3.

Electroactive surface area (EAS)

The cyclic voltammograms for GDEl, GDE2, GDE3, GDE4, and

GDE5 are shown in Fig. 5. The coulombic charge for hydrogen
desorption was used to calculate the electroactive surface
area (EAS) of each electrode (Table 2) [36]:

Fig. 4 shows the XRD patterns of the Pt/MWCNT and PtMWCNT/Nafion composite nanocatalysts. The peak at
2q 26.5 corresponds to the (002) planes of the graphitized
MWCNTs and the peaks at 2q 39.8 , 67.5 , and 46.2 are
associated with the (111), (220), and (200) planes of fcc (face
centered cubic) Pt, respectively. These results indicate that Pt
has been successfully reduced. The average sizes of the Pt
particles were calculated from the line broadening of the (111)
peak by using the Scherrer equation after background
subtraction and found to be 0.76, 3.57, 3.59, 1.64, and 0.75 nm
for the five samples, respectively (Table 2).

where Qh is the charge for hydrogen desorption (mC cm
2) and

[Pt] is the platinum loading (mg cm
2) and 0.21 (mC cm
2) is
the charge required to oxidize a monolayer of H2 on bright Pt.
The roughness factor (Rf) can then be calculated by using the
following equation:

Fig. 11 e SEM image of the catalyst layer of GDE3

(1 mg cmL2 Nafion in a MWCNT/Nafion composite) at
a magnification of 15,0003.

Fig. 12 e SEM image of the catalyst layer of GDE4

(1.25 mg cmL2 Nafion in a MWCNT/Nafion composite) at
a magnification of 15,0003.

EAS

Qh
0:21  Pt

(2)

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Rf

EAS
S

(3)

where S is the geometric surface area (m2 g
1). These results

are tabulated in Table 2 and are consistent with those of other
studies [2,17,29].
The polarization curves for the GDEs in conventional threeelectrode cells are presented in Fig. 6. The current density
values are considerably greater for GDE3 than for the others,
which indicate that the performance of this cell is much better
than that obtained when using an electrode containing the
MWCNT/Nafion composite (1 mg cm
2 of Nafion). The superior performance of GDE3 is attributed to an increase in the
size of the three-dimensional reaction zone and to the
optimum value of Nafion in the MWCNT/Nafion composite. As
a result, the concentrations of the reactants near the surface
of the catalyst are increased, and hence the reaction rate is
improved.
The performances of GDE1 and GDE4 are very poor. The
poor electrode performance for a low Nafion content (GDE1)
might be due to the presence of fewer electrochemically active
sites in the three-phase zone, and the decrease in performance for a high Nafion content (GDE4) might be due to
reduced gas permeability and increased mass transfer polarization. Further, the electrochemically active surfaces of the
GDEs were calculated from the CV data and are shown in
Table 2. These results indicate that the performance of GDE3 is
better than that of GDE5. This superiority of GDE3 is attributed
to better catalyst accessibility; in other words, when the
MWCNT/Nafion composite is used as the Pt support, the
accessible catalyst surface is greater in GDE3 than in Pt/
MWCNT (GDE5), in which the surface of Pt particles is blocked
by the Nafion ionomer. As mentioned above, the reactions in
these catalysts occur in a three-phase zone, i.e., where the
ionomer, solid, and empty space phases meet (Fig. 7a). The
reaction zone can be expanded by either roughening the
surface of the membrane or by adding ionomer to the catalyst
layer (Fig. 7b). The whole surface of the catalyst can be
screened by a thin ionomer layer (Fig. 7c), except at the electrical contacts. In two extreme cases, the entire catalyst layer
can be protected by the ionomer layer and there is then no

Fig. 13 e SEM image of the catalyst layer of GDE5

(1 mg cmL2 Nafion) at a magnification of 15,0003.

13331

electrical contact with the electrically conductive support

(Fig. 7d) or there is no ionomer in contact with the Pt particles
(Fig. 7e). These considerations show that the ratios of the
catalyst area covered by ionomer to the catalyst area open to
empty space and to the catalyst area in contact with other
catalyst particles or the electrically conductive support should
be optimized [32].

3.4.

Kinetic parameters

The kinetic parameters of the ORR for a GDE can be obtained

from the polarization data. Our analysis of the experimental
polarization data was performed by using the Tafel equation
[37]:
h
blog

i
i0

(4)

where:
h E
Eeq

(5)

h is the over-potential, Eeq is the open-circuit voltage, b is the

Tafel slope, i is the current density, and i0 is the exchange of
current density for the ORR. The kinetic parameters of the ORR
for the GDEs can be obtained from the IeV curves and these
equations.
The Tafel slopes and the current densities of the GDEs at
0.9 V are shown in Table 2. These results indicate that the best
performance is exhibited by GDE3. To achieve maximum
efficiency, it is necessary to prepare an environment with
a triple interface comprised of Nafion, platinum, and oxygen.
Therefore, we conclude that in GDE3 the amount of Nafion is
optimized and the triple zone is more reliable. As mentioned
in the previous section, catalyst accessibility is better in GDE3
than in GDE5, and thus the rate of the ORR and the current
density are improved.

Fig. 14 e TEM image of the catalyst layer of GDE2

(0.75 mg cmL2 Nafion in a MWCNT/Nafion composite).

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Fig. 16 e TEM image of the catalyst layer of GDE5

(1 mg cmL2 Nafion).

Fig. 15 e TEM image of the catalyst layer of GDE3

(1 mg cmL2 Nafion in a MWCNT/Nafion composite).

3.6.
3.5.

Chronoamperometry

The diffusion coefficients of O2 in the GDEs were determined

with chronoamperometry. For large electrodes, the information obtained was limited by the Cottrellian decay with time.
According to Winlove et al. [38], the time window for these
experiments follows the relation 1 > s
1/2 > 0.5, where s is
a dimensionless parameter equal to 4Dt/r2. The Cottrell [39]
equation is:
i nFAD=pt1=2 C)

(6)

where i is the limiting current (mA), n the number of electrons,

F is the Faraday constant (96485 C mol
1), A is the surface area
of the electrode (cm2), D is the diffusion coefficient (cm2 s
1), t
is the time (s), and C* is the concentration of the reactant.
The highest value of the permeability (D1/2  C*) was
obtained for GDE3 (Fig. 8 and Table 2). This result is consistent
with the enhancement of the diffusion of oxygen in the
reaction layer of this MWCNT/Nafion composite due to its
optimum level of Nafion.

SEM and TEM results

The electrode layer is composed of Pt agglomerates and

a Nafion film. The catalytic layer usually has a dual pore
distribution: micro pores are present in the agglomerates,
and macro pores are located between the agglomerates. The
Nafion is likely to be localized in the macro pores in contact
with the Pt agglomerates. A further complication arises
because reactant diffusion does not often occur in the
gaseous phase through the electrode; instead, the reactant
dissolves in the electrolyte and then diffuses into the solution. In this model, we expect that the reaction of oxygen
(electro-reduction) is controlled by the following transport
processes: (1) oxygen diffusion into the pore space of the
electrode and dissolution into Nafion; (2) oxygen diffusion
through the Nafion layer; and (3) proton transfer in the
Nafion layer. We carefully controlled the fabrication process
to prevent the effect of fabrication process on the Pt
morphology. We emphasize that the loading of Nafion varies
in the GDEs (GDE1eGDE4), which means that the
morphology of the reduced Pt particles will vary from
support to support, as shown by the XRD results (Fig. 4).

Table 2 e Tafel slopes, current densities, permeabilities, charge transfer resistances, ionic resistances, electroactive surface
areas, and roughness factors of the GDEs.
GDE
1
2
3
4
5

b
(mV dec
1)

i  10
4
at 0.9 V (A cm
2)

(D1/2  C*) 10
9

(mol cm
2 s
1/2)

EAS
(m2 g
1)

Rf

Rp ( ohm)

Rion/3 (ohm)

d (nm)

71
73
70
86
75

11.3
15.1
16.8
10.4
13.7

11.9
28.0
32.1
11.5
24.0

15.4
39.7
44.1
22.4
36.6

51
132
147
74
122

1.4
1.2
0.8
1.3
1.3

66.7
10.9
5.3
64.6
31.0

0.76
3.57
3.59
1.64
0.75

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 6 ( 2 0 1 1 ) 1 3 3 2 5 e1 3 3 3 4

Therefore, a low Nafion content (less than 0.75 mg cm
2) is

not desirable since good contact between the catalyst, electrolyte, and reagents is reduced; without such contact the
integrity of the catalyst layer and the membrane, and the
proton conductivity are insufficient. At high ionomer loadings (1.25 mg cm
2, GDE4), the proton conductivity is
enhanced, but the catalyst active area is then expected to be
limited (Table 2) by the formation of a thick Nafion layer on
the catalyst surface, which then reduces the electroconductivity of the Pt layer. We also note that the mechanical integrity of the catalyst layer is insufficient for Nafion
contents below 0.75 mg cm
2, which means that the incorporated Nafion cannot properly bind the catalyst particles.
At a Nafion content of 1.25 mg cm
2, as in GDE4 which
exhibits reduced performance, the thick Nafion layer
reduces the catalyst active area in spite of the enhanced
proton conductivity in the catalyst layer. On the basis of our
results, a Nafion content of 1 mg cm
2 (GDE3) optimizes
proton transfer within the catalyst layer without limiting
oxygen diffusion. Figs. 9e13 show that the number and size
of the pores are different in each catalyst. Thus the number
and the size of the pores in GDE3 have optimum values,
which improve its performance in the ORR. As we expected,
Fig. 13 shows that the Pt/MWCNT surface is covered by the
Nafion ionomer; this means that some active sites are
blocked and the performance of GDE5 in the ORR is inferior
to that of GDE3.
TEM images of GDE2, GDE3, and GDE5 are shown in Figs.
14e16; these images confirm the details of the above
discussion.

4.

13333

Appendix. Nomenclature

A
geometricarea of electrode
b
Tafel slope
width of the peak at half-height
B2q
C*
concentration of the reactant
d
average particle size
D
diffusion coefficient
D1/2  C* permeability
EAS
electroactive surface area
open-circuit voltage
Eeq
F
Faraday constant
i
current density
exchange current density
io
MEA
membrane electrode assembly
MPL
micro pore layer
n
number of electrons
OCV
open-circuit voltage
polarization resistance
Rp
roughness factor
Rf
S
catalyst surface area
t
time
h
over-potential
q
angle at the maximum of the peak
l
wavelength of the X-ray
r
density

references

Conclusion

The influence of the Nafion loading in the catalyst layer

on electrode performance was studied; four different
GDEs were prepared by using MWCNT-Nafion composites
(with varying amounts of Nafion) as Pt supports, and the
performances of these GDEs and of Pt/MWCNT were
compared.
A simple, fast, and energy-efficient method for the preparation of Pt/MWCNTeNafion composites and Pt/MWCNT
catalysts with high electrocatalytic activity was developed.
We have shown that the timing of the addition of Nafion to the
catalyst layer is very important and prepared an electrode
(GDE3) that exhibits excellent performance in the ORR. Our
XRD results indicate that the Pt particles were reduced
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GDE2, GDE4). The superior performance of this electrode can
be attributed to better reactant accessibility to the three-phase
zone. The present technique can be used as a general method
for the preparation of supported metal particles from metal
precursors.

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