Advances in Fuel Cells - Chapter 2

Research Signpost
37/661 (2), Fort P.O., Trivandrum-695 023, Kerala, India
Advances in Fuel Cells, 2005:

Editor: Xiang-Wu Zhang
ISBN: 81-308-0026-8
Privileged materials for direct

methanol fuel cells
Loka Subramanyam Sarma and Bing Joe Hwang
Nanoelectrochemistry Laboratory, Department of Chemical Engineering
National Taiwan University of Science and Technology, Taipei 106, Taiwan
Republic of China
Abstract
Direct methanol fuel cells (DMFCs) have a
continuous supply of methanol as the fuel to the anode
and convert chemical energy directly into electrical
energy with high-energy density and low emission of
pollutants. DMFCs are about to come of age as power
sources for electric vehicle, transport applications
and portable electronic devices including lap tops,
cell phone power packs, generators, and other powerhungry products. One of the major challenges in the
commercialization of DMFCs is the high cost of noble
metal-based electrocatalysts and state-of-the-art
Correspondence/Reprint request: Dr. Bing Joe Hwang, Nanoelectrochemistry Laboratory, Department of
Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan, Republic
of China. E-mail: bjh@ch.ntust.edu.tw
Loka Subramanyam Sarma & Bing Joe Hwang
Nafion membranes. In this regard major research efforts have been directed
towards finding innovative materials with attributes such as decreased catalyst
loadings, optimum fuel and proton access to the active sites, electronic
continuity in the carbon supports and low methanol permeability in the proton
exchange membranes. In this chapter we described the recent progress
including our own work in search and development of innovative
electrocatalysts both for methanol oxidation reaction (MOR) and oxygen
reduction reaction (ORR), carbon supports, and proton exchange membranes
alternative to Nafion.
1. Introduction
Direct methanol fuel cells (DMFCs) are promising energy sources for
vehicle and portable devices because of its high-energy conversion efficiency,
low-to-zero pollutant emission, methanol fuel availability, high-energy density
of the fuel (6000 Wh/kg), and low operating temperatures (60 to 100 oC) [13].
When compared to the emissions from conventional internal-combustionengined vehicles (ICEVs), the emissions from DMFCs at an operating
temperature range from 60 to 80 oC are significantly lower. Apart from the
principle emitters such as CO2 and H2O traces of formaldehyde can also be
found. However, due to the inherent higher efficiency of DMFCs, the extent of
carbon monoxide emission is substantially lower than that from ICEVs [4].
With the strict environmental laws and due to the increased concerns on the
consequences of fossil fuel usage in power generation and propulsion of
vehicles, much efforts have been focused on the development of powerful,
clean and finely distributed power generation and development of DMFCs
comes under this aim. Despite the significant progress, DMFCs still suffer
from many obstacles such as low power density, which has been attributed to
the poor kinetics of both anode [5], and cathode [6], high flux of
water/methanol across membranes [7], and mixed potential at cathode [8].
These phenomena lead to high overpotentials involving methanol cross-over
overpotential, activation overpotential, and concentration overpotential at both
the anode and the cathode sides and, hence, reduction in cell voltage. Other
important constraints are the high cost of noble metal catalysts and
perfluorosulfonic membranes and higher production costs of the various
components of the device.
A great deal of effort has been devoted over the years to the development
of innovative materials for DMFCs and in this chapter; we describe recent
progress in the development of carbon supports, electrocatalysts both for
methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR), and
proton exchange membranes alternative to state-of-the art Nafion membrane
for DMFCs. Before discussing these issues in details we will discuss briefly
Privileged materials for direct methanol fuel cells
the two principle reactions in DMFCs such as methanol oxidation reaction

(MOR) and oxygen reduction reaction (ORR) in the following paragraphs.
2. Principle reactions in DMFCS

The principle and schematic diagram of a DMFC is shown in Figure 1. In
a typical DMFC, methanol and water molecules are simultaneously electrooxidized at anode to produce CO2, electrons and protons through the reaction
(methanol oxidation reaction, MOR):
CH3OH + H2O CO2 + 6H+ + 6e [Ea = 0.02 V vs. SHE]
(1)
Protons generated at the anode pass through the proton exchange

membrane to cathode and combine with the electrons and the oxidant air or
oxygen simultaneously reducing to water as (oxygen reduction reaction, ORR):
3/2O2 + 6H+ + 6e 3H2O [Ec = 1.23 V vs. SHE]
(2)
Reactions (1) and (2) can be combined to give the overall reaction:
CH3OH + 3/2O2 CO2 + 2H2O [Ecell = 1.21 V]
(3)
The free energy (G) of overall reaction at 25 oC and 1 atm is 686

kJmol1CH3OH [9].
The free energy (G) of overall reaction at 25 oC and 1 atm is 686
kJmol1CH3OH [9].
Figure 1. Schematic drawing and principle of a DMFC single cell depicting H+, H2O
and CH3OH transport through the proton exchange membrane (PEM).
2.1. Methanol oxidation reaction (MOR)

The oxidation of methanol and water molecules is the principle reaction
occurring at anode of DMFCs. Pt is the best material for the adsorption and
dehydrogenation of methanol. However, formation of intermediate species
such as CO [10], formic acid and formaldehyde poison the platinum anode and
impede the catalytic performance for methanol oxidation. Among them
poisoning from CO species is severe on Pt electrode surface during the electrooxidation of methanol. The detailed methanol oxidation mechanism for the
oxidation of methanol at Pt electrodes, involving the adsorption of CH3OH and
its successive dehydrogenation, yielding linearly bonded CO, has been
proposed by Beden et al. [11]. The methanol is adsorbed on Pt surface
(equation 4) and then undergoes a sequence of dehydrogenation steps to yield
linearly bonded CO species (equations 5a to 5d), as represented below:
Pt + CH3OH Pt (CH3OH)ads
(4)
Pt (CH3OH)ads Pt (CH3O)ads + H+ + e
(5a)
Pt (CH3O)ads Pt (CH2O)ads + H+ + e
(5b)
Pt (CH2O)ads Pt (CHO)ads + H+ + e
(5c)
Pt (CHO)ads Pt (CO)ads + H+ + e
(5d)
On the pure Pt surface water dissociation will occur only at higher anodic
overpotentials to form Pt(OH)ads species (equation 6):
Pt + H2O Pt(OH)ads + H+ + e
(6)
The last step is the reaction of PtOH species with Pt-adsorbed CO to give
carbon dioxide (equation 7):
Pt (CO)ads + Pt(OH)ads 2Pt + CO2 + H+ + e
(7)
At potentials of technical interest for DMFCs (<0.6 V vs. RHE) the

dissociation of water on Pt surface is the rate determining step [12].
However, water dissociation will occur at less positive potentials on
promoter metal M like Ru (0.2 V vs. RHE) and Ru0 transfers oxygen more
effectively than Pt0 (equation 8 to equation 10) [13, 14]:
M + H2O M(H2O)ads
(8)
M(H2O)ads M(OH)ads + H+ + e
Pt (CO)ads + M(OH)ads Pt + M + CO2 + H+ + e
(9)
(10)
During methanol oxidation the efficient catalyst must allow a complete

oxidation to CO2. Currently, carbon-supported PtRu catalysts have been
shown to be among the best candidates for electrochemical oxidation of
methanol at anodes of DMFCs [15, 16]. A Pt/Ru atomic ratio of 1:1 was
reported as the preferred atomic composition [17, 18].
The enhanced electrocatalytic activities enabled by promoter metals such
as Ru, Sn, Mo or Os in mixed PtM catalysts have been explained by the socalled bifunctional mechanism [13, 14, 19, 20] and the ligand (electronic)
mechanism [2124].
In the bifunctional mechanism the promoter metal is oxophilic and
thought to provide sites for water adsorption thereby increasing the methanol
oxidation rate through bimolecular surface reaction. In the ligand effects the
promoter metal can alter the electronic state of the Pt by contributing delectron density, facilitates weakening of PtCO bond and thus easy removal
of CO is expected. Lu and Masel have noticed that bifunctional effect has a
larger effect on CO removal than the ligand effect when they used 0.25
monolayers of Ru deposited on Pt (110) surface in ultra-high-vacuum (UHV)
conditions. They found that out of the 46 kcal/mol (170260 meV) reduction
in the potential for CO removal, only about 1 kcal/mol (40 meV) is associated
with the ligand effect, whereas 35 kcal/mol (130 to 220 meV) is associated
with the bifunctional mechanism [25].
With the advent of computational methods more fundamental insights into
the CO oxidation mechanism can be obtained. Ishikawa et al have studied the
adsorption of CO on PtM metal surfaces (M = Ru, Sn or Ge) with the
relativistic density-functional self-consistent field X method. From their
results it was found that the presence of M atoms weakens the PtC bond, and
generally slightly lowers the CO stretching frequency of adsorbed CO.
Substitution of Ru and Sn for platinum is found to alter the dissociation energy
of H2O. The results indicate that the promoting effect of alloying atoms
involves both modification of PtCO binding and water activation [26].
2.2. Oxygen reduction reaction (ORR)

The electroreduction of O2 is a multielectron reaction and depending on
the experimental conditions it is known to take place through two different
reaction pathways: the direct four-electron pathway (equation 11) in which O2
is reduced directly to water and the two-electron pathway (equation 12) in
which O2 is reduced to peroxide followed by the decomposition or further
reduction to water [2729]
O2 + 4 H+ + 4 e 2 H2O (E0 = 1.23 V vs. SHE)
(11)
O2 + 2 H+ + 2 e H2O2 (E0 = 0.67 V vs. SHE)
(12)
Platinum has long been the best electrocatalyst for ORR, and oxygen
reduction over platinum and other Pt bimetallic surfaces has been reviewed
recently [3032]. As discussed in these reviews, over the three low-index
(100), (111), and (110) platinum surfaces in aqueous perchloric and sulphuric
acid, the complete four-electron reduction to water can be observed. Two
electron reduction to hydrogen peroxide occurs on the Pt (111) surface in the
hydrogen adsorption region which is an evident of surface site blocking by
H(ads). Equally OH(ads), which begins forming from water decomposition at
about 0.6 V on platinum electrodes, is also believed to inhibit oxygen
reduction by blocking surface sites, and it may contribute to the need to
operate oxygen electrodes at several millivolts relative to the 1.23 V reversible
potential on the standard hydrogen scale.
On Pt electrode surface the adsorption and reduction of O2 via fourelectron reduction pathway follows the steps (equation 13a13d):
PtO2 + H+ + e PtOOH
(13a)
PtOOH + H+ + e
(13b)
PtO + H2O
PtO + H+ + e PtOH
(13c)
PtOH + H+ + e PtOH2
(13d)
Sidik and Anderson have applied density functional theory to study the
four-electron reduction mechanism of O2 on platinum in aqueous acidic
electrolytes [33]. Their studies suggest that the first electron transfer step
(equation 13a) is the rate determining step. They have calculated the activation
energy for the rate determining step which is of about 0.60 eV at 1.23 V and
close to the experimental value of 0.44 eV on Pt (111) in H2SO4.
In the two-electron reduction pathway the O2 reduction follows the steps
(equation 14a14b):
PtO2 + H+ + e PtOOH
(14a)
PtOOH + H+ + e Pt(OHOH)ads
(14b)
The adsorbed peroxide in equation 14b can be electrochemically reduced to

water (14c14d):
Pt(OHOH)ads + H+ + e Pt(OH) + H2O
(14c)
Pt(OH) + H+ + e PtOH2
(14d)
or catalytically decomposed on the electrode surface, or can be desorbed into

the bulk of the solution. Although a number of important problems pertaining
to the interpretation of the reaction pathway for the ORR on Pt (hkl) have not
yet resolved, recent studies of Markovic et al suggest that a series pathway
via an (H2O2)ad intermediate may be operative on Pt and Pt bi-metallic surfaces
[30, 3436].
Because of the high cost of platinum and the slow kinetics of the oxygen
reduction, many efforts have been directed on finding alternative catalysts [37,
38]. Studies involving partial substitution of Pt with other transition metals like
Co, Cr and Ni have indicated that these alloyed materials showed better
performance towards ORR [3941]. Even though significant progress has been
achieved in improving the ORR kinetics, mixed potential at the cathode due to
the methanol cross over from anode makes the overpotential of this reaction at
the desired current densities (e.g. 500 mA cm2) about 420450 mV in
DMFCs.
3. Privileged materials for DMFCS

At present the two most technical challenges for commercialization of
DMFCs are the high cost of noble metals used in both anode and cathode
materials and methanol crossover to the cathode [42, 43]. One way to solve the
issue of high cost of noble metals is to decrease the amount of Pt used in
DMFC catalysts via the increase of the utilization of Pt and this attains priority
research during the past decade. For the effective utilization of the Pt-based
catalyst, the Pt must have simultaneous access to the fuel, the electron and the
proton-conducting mediums. In general this could be achieved by blending the
carbon-supported Pt catalyst and proton conducting Nafion solution in a
skillful manner. However, Pt utilization rates are at only 2030% even in
commercially available advanced electrodes. Efforts directed at improving the
utilization efficiency of the Pt catalyst have focused on finding the optimum
material configurations while minimizing the Pt loading and satisfying the
requirements of gas access, proton access, and electronic continuity. In order to
avoid the mixed potential at cathode, methanol-tolerant cathode catalysts need
to be developed.
3.1. Carbon supports

During the recent years many efforts are aimed to decrease the amount of
Pt used in a DMFC via the increase of the utilization efficiency of Pt by
finding innovative carbon materials capable of accommodating high metal

dispersion. In order to achieve the highest Pt utilization efficiency, the Pt
catalytic site must have simultaneous access to the fuel, the electronconducting medium, and the proton-conducting medium. Carbon is a suitable
material for supporting metallic nano particles in the electrode for DMFCs
[4446]. Carbon material is the best choice owing to its essential properties
such as electronic conductivity, corrosion resistance, surface properties, and
the low cost required for the commercialization of fuel cells. The important
requirements of carbon materials as supports for platinum-based electrocatalyst
include (1) high surface area for a high degree of dispersion of nanosized
catalysts, (2) good crystallinity or low electrical resistance to facilitate electron
transport during the electrochemical reactions, (3) pore structure suitable for
maximum fuel contact and byproduct release, and (4) good interactions
between the catalyst nanoparticles and the carbon support. Recent research
works have been focused to find out carbon materials with these properties.
So far the most widely used commercial carbon support is the Vulcan XC72 (Cabot) with a BET surface area 240 m2 g1. However in order to achieve
the highest catalyst utilization efficiency the carbon materials with a good
electron conductivity and a well-controlled nanostructure involving high
surface area together with a well developed porosity are developed and
demonstrated as supports for fuel cells.
3.1.1. Carbon nanotubes (CNTs)

In recent years carbon nanotubes have been developed as supports for
low-temperature fuel cells due to their unique structural, mechanical, and
electrical properties. Carbon nanotubes have found to be promising materials
to replace traditional carbon black powders [4751]. Xin research group has
synthesized carbon nanotubes (CNTs) from high-purity graphite by a classical
arc-discharge evaporation method (47). The BET surface area of the
synthesized CNT is about 42 m2 g1 and Pt nanoparticles of spherical shape
with an average particle sizes from 2 to 4 nm can be dispersed homogeneously.
Using the Pt/CNT as cathode catalysts in DMFC single cell produces better
performance compared to Vulcan XC-72 carbon. The high electro-catalytic
activity may be attributed to the unique structure and better electronic
properties of the CNTs, as well as to the specific interaction between Pt and
CNTs. However, these results did not address the Pt utilization within the
catalyst layer.
In a modified approach Yan et al have demonstrated the increased
utilization of Pt by growing multiwalled carbon nanotube arrays directly on the
carbon paper and then subsequently electrodepositing the Pt selectively on the
carbon nanotubes [52]. They explained that this strategy can promise to
improve the Pt utilization by securing the electronic route from Pt to the
supports in a PEMFC. The use of carbon nanotubes and the resulting feasible
electronic pathway eliminate the problem of isolation of carbon particles from
the electrode support due to the presence of Nafion used in conventional
PEMFC strategies. This approach will improve the Pt utilization. The authors
have reported that Pt catalyst loadings can be achievable up to 0.2 mg cm2
with the obtained MWNT-carbon.
Girishkumar et al have demonstrated a method to obtain films of varying
amounts of single-walled carbon nano tubes (SWCNTs) on optically
transparent electrode (OTE) surfaces using electrophoretic deposition.
Platinum is electrodeposited on the SWCNT-OTE and the electrodes are
studied for methanol oxidation as well as for oxygen reduction [53]. The high
surface area and porosity of the SWCNT-OTE films enable them to use
relatively small amounts of platinum and yet obtain excellent currents.
Multiwalled carbon nanotube-supported Pt (Pt/MWNT) nanocomposites
were prepared by the aqueous solution reduction of a Pt salt (HCHO
reduction), Pt/MWNT (A) and the reduction of a Pt ion salt in ethylene glycol
solution, Pt/MWNT (B) by Liu et al [48]. The Pt/MWNT catalyst prepared by
the EG method has a high and homogeneous dispersion of spherical Pt metal
particles with a narrow particle-size distribution and the Pt particle size is in
the range of 25 nm. From their results it is found that the surface chemical
modifications of MWNTs and water content in EG solvent are the key factors
in depositing Pt particles on MWNTs. In the case of the direct methanol fuel
cell (DMFC) test, the Pt/MWNT catalyst prepared by EG reduction is slightly
superior to the catalyst prepared by aqueous reduction and displays
significantly higher performance than the Pt/XC-72 catalyst. The limited
current density and maximum power density of the single cell with the
synthesized Pt/MWNTs and Pt/XC-72 decrease in the following order:
Pt/MWNT (B) > Pt/MWNT (A) > Pt/Carbon XC-72. The authors have
concluded that by using MWNTs as supports the lower platinum loadings (1.0
mg/cm2) can be achieved. Also by lowering the agglomeration degree of metal
particles in the Pt/MWNT (B) catalyst, the reactants easy access to the
catalytic active sites, which would help to enhance the mass transport in the
cell system further, can be improved. These differences in catalytic
performance between the MWNT-supported or the carbon black XC-72supported catalysts are attributed to a greater dispersion of the supported Pt
particles when the EG method is used, in contrast to aqueous HCHO reduction
and to possible unique structural and higher electrical properties when
contrasting MWNTs to carbon black XC-72 as a support.
Liu et al have provided a method to deposit Pt nanoclusters of about 15
nm in diameter on MWCNTs by electroless deposition [49]. The MWCNTs
are first pretreated with a solution of SnCl2/HCl and next placed in a platinum
10
electroless plating solution and MWCNTs with this plating showed higher
electrocatalytic activity for oxygen reduction in a single stack PEM fuel cell.
Rajesh et al have demonstrated a method to place the catalyst on the inside
of the CNTs. Their approach involves; first the CNTs are immersed in
hexachloroplatinic acid and ruthenium chloride [54]. Then the incorporated
metal ions are reduced to the corresponding metals by exposure in hydrogen
gas at 823 K which yields a Pt or PtRu nanocluster loaded on CNT. In order
to load the inside of the CNTs with WO3, which later will be bonded to Pt for
lower activation energy in DMFCs; the CNT is immersed in peroxo tungstic
acid. This immersion allows the peroxo-tungstic acid to penetrate inside the
pores of the CNTs. Finally, the WO3/CNT structure is immersed in
hexachloroplatinic acid, dried, and reduced with hydrogen gas at 623 K. Thus
the result is a CNT with platinum tungsten-oxide nanoclusters inside.
The literature reports described in this section on CNTs as supports to
noble metal particles have reached almost similar conclusions. Most of the
researchers have concluded that the high electrocatalytic activities have been
attributed to the: (i) high and homogeneous distribution of noble metal
particles on CNTs, (ii) unique structural and high electrical properties, (iii)
larger surface area provided by the CNT architecture, (iv) specific interaction
between Pt and CNTs, and (iv) enhanced mass transport via facile access of
reactants to the catalytically active site in the fuel cell operation.
3.1.2. Graphite carbon nanofibers (GCNFs)

Graphite nanofibers (GCNFs) have been explored as potential supports for
Pt catalysts and metal supported GCNFs have been studied as electrodes for
both oxygen reduction reaction (ORR) and methanol oxidation reaction
(MOR) in single fuel cells [5557]. In their studies Bessel et al have examined
three types of GCNFs as platinum support media during MOR. The GCNF
materials possess, platelet, ribbon, and herring-bone structures [55].
These GNFs can be prepared by the catalytic decomposition of
hydrocarbons over metal catalysts composed of copper, nickel, iron, or other
bimetallic compounds. The advantage of this method is that metal nano
particles can be supported on carbon with a preferred crystallographic
orientation. For example when 5 wt% Pt is supported on platelet and ribbon
type GNFs exposes mainly edge sites to the reactant during ORR. They have
demonstrated that 5 wt% Pt on platelet and ribbon type GNFs exhibit improved
oxidation activities of 400% when compared to the Vulcan XC-72 in methanol
oxidation studies. They have explained the increased catalytic activity and
lower self-poisoning ratios of the GNF supported Pt catalysts due to various
reasons, including (a) more efficient mechanisms for the removal of the
adsorbed species, (b) increased electrical conductance of the GNF when
compared with the Vulcan carbon, (c) decreased impurities in carbon support,
11
and (d) the attainment of a preferred crystallographic orientation by the

platinum particles as a result of the interaction with the highly ordered GNF
substrate. Lukehart group has prepared a PtRu/herringbone GNF
nanocomposite using a single-source molecular precursor as the metal source
[56, 57]. The performance of the DMFC with this nanocomposite as the anode
catalyst was enhanced by 50% relative to that recorded by an unsupported Pt
Ru colloid anode catalyst. The enhanced performance of PtRu/herring bone
GNF has been attributed to the specific support effects.
3.1.3. Carbon nanocoils (CNCs)

Carbon nanocoils (CNCs) composed of nanometer thick graphitic fibers
have been successfully explored as electrode materials for DMFCs [5860].
Hyeon group has prepared the CNCs by simply heat-treating composites
composed of a resorcinol-formaldehyde gel as a carbon precursor, silica, and a
mixture of cobalt and nickel salts as a transition metal salt. The purpose of
silica sol used in the preparation procedure is to obtain carbon materials with
high surface area, and to achieve a good dispersion of the transition metal
nanoparticles, which catalyze the formation of the graphitic nanostructure [58].
They have achieved high surface area of 318 m2 g1 with good crystallinity.
PtRu alloy catalyst particles (60 wt%) with an average particle size of 2.3 nm
are highly dispersed on CNCs. When applied as an anode material in DMFCs,
these PtRu/CNCs have shown high electrocatalytic activity for methanol
oxidation. The uniform distribution of the catalyst along with a small particle
size, which is key factors for the stable and efficient operation of a DMFC
seems to result from the good characteristics of CNCs, such as high
crystallinity and large surface area. In addition, the unique pore structure of the
support, which favors the diffusion of methanol fuel and the removal of by
product CO2 gas, could be responsible for the improved fuel cell performance.
3.1.4. Porous carbon nanostructures

In search for novel nanocarbon materials as supports porous carbon tubule
membranes are prepared by template-synthesis method [61]. The method
involves the chemical-vapour deposition of carbon within the pores of alumina
membranes. The carbon comprising these tubules can be transformed from a
disordered material to highly ordered graphite. These C/alumina tubules can
then be immersed into a solution of the desired metal ion and reduced to the
corresponding metal or alloy by H2 gas. The underlying alumina can be
removed by dissolving it in HF solution to obtain the desired free-standing
carbon-tubule membrane supported electrode materials. Pt particles with an
average particle size of about 7.1 nm and PtRu particles with particle size of
about 1.7 nm can be dispersed on the synthesized carbon nanotubules. The
12
carbon nanotubule supported Pt electrodes have been studied for oxygen

reduction.
Ryoo et al have showed that a periodic array of uniform ordered
nanoporous carbon using the mesoporous aluminosilicate molecular sieves
known as SBA-15 as templates [62]. These nanoporous carbon materials have
tunable pore diameters and rigid structural order. The structure of the
synthesized carbon is composed of ordered nanoporous carbon, which was
originally formed inside the cylindrical nanotubes of the SBA-15 template.
The ordered nanoporous carbon is rigidly interconnected into a highly ordered
hexagonal array by carbon spacers even after SAB-15 removal. In this kind of
nanostructured carbon, the pores or channels behave as individual nanoscale
reactors so that chemical reactions are confined to take place inside the pores,
with only limited diffusion between them.
They have found that even when the Pt loading is increased to the same
weight of carbon (50 wt% Pt of the total weight), the Pt clusters show a very
narrow particle-size distribution and average particle size of Pt cluster is
around 2.5 nm. In the case of other porous carbons such as carbon black,
activated charcoal and activated carbon fiber, the same experiments have
resulted in the formation of much larger Pt particles with a wide distribution of
diameters ranging up to 30 nm. Nanostructured carbon, capable of supporting
Pt clusters with such high and uniform dispersion has been tested for O2
reduction. The mass activities obtained with the 2050 wt% Pt loadings are
much higher than those of the Pt/carbon black samples onto which the Pt
particles were supported, using the same procedure as for the ordered
nanoprous carbon. The uniform distribution and decreased Pt cluster size using
the nanostructured carbon as support is advantageous for DMFC applications.
Recently, Woo et al [63] have demonstrated a novel procedure to
synthesize a new mesoporous platinum-carbon nanocomposite with a well
control over particle size and shape. This method is based on the pyrolysis of
carbon and platinum precursors in silica mesopores such as SBA-15 in order to
take advantage of the excellent size- and shape-control achievable in the
synthesis of nanodispersions. With the developed method they have
synthesized Pt nanoclusters studded in the microporous nanowalls of ordered
mesoporous carbon. They found that the materials is composed of regularly
interconnected PtC nanocomposite arrays, and can be successfully used as a
methanol tolerant cathode material in DMFC.
A new type of periodically ordered bimodal porous carbon (POBPC) frame
work with three-dimensionally interconnected, ordered, and uniform
mesopores surrounded by mesostructured walls has been proposed as catalyst
support in DMFCs [64]. The POBPC was determined to have a BET surface
area of 465 m2 g1 and PtRu catalyst loadings to the tune of 80 wt% are
possible. The methanol-oxidation activity of the POBPC supported PtRu
13
catalyst showed 79% high maximum power density than that of the E-TEK and
Vulcan carbon-supported catalysts. The enhanced catalytic activity found with
POBPC materials is attributed to their high surface areas and larger pore
volumes of porous carbons which allow greater degree of catalyst dispersion.
Due to the three-dimensionally interconnected macroscale and mesoscale
bimodal porosity provides an open-highway network around the active
catalyst for the facile diffusion of fuels and products to and from the catalyst.
In the case of Vulcan carbon with its randomly distributed pores of varying
size, respectively which may make fuel and product diffusion less efficient.
Some of these carbon materials discussed above when applied as supports
exhibit promising activities towards electrochemical reactions in DMFCs
(Table 1).
Table 1. Summary of carbon supports for DMFCs under development.
3.2. Electrocatalysts
3.2.1. Electrocatalysts for methanol oxidation reaction
Electro-oxidation of methanol occurring at anode of DMFCs received
great attention of both the academic and industrial researchers and a significant
number of investigations have been carried out [65, 44]. To establish the best
electrocatalyst composition, methanol oxidation on smooth electrode surfaces
has been carried out in half-cell configuration. Electrochemical investigations
coupled with spectroscopic techniques have been used to understand the
oxidation mechanism and to find out the nature of the adsorbed species on the
14
electrode surfaces. Platinum is considered to be the best material for both the
absorption and dehydrogenation of methanol [10]. The progressive
dehydrogenation of the adsorbed methanol produce either linear or bridgebonded carbon monoxide (CO) species which are strongly adsorbs on Pt
surface (COads). COads species will poison the Pt electrode by blocking the
active sites for methanol absorption and it is a significant impediment to the
development of DMFCs [66]. Alloys with Pt have been sought as a means of
enhancing the efficiency of methanol oxidation and this alloying route has
achieved most successful results so far. PtRu was among the first binary
systems to be studied and it remains the most effective [15, 67]. Alloying Pt
with Sn also showed promising results for methanol oxidation and CO
removal.
3.2.1.1. Binary Pt-based alloy electrocatalysts

The well-known anode deactivation due to adsorbed CO on Pt when
methanol is used as fuel has encouraged to extensive research on platinumbased alloy catalysts, which have better CO tolerance than pure Pt. When Pt is
alloyed with Ru, water dissociation occurs on Ru sites to produce RuOH
groups at (at 0.2 0.3 V vs. RHE) less positive potentials than on pure Pt
surface (0.7 V vs. RHE) [13] and the RuOH groups reacts with neighboring
CO adsorbed on Pt to give carbon dioxide (See section 2.1. for detailed MOR
mechanism on PtRu catalysts) according to the bifunctional mechanism [13,
14, 19, 20]. Another model proposed to explain the Ru promoting effect is the
ligand model [2124]. The ligand model is based on the modification of Pt
electronic structure by the presence of Ru rendering Pt atoms more susceptible
for OH adsorption [68] or even dissociates adsorption of methanol [69].
Recently Waszczuk et al have shown that both bifunctional and ligand effect
will be operative in PtRu catalysts [70]. For an efficient catalysis, it appears
to be favorable to provide efficient adjacent sites for adsorption and desorption
of reactant and product species. The presence of two complementary
functioning catalytic sites in close proximity would seem to be a very
favorable condition for the catalytic process of oxidation of methanol.
Optimum Pt:Ru ratio: The influence of atomic bulk composition of PtRu
catalysts towards methanol electro-oxidation was extensively studied and the
subject is of much debate [7175]. The atomic composition of 50:50 (Pt:Ru) is
found to be the optimum composition for methanol oxidation reaction at high
temperature 90130 oC. According to Gasteiger et al, at room temperature,
methanol is easily oxidized on PtRu catalysts with low (~10%) Ru content,
but at intermediate temperature (for example at 60 oC) methanol oxidation
occurs on PtRu catalysts with ~33% Ru content [73]. An increase in
operation temperature would play a favorable role for the initial
15
dehydrogenation of methanol and it would facilitate the CO desorption,

decreasing the coverage of irreversibly adsorbed species. However, Lamy and
co-workers have found that, in a three electrode half cell as well as in a DMFC
single cell, higher power densities were obtained with a PtRu atomic ratio of
80:20 irrespective of the temperature in the range from 20 to 110 oC. This
controversy about the optimum composition of PtRu catalysts has not yet
been resolved and needs further investigations.
Catalyst preparation methods: PtRu/carbon catalyst, in which the PtRu
alloy nanoclusters require several characteristics: (1) optimum compositions of
at least 50 atomic percent Pt, (2) uniformity in alloy stoichiometry throughout
the bulk sample, (3) well-defined surface structure, a preferred (111) face for
structural effect, (4) an average particle size near 5 nm [76], and (5) total metal
loadings sufficiently high to give acceptable performance in an operating
DMFC, is a challenging goal. A variety of methods are available for the
preparation of PtRu nanoparticles: The most common among them is the
chemical reduction via sulfite-complex route [15, 77, 78]. Bnnemann and coworkers developed a new route using an organometallic compound to
synthesize colloidal precursors for the PtRu/C catalyst, where the organic
molecules are used to prevent to agglomeration and coalescence of the
particles [79, 80]. High-area catalysts with completely alloyed bimetallic Pt
Ru particles and a narrow particle size distribution with less than 3 nm
diameter were prepared by adsorbing surfactant stabilized pre-formed PtRu
colloids on high-surface area Vulcan XC 72 [81]. Impregnation method
[56, 61, 8285], reverse micelles method [8688], microwave-assisted polyoly
method and alcohol-reduction method [90] have also been available for the
preparation of PtRu catalysts [89]. Recently we have produced a nano-sized
PtRu/C catalysts via a modified alcohol-reduction method in which a small
amount of Nafion is introduced during the preparation step [91]. The presence
of Nafion is believed to enhance the activity of PtRu/C catalysts for the
electro-oxidation of methanol by acting as a better dispersing agent and by
increasing the ionic (proton) conductivity. With this method it is possible to
prepare the PtRu/C catalysts with particle size of about 3 nm with a well
dispersion over carbon (see figure 2).
Waszczuk et al have decorated platinum nanoparticles with ruthenium to
obtain a Pt/Ru catalyst with a packing density of up to 0.65 Ru atoms per Pt
surface atom by using spontaneous deposition method [92]. The activity of this
catalyst toward methanol electrooxidation was tested at electrode potentials of
interest for fuel cells. The catalyst activity maximizes at ruthenium packing
density 0.4 0.5, and the catalyst activity was enhanced by two orders when
compared to the commercial Pt/Ru alloy catalyst with 50:50 atomic
compositions.
16
Figure 2. TEM image of PtRu/C catalyst prepared by a Nafion-stabilized alcoholreduction method [91].
Recently, Nuzzo and Shapley have reported that the PtRu carbonyl
cluster complexes, PtRu5C(CO)16 and Pt2Ru4(CO)16 can serve as single-source
molecular precursors for the preparation of PtRu5 and PtRu2/C nanocomposites
[9395]. They prepared carbon-supported PtRu nanoparticles with a 1:5
Pt:Ru composition by the reductive condensation of a carbon-supported
molecular cluster precursor PtRu5C(CO)16. During the H2 reduction process at
473 K the PtRu nanoparticles form a disordered structure in which Pt is found
preferentially at the core of the condensing particle. After further hightemperature treatment to 673 K the nanoparticles adopt an inverted structure in
which Pt appears preferentially at the surface of the bimetallic nanoparticle.
With this process it is possible to prepare the PtRu nanoparticles with an
average diameter of 1.5 nm.
Lukehart et al have described the preparation of a Pt1-Ru1/carbon
nanocomposite
using
(-C2H4)(Cl)Pt(-Cl)2-Ru(Cl)(3:3-2,7dimethyloctadienediyl) as a noncluster, 1:1 Pt:Ru bimetallic molecular
precursor [57]. Vulcan carbon (Cabot Corporation, XC72R) serves as the
traditional carbon powder support. Microwave dielectric loss heating permits
rapid conversion of precursor/carbon composites to the desired
nanocomposites under appropriate conditions. This method can produce the
PtRu nanocomposites with arbitrary total metal loadings of 16 and 50 wt%
having metal alloy nanocrystals of 3.4 and 5.4 nm average diameters,
respectively. The PtRu nanocomposites with 16 wt% metal loading shows
catalytic performance comparable to that of related commercial catalysts
17
whereas the nanocomposite with 50 wt% shows higher performance when

compared with the commercial supported catalysts having higher metal
loadings. The summary of the preparation methods available for PtRu
catalysts is shown in table 2.
Role of Ru as a promoter metal: The promotional effect of Ru is explained
by two effects: in bifunctional effect, the Ru sites acts as adsorption centres for
the oxygen containing surface species formed by the dissociation of water (e.g.
OH) at 0.20.3 V lower potentials than the pure Pt surface. The adsorbed
oxygen-containing species on Ru are then reacts with CO to yield CO2. It is
worthwhile to mention about the ensemble effect also. PtRu pair sites adsorb
a more active form of oxygen-containing species rather than RuRu sites or Ru
clusters. The optimum surface composition of Ru maximizes the PtRu pair
sites within the constraints of the optimum ensemble for adsorption of the
molecule. In the case of CO and HCOOH, adsorption is equally facile at the
RuRu, PtPt and PtRu sites and the optimum surface composition is 50 at%
Ru. For methanol, the situation is quite different as its adsorption occurs
through consecutive dissociative steps. In terms of geometry, the optimum
adsorption site seems to be a C3 Pt ensemble, and the composition which
simultaneously maximizes the number of these ensembles and PtRu pairs is
10 at.% Ru [44, 9699] According to the ligand mechanism, Ru changes the
Table 2. Preparation methods for PtRu catalysts and their performance in DMFC.
18
electronic states of Pt, which affects both the activation of methanol CH bond
and weakening of CO binding to Pt facilitates the CO2 removal. The increase
in Pt d-band vacancies upon alloying with Ru as studied by X-ray absorption
spectroscopy supports the ligand effect of Ru on Pt [100]. Increase in Pt dband vacancies upon alloying with Ru can be evidenced in PtRu catalysts
from the increase in white line area of Pt absorption edge from the X-ray
absorption near-edge spectra (Figure 3).
Figure 3. Pt LIII-edge XANES spectra of a PtRu catalyst prepared by Nafionstabilized alcohol-reduction method (solid line) and a Pt foil (line with triangles).
FTIR data on PtRu samples shows a CO stretching frequency shift to

higher wavenumbers with respect to Pt which is an evidence of Ru role in
modifying the Pt electronic state [101]. In a similar study Frelink et al have
observed a shift in linearly bonded CO stretching frequency to higher wave
numbers at various coverages further supports the Ru effect on Pt electronic
state [102, 14]. Differential electrochemical mass spectrometry (DEMS), a
technique which provides unambiguous identification of transient species
generated during electrochemical reaction, and in-situ ellipsometric studies on
Pt and PtRu electrodes support the bifunctional mechanism [102]. From these
in-situ experiments described above one can realize that the promotional effect
of Ru could be due to the contribution of both the bifunctional and ligand
effects. However, XPS results on PtRu dont show any change in Pt 4f
spectra, indicating that the effect of Ru on Pt electronic state is less significant
when compared to the bifunctional effect [103]. Wieckowski and co-workers
have studied the relative magnitudes of the ligand and bifunctional effects by
using 13C-NMR, temperature programmed desorption spectroscopy and cyclic
voltammetry [104]. According to their results, Ru addition leads to a total
19
reduction in the overpotential by 170260 mV. Out of this total only 40 mV is

due to the ligand effect and the remaining 130220 mV is contributed by the
bifunctional effect. From all this work, one may conclude that the addition of
Ru to Pt significantly increases the electrocatalytic activity of Pt through the
adsorption of oxygenated species on Ru-sites. It becomes clear that PtRu
catalysts are more effective for methanol oxidation since the reaction wants the
electrocatalysts to be used in a potential regime where labile-bonded oxygen
should be present on the surface. In this situation, the supply of active oxygen
to the surface is of paramount importance since this, apparently, would
facilitate the oxidation of adsorbed methanolic residues to CO2.
Alloying extent or atomic distribution in fuel cell catalysts: It has been
fairly observed that our knowledge of the catalytic reaction mechanisms will
be improved if we can relate the catalytic activity to the structural aspects of
the materials because most of the catalytic reactions are structure sensitive and
hence methods to get more insights into structural aspects are highly needed.
Of interest is to control the homogeneity, dispersion, alloying extent and
structure as they have profound influence on the surface properties which
affect the catalytic activity, selectivity and stability of the bimetallic
nanoparticles. Even though alloying is a well-known phenomenon, detailed
studies on quantitative assessment of alloying extent (or) atomic distribution in
bimetallic NPs have been lacking so far. Due to the constraints exists in
choosing the number of atoms used in the simulation process it is hard to
predict the structure and atomic distribution of NPs with so-called theoretical
methods. Also the theoretical prediction that the bimetallic systems reach the
thermodynamic equilibrium is not accessible during real-time synthesis of
NPs. Even in case of bimetallic NPs having similar compositions, differences
in atomic distribution, depending on the preparation conditions, will have
strong influence on their catalytic properties. In our recent studies, we have
explored a method which can estimate the atomic distribution of NPs which is
most beneficial for physicochemical properties and their applications by X-ray
absorption spectroscopy [105].
The extent of alloying of element A (JA) and element B (JB) for 1:1 AB
bimetallic NPs can be calculated quantitatively by using the equations (1) and
(2) respectively.
(1)
(2)
20
The parameters Pobserved, Robserved, Prandom, and Rrandom are defined as follows. The
parameter Pobserved can be defined as a ratio of the scattering atoms B
coordination number around absorbing A atoms (NAB) to the total
coordination number of absorbing atoms (NAi), (Pobserved =NAB/NAi).
Similarly, Robserved can be defined as a ratio of the scattering atoms A
coordination number around absorbing B atoms (NBA) to the total
coordination number of absorbing atoms (NBi), (Robserved = NBA/NBi).
Whereas, Prandom and Rrandom can be taken as 0.5 for perfect alloyed bimetallic
NPs if the atomic ratio of A and B is 1:1. This value can be achieved by
assuming NAA = NAB and NBB = NBA which is generally true for perfect
alloyed bimetallic NPs. In a similar way Prandom can be taken as 0.67 and 0.8
for 1:2 and 1:4 bimetallic NPs respectively. The parameter Rrandom can be taken
as 0.33 and 0.2 for 1:2 and 1:4 bimetallic NPs respectively.
It is possible to construct the structural models emphasizing the atomic
distribution in the bimetallic NPs with the knowledge of the NAi, NBi, JA
and JB values derived from XAS. With the help of extent of alloying values
and structural parameters extracted from EXAFS it is possible to predict the
structure models of PtRu/C catalysts. We have calculated the alloying extent
of Pt (JPt) and Ru (JRu) for commercial 30 wt% PtRu/C catalysts.
In case of JM 30 catalyst the coordination numbers of Pt and Ru atoms
around the Pt atom are found to be 5.6 0.3 and 1.4 0.1, respectively, and
the total coordination number NPti is 7.0. The coordination numbers of Ru
and Pt atoms around the Ru atom are determined as 3.4 0.2 and 2.2 0.3,
respectively, and the total coordination number NRui calculated as 5.6. From
these values Pobserved and Robserved determined as 0.20 and 0.39, respectively, and
JPt and JRu values are calculated as 40 and 78%, respectively. For E-TEK 30
catalyst we have calculated the coordination numbers of Pt and Ru atoms
around the Pt atom as 6.2 0.3 and 0.9 0.1, respectively, and NPti as 7.1;
the coordination numbers of Ru and Pt atoms around the Ru atom are
determined as 3.7 0.2 and 1.2 0.2, respectively, and the NRui as 4.9. The
other two structural parameters Pobserved and Robserved in the case of E-TEK 30
are calculated as 0.13 and 0.24, respectively, and the JPt and JRu values are
calculated as 26 and 48%, respectively. It is clear from the structural
coordination parameter values of both the catalysts that NPti > NRui and JRu
> JPt, which indicates that the catalysts adopt a Pt rich in core and Ru rich in
shell structure. A schematic representation of the catalyst structures is given in
figure 4.
From the quantitative extent of alloying values, we can see that in both the
catalysts considerable amount of Ru is segregated on the shell layer but the
extent of segregation of Ru is higher in E-TEK 30 when compared to the JM
30. The increased value of JRu in JM 30 catalyst indicates that most of the Ru is
involved in alloying and hence less segregation of Ru in the shell whereas in
21
Figure 4. Structural models deduced for JM 30 (a), and E-TEK 30 PtRu/C catalysts
(b) based on XAS parameters.
the case of ETEK 30 catalyst lesser extent of Ru is involved in the alloying and
considerable extent of segregation of Ru can be expected in the shell region.
The segregation of Ru in the case of ETEK 30 in part may be responsible for
its lower methanol oxidation activity compared to JM 30. Recent infrared
measurements on the PtRu alloy particle electrodes indicates two modes of
adsorbed CO vibrations related to both Pt and Ru domains present on the
surface supports the surface segregation of Ru in commercial catalysts [106].
The XAS results support the Pt-rich core and Ru rich shell structure for
commercial carbon-supported PtRu catalysts. Increase in JPt and JRu values in
JM 30 compared to E-TEK 30 indicates that the atomic distribution of Pt and
Ru atoms are much facilitated. Increase in atomic distribution can be taken as a
measure for enhanced homogeneity.
3.2.1.2. Binary Pt-based alloy electrocatalysts other than PtRu

PtSn system has found considerable interest, probably only second to that
in PtRu system. Theoretical studies suggest that Sn alloyed into Pt is inactive
in generating OHads [107]. In agreement with this, it was found experimentally
that PtSn alloys are not active [108, 97], while electrosorbed or
electrodeposited Sn on Pt is a reasonably good catalyst for methanol oxidation
[109113]. However, the conclusion that PtSn alloys are inactive for
methanol oxidation is disputed [114], even though the majority of
experimental and theoretical evidence suggests otherwise. According to
Wasmus and Kuver, this contradiction might well be an apparent one since (i)
it is sometimes unclear whether a binary system is an alloy or just a mixture of
two metals, and (ii) Sn may leach out under acid conditions being in turn
readsorbed electrolytically at Pt sites [44]. Under less well controlled
22
experimental conditions, the latter effect may stimulate a catalytic activity of

PtSn mixtures or alloys. Generally, it is thought that the adsorbed Sn on Pt is
active while this is not the case for PtSn alloys might be due to the ionic
nature of adsorbed Sn [111]. Neither chemisorbed nor electrosorbed foreign
metals on Pt are a practical way for fuel cell catalysts since a load variation
during fuel cell operation may lead to a change of the anode potential, resulting
in desorption of the foreign metal so that its ions may diffuse into the
electrolyte, and in turn to the cathode, which is a highly undesirable effect. Pt
Re [115], PtMo [116118], PtOs [119], PtWO3 [120, 121] and PtNi [122,
123] systems have been explored for methanol oxidation. For all these species,
the determining factor for promotion is the formation of an adsorbed oxygen
containing species on the secondary metal at potentials lower than for Pt. The
oxygen containing species are needed for the oxidation of intermediate
adsorbates. It is still necessary, however, to employ higher loadings for the
catalysts than are needed for H2 oxidation. Other factors that influence the
catalytic activity of the electrode are the support [124], the ionomer content in
the active layer [125], and the fuel feed. It was found that the specific activity
of supported PtRu/C is much higher than for a PtRu black. The maximum
attainable voltage in cell is, however, much lower for the supported catalyst.
The cell employing the unsupported catalyst also features a lower cross-over
rate suggesting higher methanol utilization. The advantage of using a
supported metal catalyst lies in the possibility to reduce the metal loadings
drastically. The difference in performance may be due to the difference in
morphology between the two types of catalyst. It is therefore necessary to
improve the stability of both supported and unsupported metal catalysts [126,
127].
3.2.1.3. Ternary Pt-based electrocatalysts

Mallouk et al have produced PtRuOs ternary alloys and predicted the
improved methanol oxidation activity by considering the phase equilibria and
relative PtC and MO (M = Ru, Os) bond strengths. From their studies it was
found that Os is more oxophilic than Ru but significantly less soluble in facecentered cubic (fcc) Pt. The best catalytic activity was therefore found at
ternary compositions near the Os solubility limit [128, 129]. They also have
developed combinatorial screening method for ternary and quaternary alloy
catalysts and found that the addition of small amounts of Ir to the PtRuOs
ternary catalysts (Pt44Ru41Os10Ir5) significantly improved their performance
[5]. The Os plays a role similar to the Ru where as the role of Ir appears to be
accelerating CH bond activation processes. The other ternary systems
developed for methanol oxidation are PtRuSn [130], PtRuW [131], PtRuSnW
[132], PtRuSnW/C [133], PtRuMeOx (Me =W, Mo and V) [134], PtRuRh
[135], and PtRuRhNi [136]. Some of these catalysts exhibit promising
23
properties towards methanol oxidation, however methods describing the role of

third functionality in improving the catalytic activity are lacking so far. Even
in the case of bimetallic systems, a detailed understanding of the metallic
interactions and catalytic activity enhancement is also needed. For this a
complete strategy is required in developing the catalyst systems and in this
regard theoretical work [107, 137] coupled with combinatorial analysis [5] to
improve screening efficiency are beneficial. To compare the catalytic activities
of different catalysts, acceptable methods are needed to be developed.
3.2.2. Electrocatalysts for oxygen reduction reaction

In DMFCs the overpotential at the state-of-the-art Pt cathode is about 0.3
V even under open-circuit conditions. The high degree of irreversibility of the
oxygen reduction reaction (ORR) is responsible for 0.2 V losses whereas short
circuits in the cathode reaction resulted from the methanol cross-over causes
0.1 V losses. It means that about 25% potential losses from the theoretical
maximum efficiency happen only in the cathode of a DMFC [138, 139]. The
important strategies appeared in the literature to avoid the above mentioned
problems are (i) the development of novel less-methanol permeable
membranes, or modification of the existing membranes, (ii) use of methanoltolerant ORR catalysts which are highly inactive towards methanol oxidation,
and (iii) alloying Pt with transition metals such as Co, Ni, Fe, V, Mn and Cr.
Transition-metal macrocycles, namely transition-metal tetra methyl phenyl
porphyrins (TMPPs) (such as FeTMPP, CoTMPP, and FeCoTMPP), and
transition-metal tetra azaanulenes (such as CoTAA [140144], ruthenium
based chalcogenides [145149] based on Chevrel-phase of the type
(MoxRuySez) (0.02 < x < 0.04, 1 < y, z = 2y) [150], transition metal sulfides
(MoxRuySz, MoxRhSz), or other transition metal chalcogenides (Ru1xMox)
[151]) have been introduced as methanol tolerant oxygen cathodes because
these compounds are inactive toward the oxidation of methanol. The
ruthenium chalcogenides of type RuxXy (where x = S, Se, and Te) have also
been explored as methanol-tolerant ORR catalysts [147]. Among these, the
latter class of catalyst materials and, in particular, ruthenium-based cluster
catalyst with selenium (RuSe) has been reported to be attractive for its
selective catalytic activity towards ORR in the presence of methanol [152].
The tolerance of these materials to methanol is due to the absence of
adsorption sites for methanol dehydrogenation. However, the intrinsic catalytic
activities of these catalysts for the ORR are still lower than those of Pt-based
catalysts, and the long-term stability under fuel cell operation at high potentials
has not been well tested as compared to the Pt-based catalysts.
Alloying Pt with transition metals is a priming approach and this strategy
not only improves the ORR activity but also decrease the cost. Many
investigations have shown that Pt-based binary and ternary-alloy catalysts,
24
namely, PtCr/C [153155], PtFe/C [156, 157], PtNi/C [158], PtCo/C

[158], and PtCoCr/C [159161] exhibits superior electrocatalytic activities
towards ORR when compared to the Pt alone. Generally, most of the authors
reported an activity enhancement of the ORR on the alloy catalysts by factors
of 1.5 to 3 in comparison to pure Pt. The improvement in the ORR
electrocatalysis on Pt-based alloy catalysts has been explained by several
factors such as changes in short-range atomic order, particle size, Pt d-band
vacancy, Pt skin effects and PtOH inhibition [162166]. More details about
these electronic and structural effects are reviewed by Mukerjee [167] and
Adzic [168]. Inhibiting the PtOH formation (approximately 0.8 V vs. RHE
for Pt) will generally lower the overpotential losses by providing free sites for
molecular oxygen adsorption. A number of prior reports have provided indirect
evidence to the possibility of inhibiting the formation of anodic activation of
water for PtOH formation [169171]. Shifting the onset potential for PtOH
formation on Pt is dependent on (a) the ability of the alloying elements to
modify the Pt electronic and short-range atomic order for inhibiting activation
of H2O and (b) the ability of the alloying element to attract and hold H2Oads
more strongly than the surrounding surface Pt atoms.
One of the difficulties in determining the effect of alloying components
using supported catalysts is that the activity of a pure Pt supported catalysts
can have a wide range of values depending on its microstructure and/or method
of preparation. The intrinsic activity of Pt for the ORR depends on both
particle shape and size [172, 173]. Since the alloyed Pt catalysts particles may
not have either the same particle size or shape as the Pt catalysts to which they
are compared, a simple comparison of activity normalized either by mass or
surface area is insufficient to identify a true alloying effect and more detailed
discussion of this point can be found in the literature [174]. The other
important factors of the alloy clusters to obtain a good electrocatalytic activity
are the dispersion and composition homogeneity [175, 176]. Significant
improvement of the ORR catalysis on Pt-based alloy systems will require the
inhibition of PtOH formation beyond 0.8 V.
Recently, Markovic group has studied the intrinsic catalytic activity of
Pt3Ni and Pt3Co alloy catalysts with model bulk alloys characterized in UHV.
The ORR of the Pt3Ni and Pt3Co catalysts has been studied in acid electrolytes
using the rotating ring disk electrode (RRDE) method [177]. In their studies
Pt3Ni and Pt3Co catalysts with two different surface compositions one with
75% Pt and the other with 100% Pt were prepared. They named the alloy with
100% Pt as Pt-skin structure and it was produced by an exchange of Pt and Co
in the first two layers. They observed that the ORR activity order on these
catalysts is dependent on the nature of the supporting electrolytes. It was found
that the activity increases in the order Pt3Ni > Pt3Co > Pt in H2SO4. However,
in HClO4 at 333 K, the ORR activity increases in the order Pt-skin > Pt3Co >
25
Pt3Ni > Pt. The catalytic enhancement of the ORR on Pt3Ni and Pt3Co vs. Pt is
attributed to the inhibition of PtOHad formation on Pt sites surrounded by
oxide-covered Ni and Co atoms beyond 0.8 V. Kinetic parameters for the
ORR and the production of H2O2 on the Pt3Ni, Pt3Co, and Pt-skin alloys are
the same as the pure Pt. The reaction order (m) was found to be one. The Tafel
slope (90110 mV/dec) and the activation energy (20 to 25 kJ/mol) discerned
for pure Pt is almost the same with values obtained for Pt3Ni and Pt3Co
bimetallic surfaces. The fact that the same kinetic parameters are assessed from
the analysis of the ORR data on all three surfaces implies that the reaction
mechanism on Pt3Ni and Pt3Co alloy surfaces is the same as on proposed for
pure Pt, i.e., a series 4 e reduction pathway.
Very recently, platinum monolayers supported on Au (111), Rh (111), Pd
(111), Ru (001), and Ir (111) surfaces in HClO4 solutions have been studied as
ORR catalysts [178]. The experimentally measured electrocatalytic activity of
platinum monolayers for the ORR shows a volcano-type dependence on the
centre of their d-bands as determined by density functional theory (DFT)
calculations. The platinum monolayer supported on Pd(111) (PtML/Pd(111)) is
at the top of the volcano curve and shows improved ORR activity over pure Pt
(111). They have demonstrated this behavior by two opposite trends: while a
higher lying d-band center tends to facilitate OO bond breaking, a lower lying
one tends to facilitate bond formation (e.g., hydrogen addition).
In an another study Adzic group have demonstrated the kinetics of ORR in
acid solutions on Pt monolayers deposited on a Pd (111) surface and on
carbon-supported Pd nanoparticles using the rotating ring-disk electrode
(RRDE) technique [179]. The kinetics of O2 reduction shows a significant
enhancement at Pt monolayers on Pd (111) and Pd nanoparticle surfaces in
comparison with the reaction on Pt (111) and Pt nanoparticles. They have
suggested four-electron reduction mechanism for both the surfaces. The
observed increase in the catalytic activity of Pt monolayer surfaces compared
with Pt bulk and nanoparticle electrodes may reflect decreased formation of
PtOH.
Development of Pt-alloys and Pt monolayers on Pd electrocatalysts are
showing promising results towards oxygen reduction reaction. These catalysts
enable a reduction of ORR overpotential losses by approximately 50 mV and a
summary of these catalysts is shown in Table 3. The most important points to
be considered for the development of ORR catalysts are:
(i)
Particle size effects need to be studied carefully. The majority of

prior results on ORR activity variations with Pt cluster size
showed a sharp drop in activity when cluster sized dropped
below 2 nm. High-resolution transmission electron microscopy
26
Table 3. Summary of oxygen reduction reaction catalysts under development.
(ii)
(iii)
(iv)
(HRTEM) analysis provides information on the particle size and

shape.
Dispersion of metal crystallites in a conductive support like
carbon is most important. The use of novel carbon materials can
extend the electrode-electrolyte interface and thereby increase the
catalyst and reactant utilization.
Preparation methodologies are needed to produce Pt alloys
systems which can inhibit the formation of PtOH beyond 0.8 V.
Quantitative kinetic measurements for the ORR should be made
to get more insights into the mechanism and activity. The rotating
ring-disk electrode (RRDE) method allows the accurate
determination of kinetic data such as Tafel slopes, reaction orders
and (apparent) activation enthalpies in the absence of mass
transport effects. Ring current measurements provide the parallel
determination of the product distribution (H2O2) versus H2O
formation under fuel cell relevant conditions and give insight to
the reaction pathway.
4. Proton exchange membranes (PEMS)

DMFCs require membranes having reduced methanol permeability and
water transport, which usually happen through diffusion and electro-osmotic
drag. Solid polymer electrolytes such as perfluorosulfonic acid membranes
(PFSA) (e.g., DuPonts Nafion) have been demonstrated [180183] in
DMFCs. The PFSA membranes have a phase-separated structure comprising a
hydrophobic matrix and interconnected hydrophilic cluster, called ionic
27
channels [184]. Proton conductance occurs through the ionic channels of the
membranes [185]; these channels are formed by micro- or nanophase
separation between the hydrophilic proton exchange sites and the hydrophobic
domain. The Nafion membranes assure high proton conductivity ( 102
S.cm1) and high chemical stability. However during the DMFC operation the
unreacted methanol at the anode can diffuse through the membrane and utilizes
the cathode Pt sites for the direct reaction between methanol and oxygen,
generating a mixed potential that reduces the cell voltage [186, 187]. Possible
ways to mitigate this problem include using the thick Nafion 117 membranes
(1100 EW, 7 mil ~ 178 m thick) and supplying the anode with dilute
methanol, for example, 1 M or less to reduce the methanol crossover. However
it is pointed out that the use of dilute methanol feed increases the systems
complexity and reduces the energy density of the fuel, while the use of thick
Nafion membrane increases the resistive losses of the cell [188]. Another way
to overcome the methanol cross-over problem is to develop new polymer
systems, or modify the existing membranes in order to achieve high ionic
conductivity, low permeability to DMFC reactants, long-term stability under
operating conditions and low cost [189].
There have been several attempts to explore non-perfluorinated polymers
without the disadvantages of Nafion [190195]. Most of the works discussed
about the incorporation of inorganic acid groups in to the basic polymer
matrices like poly (sulfones)s, poly (ether ether ketone)s, poly (imides),
polybenzimidazole, and polyacrylamide etc. The cost of these membranes is
comparatively lower than the state-of-the-art Nafion membranes and
properties are improved [196, 197]. Review articles dealing with the
development of polymer-based proton conductors [198201], organic
inorganic composites [202], polymer electrolyte membranes for fuel cells
operating above 100 oC [203], and alternative polymer systems for proton
exchange membranes (PEMs) [188] have been recently published.
The common requirements for proton exchange membranes include (1)
high proton conductivity, (2) low electronic conductivity, (3) chemical
stability, (4) thermal stability, (5) good mechanical properties in both the dry
and hydrated states, (6) low water drag through diffusion and electro-osmosis,
and (7) reasonable cost. In order to select the proper membrane for DMFC
applications the most important parameters need to be characterized are proton
conductivity, methanol permeability, and water swelling. The proton
conductivity of the membranes can be evaluated by impedance spectroscopy
[204, 205]. The methanol permeability can be estimated by pervaporation
[206, 207] and diffusion cell experiments [208, 209]. Water swelling which
gives a measure of the water solubility in the membranes is usually evaluated
using batch experiments in liquid solutions at room temperature [210].
28
4.1. Sulfonated polyetheretherketones as an alternative

to PFSA membranes
For developing non-Nafion membranes as proton exchange membranes
(PEMs), the most widely investigated system is the sulfonation of
polyetheretherketone (PEEK) [211214] or polyetheretherketoneketone
(PEEKK) [215]. These polymers are believed to be having low cost and
enhanced stability when compared to the perfluorinated polymer backbones
[216]. The enhanced properties of sulfonated PEEK and PEEKK membranes
when compared to the Nafion are qualitatively explained by differences in
the microstructure and the acidity of the sulfonic acid functional groups [217].
In the case of perfluorosulfonic polymers the presence of water gives rise
to some hydrophobic/hydrophilic nano-separation [217]. The sulfonic acid
groups aggregate to form hydrophilic domain. In the presence of water only
the hydrophilic domain of the nanostructure is hydrated to maintain the proton
conductivity, while the hydrophobic domains provides the polymer with the
morphological stability. However, in the case of SPEEK membranes the nanoseparation of hydrophobic and hydrophilic domains is less pronounced. This is
resulted from less hydrophobicity and smaller flexibility of the polymer
backbone and the sulfonic acid group is less acidic and therefore less polar. As
a result upon hydration the water molecules may be completely dispersed in
the nanostructure of the sulfonated polymers [218]. The less hydrophobic
nature of hydrocarbon backbone in SPEEK membranes may result in less
dependence of conductivity on humidity in the low water activity range,
allowing for good proton conductivity at high temperatures. Even at high water
contents the water swelling in SPEEK membranes can be significantly
improved by employing cross linking techniques such as ionic cross-linking by
mixing with polymeric bases [219] and covalent cross-linking by applying
sulfonate group containing polymers [220] or by blending with
polybenzimidazole [221], heteropoly acids such as molybdophosphonic acid
(H3PMo12O40xH2O) and tungstophosphoric acid (H3PW12O40xH2O) [222]. By
incorporating heteropolyacids (HPA) into sulfonated PEEK polymer matrices,
proton conductivity exceeded 102 S/cm at room temperature and reached
values of 101 S/cm above 100 oC [193]. Increasing the degree of sulfonation
also increases the proton conductivity of PEEK membranes, but higher
sulfonation especially at higher temperatures leads to high swelling and poor
mechanical properties of the membranes [223].
4.2. Inorganic acid-doped polybenzimidazole (PBI)

membranes
Inorganic mineral acids such as phosphoric acid, sulphuric acid can be
doped into polybenzimidazole (PBI) polymeric electrolytes. These acid-doped
29
PBI membranes show excellent proton conductivities at temperatures up to

130150oC [224226]. Strong bases can also be doped into polybenzimidazole
(PBI) and the resulting membrane show higher proton conductivity at
temperatures above 100 oC [227, 228]. The proton conductivity of the aciddoped PBI membranes is dependent on the acid-doping level, temperature and
humidity. For example He et al have observed proton conductivity about 2.5
102 S/cm at 200 oC for H3PO4-doped PBI membrane with 2 mol H3PO4 per
repeat unit of PBI [229]. At increased H3PO4-doping level of about 5.7 mol per
repeat unit of PBI, the proton conductivity is 4.6 102 S/cm at room
temperature and increases to 7.9 102 S/cm at 200 oC. Due to the high proton
conductivity at temperatures above 100 oC acid-doped PBI membranes are
suitable for DMFC applications.
4.3. Polyphosphazene membranes

Owing to their better chemical and thermal stabilities polyphosphazenebased membranes have been explored for both hydrogen-air and DMFC
applications [188]. Chemical attachment of various side chains for ion
exchange sites and polymer cross-linking onto the PN polymer backbone
is considered to be easy [230]. Pintauro et al. have shown that poly[(3methylphenoxy)(phenoxy)phosphazene] and poly[bis(3-methyl phenoxy)
phospazene] can be sulfonated by adding SO3 solution in dichloroethane
solution dropwise to the polymer solution. A high polymer ion-exchange
capacity of up to 2.0 mequiv/g was obtained when compared to the Dupont
Nafion (IEC, 0.9 mmol/g) for the similar thicknesses of 0.2 mm [231, 232].
In another report, they described the fabrication of PEMs with sulfonate fixed
charge sites from poly [bis(3-methyl phenoxy) phosphazene] [233]. To achieve
sufficient mechanical properties polymer blending, cross-linking and other reenforcement should be performed on these membranes.
4.4. Organicinorganic composite membranes

By incorporating inorganic proton conductors into the sulfonated
hydrocarbon matrix, membranes with many interesting characteristics such as
(i) low electro-osmotic drag, (ii) limited methanol cross-over, (iii) good
mechanical strength, (iv) high proton conductivity, and (v) excellent thermal
stability can be obtained. Polymer components without functional groups
studied for organicinorganic composites include polyethylene oxides, PEO;
polypropylene oxide, PPO; polytetramethylene oxide, PTMO [234238];
polybenzimidazole, PBI [239, 240]. Polymer components with functional
groups such as sulfonated polysulfone, SPSF [241, 242]; sulfonated
polystyrene, and sulfonated polyetheretherketone, SPEEK [243245].
30
Most of the organic-inorganic composite membranes can be prepared by

the sol-gel process. Honma and co-workers have shown that nanosized silicate
species can be prepared from organically modified alkoxysilane precursors.
The nanosized silicate species are cross-linked with polyether polymers to get
inorganic oxide in the polymer matrix. These organic-inorganic hybrid
membranes become a proton conducting electrolyte by doping heteropolyacids
such as 12-phosphotungstic acid (PWA) [234238]. By adopting the similar
sol-gel approach, Lin and co-workers have synthesized organic-inorganic
composite materials based on polyethyleneglycol (PEG)/SiO2 membranes for
DMFC applications [246248]. The proton conductivity is achieved by doping
acidic moieties of 4-dodecylbenzene sulfonic acid (DBSA) [248]. Other
systems, such as phosphotungstic acid (PWA)-doped poly(vinyl alcohol)
(PVA) [249, 250], PWA-doped PVA/SiO2 [251], polyacrylic acid (PAA)doped PVA/SiO2 [252], and PWA-doped PEG/SiO2 [253], have also been
prepared and tested as membranes for direct methanol fuel cells and promising
proton conductivities have been achieved.
Polyvinylpyrrolidine (PVDF) polymers grafted with polystyrene (PSSA)
by -radiation has been explored as DMFC membranes by Horsfall and coworkers [254]. They have reported the maximum power density of 22 mW/cm2
for DMFC single cell at 80 oC with the PVDF-PSSA membrane with 52%
degree of grafting. In another report, PVDF-hexafluoropropylene (HFP)
copolymer and Nafion blends have been studied for DMFCs applications
[255]. Other organic-inorganic systems of interest reported so far are
membranes containing tin-doped mordenities [256, 257], Zr-phosphonates
[258], and zeolites [259]. Most of these membranes shows promising
properties for DMFC applications, which are summarized in Table 4.
Very recently in our group we have focused on the development of silicophosphate (SiO2P2O5) glass electrolytes as proton conductive materials [260,
261]. This kind of proton conductive electrolytes can be prepared by adopting
an accelerated sol-gel process in which the precursors of tetraethylorthosilicate and trimethyl phosphate were partially hydrolyzed in the mixture
of ethanol and water and then further hydrolyzed in the presence of
formamide. The xerogels were then obtained by gelation at 60 oC for 3 days.
With the controlled water/vapor management the gelation time needed is
significantly shortened. The xerogels were sintered to get transparent glass
electrolytes. In (SiO2P2O5) glass electrolyte protons are bonded with oxygen
to form hydroxyl groups attaching to network-forming cations such as Si4+ and
P5+. Figure 5 shows the network structure of the synthesized glass electrolytes
and the bonding environments of the water molecule and hydroxyl group on
the network structure derived from the in situ FTIR observations.
The SiO2P2O5 glass electrolyte proton conductivity is found to be
insensitive to humidity and it is an advantage when compared to the
Table 4. Properties of some proton exchange membranes under development.
Figure 5. Proposed network structure of (SiO2P2O5) glass electrolytes [260].
31
32
characteristics of Nafion. The reason may be ascribed to that the mechanisms

of proton transport in the SiO2P2O5 glass electrolyte and in Nafion are
different. In the case of Nafion the water-filled pores in the membrane form a
network of pathways for proton transport. Protons jumps between hydrated
sulfonic acid groups fixed on a stable polymer host and aqueous domains.
Membranes with high degrees of hydration exhibit substantial proton mobility
rationalized on the basis of structural diffusion mechanism resembling that in
bulk-water. At low water content, proton transports via the segmental motions
of polymer. In the matrix of Nafion, there are clusters of water molecules
and ions separated by polymer, and the proton conductivity will take place
when ions move from cluster to cluster via the polymeric segments in the
region between the clusters and the mechanism was named as a hopping
mechanism [249]. In the case of SiO2P2O5 glass electrolyte membranes, the
conductivity changes insignificantly with relative humidity at the temperature
range of 7080 oC, which suggests that the proton conducting mechanism in
the glass electrolyte membranes is different from that of Nafion. The
conduction of protons in the glass electrolytes is mainly through the hydrogen
bonding water and hydroxyl group on the network structure, like hopping. The
protons move from one bonding water or hydroxyl group to another one. We
have achieved the proton conductivity of about 9.45 103 S/cm at 70 oC and
100% relative humidity. Methanol permeability of SiO2P2O5 glass electrolyte
membranes was found to be 2.1 109 cm2/s and this value is about three
orders less than that of the state-of-the-art Nafion membrane (1.57 106
cm2/s) indicating that methanol cross-over can be reduced if we employ SiO2
P2O5 glass membranes in DMFCs.
The membrane materials which are suitable to operate at high
temperatures with high proton conductivity are the newest developments in the
membrane research. The recent progress in this field reveal that membranes
based on modification of state-of-the-art Nafion, non-Nafion systems like
sulfonated
polyetheretherketones
(SPEEKs),
inorganic
acid-doped
polybenzimidazole (PBI), polyphosphazenes, organic-inorganic composite,
and SiO2P2O5 glass electrolytes exhibit promising conductivities and most
systems are successfully operated at temperatures above 100 oC for DMFC
applications.
Figure 6 shows the proton conductivity and methanol permeability of
some of the membranes reported in the literature. The methanol permeabilities
through PEM were proportional to the proton conductivities. The ideal
membrane should possess high proton conductivity with low methanol
permeability and thus the location of the membrane should be in the upper lefthand corner. In the case of membranes in which the proton transport
mechanism is dominated by the surface hopping then the proton conductivity
of the membrane will be higher with much less degree of methanol
33
permeability. However in the case of membranes in which the proton transport

is dominated by bulk diffusion then the methanol permeability will be
significantly increased.
Figure 6. Log proton conductivity versus log methanol permeability of PEMs

developed for DMFC applications.
5. Conclusions
There is still a clear need for the synthesis and complete characterization
of new carbon supports, electrocatalysts and proton exchange membrane
materials for DMFCs. Herein we have reviewed the recent progress achieved
in the development of materials for DMFCs. In the search for carbon materials,
focus has been made in attaining well-ordered porosity, high surface area, and
good mechanical strengths. In recent years, mesostructured carbon materials
are emerging as promising supports for fuel cell catalysts because the pore
structure of the carbons can be tailored as a function of the silica that is used as
template. Other important factors to be considered in the development of
carbon materials are dispersion effect, and electronic conductivity. Regarding
the electrocatalysts stress should be made on the evaluation of better catalysts
other than PtRu catalysts, need to achieve higher loadings on carbon supports,
and care should be taken in comparing the catalytic activities of different
electrocatalysts. It is difficulty to compare the activity of different
electrocatalysts appeared in the literature as there is no standard evaluation
method available. Active surface area normalization procedures are beneficial
in this regard. Methodologies are required to determine the extent of alloying
and atomic distribution in fuel cell catalysts as these properties have profound
influence on the surface properties which affect the catalytic activity,
34
selectivity and stability of the catalyst nanoparticles. Theoretical investigations

on assessing the potential energy surfaces for both methanol oxidation reaction
and oxygen reduction reaction coupled with fundamental electrochemical
studies and combinatorial methods would emerge as best strategies in search
for privileged electrocatalysts for fuel cells. Novel proton exchange
membranes which possess suitable properties such as low methanol
permeability, high thermal and mechanical strength required for DMFCs have
been developed and the costs of the membranes are significantly lower than the
state-of-the-art Nafion membranes. Use of organic-inorganic composite
membranes in DMFCs provides promising proton conductivities. Efforts
should be made on the fabrication and design of fuel cell stacks using the
currently available materials and long-term stability of these materials should
be studied to confirm their real applications in DMFCs.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Gottesfeld, S., and Zawodzinski, T. 1997, Adv. Electrochem. Sci. Eng., 5, 195.
Shukla, A. K., Christensen, P. A., Hamnett, A., and Hogarth, M. P. 1995, J. Power
Sources 55, 87.
Jung, D. H., Lee, C. H., Kim, C. S., and Shin, D. R. 1998, J. Power Sources 71,
169.
McNicol, B. D., Rand, D. A. J., and Williams, K. R. 1999, J. Power Sources 83,
15.
Reddington, E., Sapienza, A., Gurau, B., Viswanathan, R., Sarangapani, S.,
Smotkin, E. S., and Mallouk, T. E. 1998, Science, 280, 1735.
Ralph, T. R., and Hogarth, M. P. 2002, Platinum Met. Rev., 46, 3.
Kauranen, P. S., and Skou, E. 1996, J. Electroanal. Chem., 408, 189.
Aric, A. S., Creti, P., Antonucci, P. L., and Antonucci, V. 1998, Electrochem.
Solid-State Lett., 1, 66.
Bockris, J. M., and Srinivasan, S. 1969, Fuel Cells: Their Electrochemistry,
McGraw-Hill Book Company, New York.
Hamnett, A. 1999, Interfacial Electrochemistry, Theory, Experiment and
Applications, Wieckowski (Ed.), Marcel Dekker, New York.
Beden, B., Leger, J.-M., and Lamy, C. 1992, Modern Aspects of Electrochemistry,
Bockris, J. M., Conway, B. E., White, R. E. (Eds.), Plenium Press, New York,
97.
Chandrasekaran, K., Wass, J. C., and Bockris, J. M. 1990, J. Electrochem. Soc.,
137, 518.
Ticianelli, E., Beery, J. G., Paffett, M. T., and Gottesfeld, S. 1989, J. Electrochem.
Soc., 258, 61.
Freelink, T., Visscher, W., and van Veen, J. A. R. 1995, Surf. Sci. 335, 353.
Watanabe, M., Uchida, M., and Motoo, S. 1987, J. Electroanal. Chem. 229, 395.
Watanabe, M., Furuchi, Y., and Motoo, S. 1985, J. Electroanal. Chem. 191, 367.
Gasteiger, H. A., Markovic, N., Ross, P. N. Jr., and Cairns, E. J. 1994, J. Phys.
Chem. 98, 617.
35
18. Ianniello, R., Schmidt, V. M., Stimming, U., Stumper, J., and Wallam, A. 1994,
Electrochim. Acta, 39, 1863.
19. Watanabe, M., and Motoo, S. 1975, J. Electroanal. Chem. 60, 275.
20. Davies, J. C., Hayden, B. E., and Pegg, D. 1998, J. Electrochim. Acta, 44, 1181.
21. Gasteiger, H. A., Markovic, N., Ross, P. N., and Cairns, E. J. 1993, J. Phys. Chem.
12020.
22. Jiang, X., Permeter, J. E., Estrada, C. A., and Goodman, D. W. 1991, Surf. Sci.
249, 44.
23. Goodenough, J. B., Manoharan, R., Shukla, A., and Ramesh, K. V. 1989, Chem.
Mater. 1, 391.
24. Goodenough, J. B., Hamnett, A., Kennedy, B. J., Manoharan, R., Weeks, S. A.
1988, J. Electroanal. Chem. 240, 133.
25. Lu, C., and Masel, R. I. 2001, J. Phys. Chem. B, 105, 9793.
26. Liao, M.-S., Cabrera, C. R., and Ishikawa, Y. 2000, Surf. Sci. 445, 267.
27. Damjanovic, A., Brusic, V. 1967, Electrochim. Acta, 12, 615.
28. Shukla, A. K., and Raman, R. K. 2003, Annu. Rev. Mater. Res. 33, 155.
29. Adzic, R. R., and Wang, J. X. 1998, J. Phys. Chem. B, 102, 8988.
30. Markovi, N. M., Schmidt, T. J., Stamenkovi, V., and Ross, P. N. 2001, Fuel
Cells, 1, 105.
31. Adzic, R. 1998, Electrocatalysis, J. Lipkowski, and P. N. Ross (Eds.), Wiley, New
York, 197.
32. Markovi, N. M., and Ross, P. N. 1999, Interfacial Electrochemistry. Theory,
Experiment and Applications, A. Wieckowski (Ed.), Marcel Dekker, New York,
821.
33. Sidik, R. A., and Anderson, A. B. 2002, J. Electroanal. Chem., 528, 69.
34. Grgur, B. N., Markovi, N. M., and Ross, P. N. Jr. 1997, Can. J. Chem., 75, 1465.
35. Stamenkovi, V., Markovi, N. M., and Ross, P. N. Jr. 2000, J. Electroanal. Chem.,
500, 44.
36. Markovi, N. M., Gasteiger, H. A., Grgur, B. N., and Ross, P. N. 1999, J.
Electroanal. Chem., 467, 157.
37. Toda, T., Igarashi, H., Watanabe, M. 1999, J. Electroanal. Chem. 460, 258.
38. Drillet, J. F., Ee, A., Friedmann, J., Kotz, R., Schnyder, B., and Schmidt, V. M.
2002, Electrochim. Acta, 47, 1983.
39. Mukerjee, S., Srinivasan, S., and Soriaga, M. P. 1995, J. Phys. Chem. 99, 4577.
40. Stamenkovi, V., Schmidt, T. J., Ross, P. N., and Markovi, N. M. 2002, J. Phys.
Chem. B, 106, 11970.
41. Mukerjee, S., and Srinivasan, S., 1993, J. Electroanal. Chem., 357, 201.
42. Chu, D., and Gilman, S. 1994, J. Electrochem. Soc., 141, 1770.
43. S. Narayanan et. al. 1994, J. Power Sources, 47, 377.
44. Wasmus, S., and Kuver, A. 1999, J. Electroanal. Chem., 461, 14.
45. Arico, A. S., Srinivasan, S., and Antonucci, V. 2001, Fuel Cells, 1, 133.
46. Parsons, R., VanderNoot, T. 1988, J. Electroanal. Chem., 257, 9.
47. Li, W. Z., Liang, C. H., Qiu, J. S., Zhou, W. J., Han, H. M., Wei, Z. B., Sun, G. Q.,
and Xin, Q. 2002, Carbon, 40, 787.
48. Li, W. Z., Liang, C. H., Zhou, W. J., Qiu, J. S., Zhou, Z. H., Sun, G. Q., and Xin,
Q. 2003, J. Phys. Chem. B, 107, 6292.
36
49. Liu, Z. L., Lin, X. H., Lee, J. Y., Zhang, W. D., Han, M., and Gan, L. M.
Langmuir, 2002, 18, 4054.
50. Sun, X., Li, R., Villers, D., Dodelet, J. P., Desilets, S. 2003, Chem. Phys. Lett. 379,
99.
51. Planeiz, J. M., Coustel, N., Coq, B., Brotons, V., Kumbhar, P. S., Dutartre, R.,
Geneste, P., Bernier, P., Ajayan, P. M. 1994, J. Am. Chem. Soc., 116, 7935.
52. Wang, C., Waje, M., Wang, X., Tang, J. M., Haddon, R. C., and Yan, Y. 2004,
Nano Lett., 4, 345.
53. Girishkumar, G., Vinodgopal, K., and Kamat, P. V. 2004, J. Phys. Chem. B, 108,
19960.
54. Rajesh, B., Karthik, V., Karthikeyan, S., Thampi, K. R., Bonard, J. M., and
Viswanathan, B. 2002, Fuel, 81, 2177.
55. Bessel, C. A., Laubernds, K., Rodriguez, N. M., and Baker, R. T. K. 2001, J. Phys.
Chem. B, 105, 1115.
56. Steigerwalt, E. S., Deluga, G. A., Cliffel, D. E., and Lukehart, C. M. 2001, J. Phys.
Chem. B, 105, 8097.
57. Boxall, D. L., Deluga, G. A., Kenik, E. A., King, W. D., and Lukehart, C. M. 2001,
Chem. Mater. 13, 891.
58. Hyeon, T., Han, S., Sung, Y.-E., Park, K.-W., Kim, Y.-W. 2003, Angew. Chem.
Int. Ed. 42, 4352.
59. Han, S., Yun, Y., Park, K.-W., Sung, Y.-E., Hyeon, T. 2003, Adv. Mater. 15, 1922.
60. Park, K.-W., Sung, Y.-E., Han, S., Yun, Y., Hyeon, T. 2004, J. Phys. Chem. B,
108, 939.
61. Che, G. L., Lakshmi, B. B., Fisher, E. R., and Martin, C. R. 1998, Nature, 393,
346.
62. Joo, S. H., Choi, S. J., Oh, I., Kwak, J., Liu, Z., Terasaki, O., and Ryoo, R. 2001,
Nature, 412, 169.
63. Choi, W. C., Woo, S. I., Jeon, M. K., Sohn, J. M., Kim, M. R., and Jeon, H. J.
2005, Adv. Mater. 17, 446.
64. Chai, G. S., Shin, I. S., and Yu, J. S. 2004, Adv. Mater., 16, 2057.
65. Jiang, J., and Kucernak, A. 2003, J. Electroanal. Chem., 54, 187.
66. Leung, L.-W., and Weaver, M. J. 1990, Langmuir, 6, 323.
67. Bockris, J. M., Wroblowa, H. 1964, J. Electroanal. Chem., 7, 428.
68. Christensen, P. A., Hamnett, A., and Troughton, G. L. 1993, J. Electroanal. Chem.,
362, 207.
69. Iwasita, T. 2002, Electrochim. Acta, 47, 3663.
70. Waszczuk, P., Wieckowski, A., Zelenay, P., Gottesfeld, S., Coutanceau, C., Lger,
J.-M., and Lamy, C. 2001, J. Electroanal. Chem., 511, 55.
71. Dinh, H. N., Ren, X., Garzon, F. H., Zelenay, P., Gottesfeld, S. 2000, J.
Electroanal. Chem., 491, 222.
72. Dubau, L., Coutanceau, C., Garnier, E., Lger, J.-M., and Lamy, C. 2003, J. Appl.
Electrochem., 33, 419.
73. Gasteiger, H. A., Markovic, N., Ross, P. N. Jr., and Cairns, E. J. 1994, J.
Electrochem. Soc., 141, 1795.
75. Iwasita, T., Hoster, H., John-Anacker, A., Lin, W. F., and Vielstich, W. 2000,
Langmuir, 16, 522.
37
76. Mukerjee, S., and McBreen, J. 1998, J. Electroanal. Chem., 448, 163.
77. Petrow, H. G. and Allen, R. J. 1997, US Patent No: 40444193.
78. Luna, A. M. C., Camara, G. A., Paganin, V. A., Ticianelli, E. A., and Gonzalez, E.
R. 2000, Electrochem. Commn. 2, 222.
79. Paulus, U. A., Endruschat, U. Feldmeyer, G. J., Schmidt, T. J., Bnnemann, H.,
and Behm, R. J. 2000, J. Catalysis, 195, 383.
80. Bnnemann, H., Brinkmann, R., Britz, P., Endruschat, U., Mrtel, R., Paulus, U.
A., Feldmeyer, G. J., Schmidt, T. J., Gasteiger, H. A., and Behm, R. J. 2000, J.
New Mater. Electrochem. Syst. 3, 199.
81. Schmidt, T. J., Gasteiger, H. A., and Behm, R. J. 1999, Electrochem. Commun. 1,
1.
82. Antolini, E., and Cardellini, F. 2001, J. Alloys Compd. 315 (2001) 118.
83. Hills, C., Mack, N., and Nuzzo, R. 2003, J. Phys. Chem. B, 107, 2626.
84. Takasu, Y., Fujiwara, T., Murakami, Y., Sasaki, K., Oguri, M., Asaki, T., and
Sugimoto, W. 2000, J. Electrochem. Soc., 147, 4421.
85. Aric, A. S., Bagilo, V., Di Blasi, A., Modica, E., Monforte, G., and Antonucci, V.
2005, J. Electroanal. Chem., 576, 161.
86. Zhang, X. and Chan, K.Y. 2003, Chem. Mater. 15, 451.
87. Liu, Y., Qiu, X., Chen, Z., Zhu, W. 2002, Electrochem. Commun. 4, 550.
88. Xiong, L., and Manthiram, A. 2005, Solid State Ionics, 176, 385.
89. Liu, Z., Lee, J. Y., Chen, W., Han, M., and Gan, L. M. 2004, Langmuir, 20, 181.
90. Wang, X., and Hsing, I-M. 2002, Electrochim. Acta, 47, 2981.
91. Sarma, L. S., Lin, T.-D., Tsai, Y.-W., Chen, J.-M., and Hwang, B.-J. 2005, J.
Power Sources, 139, 44.
92. Waszczuk, P., Solla-Gulln, J., Kim, H.-S., Tong, Y. L., Montiel, V., Aldaz, A.,
and Wiekowski, A. 2001, J. Catal. 203, 1.
93. Nashner, M. S., Frenkel, A. I., Somerville, D., Hills, C. W., Shapley, J. R., and
Nuzzo, R. G. 1998, J. Am. Chem. Soc. 120, 8093.
94. Nashner, M. S., Frenkel, A. I., Adler, D. L., Shapley, J. R., and Nuzzo, R. G. 1997,
J. Am. Chem. Soc., 119, 7760.
95. Hills, C. W., Nashner, M. S., Frenkel, A. I., Shapley, J. R., and Nuzzo, R. G. 1999,
Langmuir, 15, 690.
96. Gasteiger, H. A., Markovic, N. M., Ross, P. N. Jr., and Cairns, E. J. 1994,
97. Wang, K., Gasteiger, H. A., Markovic, N. M., and Ross, P. N. Jr. 1996,
98. Markovic, N. M., Gasteiger, H. A., Ross, P. N. Jr., Jiang, X., Villegas, I., and
Weaver, M. J. 1995, Electrochim. Acta, 40, 91.
99. Gasteiger, H. A., Markovic, N., Ross, P. N., and Cairns, E. J. 1994, J. Electrochem.
Soc., 141, 1795.
100. McBreen, J., and Mukerjee, S. 1995, J. Electrochem. Soc., 142, 3399.
101. Iwasita, T., Nart, F. C., and Vielstich, W. 1990, Ber. Bunsenges Phys. Chem. 94,
1030.
102. Frelink, T., Visscher, W., and van Veen, J. A. R. 1996, Langmuir, 12, 3702.
103. Shukla, A. K., Arico, A. S., El-Khatib, K. M., Kim, H., Antonucci, P. L., and
Antonucci, V. 1999, Appl. Surf. Sci. 137, 20.
38
104. Waszczuk, P., Lu, G. Q., Wieckowski, A., Lu, C., Rice, C., and Masel, I. 2002,
105. Hwang, B. J., Sarma, L. S., Chen, J. M., Chen, C. H., Liu, D. G., Lee, J. F., and
Tang, M. T. 2005, J. Am. Chem. Soc., (submitted for publication).
106. Park, S., Wieckowski, A., and Weaver, M. J. 2003, J. Am. Chem. Soc., 125, 2282.
107. Anderson, A. B., Grantscharova, E., Shiller, P. 1995, J. Electrochem. Soc. 142,
1880.
108. Ross, P. N. Jr., Gasteiger, H. A. 1995, Proceedings of the first international
symposium on new materials for fuel cell systems, Montreal, July 913.
109. Bittins-Cattaneo, B., and Iwasita, T. 1987, J. Electroanal. Chem., 238, 151.
110. Cathro, K. J. 1969, J. Electrochem. Soc., 116, 1609.
111. Sobkowski, J., Franasczuk, K., and Piasecki, A. 1985, J. Electroanal. Chem. 196,
145.
112. Frelink, T., Visscher, W., van Veen, J. A. R. 1994, Electrochim. Acta, 39, 1871.
113. Watanabe, M., Furuuchi, Y., and Motoo, S. 1985, J. Electroanal. Chem., 191, 367.
114. Wei, Z., Guo, H., and Tang, Z. 1996, J. Power Sources, 58, 239.
115. Cathro, K. J. 1967, J. Electrochem. Soc., 5, 441.
116. Shrosphire, J. A. 1965, J. Electrochem. Soc., 112, 465.
117. Grgur, B. N., Markovic, N. M., and Ross, P. N. 1999, J. Electrochem. Soc., 146,
1613.
118. Mukerjee, S., Lee, S. J., Ticianelli, E. A., McBreen, J., Grgur, B. N., Markovic, N.
M., Ross, P. N., Giallombardo, J. R., and De Castro, E. S. 1999, Electrochem.
Solid-State Lett., 2, 12.
119. Zhu, Y., and Cabrera, C. R. 2001, Electrochem. Solid State Lett., 4, A45.
120. Shukla, A. K., Ravikumar, M. K., Arico, A. S., Candiano, G., Antonucci, V.,
Giordano, N., and Hamnett, A. 1995, J. Appl. Electrochem. 25, 528.
121. Shen, P. K., and Tseung, A. C. C. 1994, J. Electrochem. Soc., 141, 3082.
122. Deivaraj, T. C., Chen, W., and Lee, J. Y. 2003, J. Mater. Chem., 13, 2555.
123. Lee, S.-A., Park, K.-W., Choi, J.-H., Kwon, B.-K., and Sung, Y.-E. 2002, J.
Electrochem. Soc., 149, A1299.
124. Burcham, L. J., and Wachs, I. E. 1999, Catalysis Today, 49, 467.
125. Thomas, S. C., Ren, X., and Gottesfeld, S. 1999, J. Electrochem. Soc., 146, 4354.
126. Arico, A. S., Shukla, A.. K., El-Khatib, K. M., Creti, P., and Antonucci, V. 1999, J.
Appl. Electrochem., 29, 671.
127. Liu, L., Pu, C., Viswanathan, R., Fan, Q., Liu, R., and Smotkin, E. S. 1998,
128. Ley, K. L., Liu, R., Pu, C., Fan, Q., Leyarovska, N., Segre, C., and Smotkin, E. S.
1997, J. Electrochem. Soc., 144, 1543.
129. Liu, L., Viswanathan, R., Liu, R., and Smotkin, E. S. 1998, Electrochem. Solid
State Lett. 1, 123.
130. Aramata, A., and Masuda, M. 1991, J. Electrochem. Soc. 138, 1949.
131. He, C., Kunz, H. R., and Fenton, J. M. 1997, J. Electrochem. Soc., 144, 970.
132. Arico, A. S., Poltarzewski, Z., Kim, H., Morana, A., Giordano, N., and Antonucci,
V. 1995, J. Power Sources, 55, 159.
133. Arico, A. S., Creti, P., Giordano, N., Antonucci, V., and Antonucci, P. L. 1996, J.
Appl. Electrochem. 26, 959.
134. Lasch, K., Jrissen, L., and Garche, J. 1999, J. Power Sources, 84, 225.
39
135. Choi, J.-H., Park, K.-W., Park, I.-S., Nam, W.-H., and Sung, Y.-E. 2004, 50, 783.
136. Park, K.-W., Choi, J.-H., Lee, S.-A., Pak, C., Chang, H., Sung, Y.-E. 2004, 224,
236.
137. Anderson, A. B., Grantscharova, E., and Seong, S. 1996, J. Electrochem. Soc., 143,
2075.
138. Shukla, A. K., Neergat, M., Parthasarathi, B., Jayaram, V., and Hegde, M. S. 2001,
J. Electroanal. Chem., 504, 111.
139. Fuel Cell Handbook, fifth ed., EG & G Services Parsons, Inc., 2000.
140. El Hourch, A., Coutanceau, C., Lger, J. M., and Lamy, C. 1997, J. Electroanal.
Chem., 426, 117.
141. Bittins-Cattaneo, B., Wasmus, S., and Vielstich, W. 1993, J. Appl. Electrochem.,
23, 625.
142. Jiang, R. Z., and Chu, D. Y. 2000, J. Electrochem. Soc., 147, 4605.
143. Convert, P., Coutanceau, C., Gloaguen, F., and Lamy, C. 2001, J. Appl.
Electrochem. 31, 945.
145. Alonso-Vante, N. 1996, J. Chim. Phys., 93, 702.
146. Schmidt, T. J., Paulus, U. A., Gasteiger, H. A., Alonso-Vante, N., and Behm, R. J.
2000, J. Electrochem. Soc., 147, 2620.
147. Alonso-Vante, N., Tributsch, H. 1986, Nature, 323, 431.
148. Alonso-Vante, N., Bogdanoff, P., and Tributsch, H. 2000, J. Cata., 190, 240.
149. Bron, M., Bogdanoff, P., Fiechter, S., Hilgendorff, M. 2001, J. Electroanal. Chem.,
517, 85.
150. Solorza-Feria, O., Ellmer, K., Gierstig, M., Alonso-Vante, N. 1994, Electrochim.
Acta, 39, 1647.
151. Reeve, R. W., Christense, P. A., Hamnett, A., Haydock, S. A. and Roy, S. C. 1998,
J. Electrochem. Soc., 145, 3463.
152. Born, M., Bogdanoff, P., Fiechtler, F., Dorbandt, I., Hilgendorf, M., Schulenberg,
H., and Tributsch, H. 2001, 500, 510.
153. Yang, H., Alonso-Vante, N., Lger, J.-M., and Lamy, C. 2004, J. Phys. Chem. B,
108, 1938.
154. Mailard, F., Martin, M., Gloaguen, F., and Lger, J.-M. 2002, Electrochim. Acta,
47, 3431.
155. Mukerjee, S., and Srinivasan, S. 1993, J. Electroanal. Chem., 357, 201.
156. Li, W., Zhou, W., Li, H., Zhou, Z., Zhou, B., Sun, G., and Xin, Q. 2003,
157. Murthi, V. S., Urian, C., and Mukerjee, S. 2004, J. Phys. Chem. B, 108, 11011.
158. Paulus, U. A., Wokaun, A., Scherer, G. G., Schmidt, T. J., Stamenkovic, J.,
Radmikovic, V., Markovic, N. M., and Ross, P. N. 2002, J. Phys. Chem. B, 106,
4181.
159. Aric, A. S., Shukla, A. K., Kim, H., Park, S., Min, M., and Antonucci, V. 2001,
Appl. Surf. Sci., 172, 33.
160. Mukerjee, S., Srinivasan, S., Soriaga, M. P., and McBreen. 1995, J. Phys. Chem.
B, 142, 1409.
161. Neergat, M., Shukla, A. K., and Gandhi, K. S. 2001, J. Appl. Electrochem. 31, 373.
162. Paffett, M. T., Beery, J. G., and Gottesfeld, S. 1988, J. Electrochem. Soc., 135,
1431.
40
163. Kinoshita, K. 1990, J. Electrochem. Soc. 137, 845.

164. Jalan, V., and Taylor, E. J. 1983, J. Electrochem. Soc., 130, 2299.
165. Beard, B. C., and Ross, P. N. 1990, J. Electrochem. Soc., 130, 3368.
166. Mukerjee, S., Srinivasan, S., and Soriaga, M. P. 1995, J. Phys. Chem. B, 99, 4577.
167. Mukerjee, S. 1990, J. Appl. Electrochem., 20, 537.
168. Adzic, R. R. 1998, Electrocatalysis, J. Lipkowski and P. N. Ross (Eds.,), WileyVCH, New York, 197.
169. Conway, B. E., and Novak, D. M. 1981, J. Electrochem. Soc., 128, 956.
170. Mukerjee, S., Srinivasan, S., Soriaga, M. P., and McBreen, J. 1995, J. Phys. Chem.
99, 4577.
171. Mukerjee, S., Srinivasan, S., and Soriaga, M. P. 1995, J. Electrochem. Soc., 142,
1409.
172. Markovic, N. M., Gasteiger, H. A., and Ross, P. N. 1997, J. Electrochem. Soc.,
144, 1591.
173. K. Kinoshita. 1992, Electrochemical Oxygen Technology, John Wiley & Sons,
New York.
174. Ross, P. N. Jr. 1998, Electrocatalysis, J. Lipkowski and P. N. Ross (Eds.,), WileyVCH, New York, 43.
175. Stonehart, P. 1992, J. Appl. Electrochem., 22, 995.
176. Maoka, T., Kitai, T., Segawa, N., and Ueno, M. 1996, J. Appl. Electrochem., 26,
1267.
177. Stamenkovic, V., Schmidt, T. J., Markovic, N. M., and Ross, P. N. Jr. 2002, J.
Phys. Chem. B, 106, 11970.
178. Zhang, J., Vukmirovic, M. B., Xu, Y., Mavrikakis, M. 2005, Angew. Chem. Int.
Ed., 44, 2132.
179. Zhang, Y., Mo, Y., Vukmirovic, M. B., Klie, R., Sasaki, K., and Adzic, R. R. 2004,
J. Phys. Chem. B, 108, 10955.
180. Ren, X., Wilsonand, M. S., and Gottesfeld, S. 1996, J. Electrochem. Soc., 143, 12.
181. Gottesfeld, S., Zawodzinski, T. A. 1997, Advances in Electrochemical Science and
Engineering, R. C. Alkire, H. Gerischer, D. M. Kolb, C. W. Tobias (Ed.,), WileyVCH, New York, 195.
182. Lamy, C., Lger, J.-M., Srinivasan, S. 2001, Modern Aspects of Electrochemistry,
J. M. Bockris, B. E. Conway., R. E. White (Eds.,), Kluwer Academic
Publishers/Plenum Press, New York, 33.
183. Scott, K., Taama, W. M., and Argyropoulos, P. 2000, J. Membr. Sci., 171, 119.
184. Haubold, H.-G., Vad, T., Jungbluth, H., Hiller, P. 2001, Electrochim. Acta, 46,
1559.
185. Kreuer, K. D., Weppner, W., and Rabenau, A. 1982, Angew. Chem. Int. Ed., 21,
208.
186. Kordesch, K., and Simader, G. 1996, Fuel Cells and their Applications, VCH,
Weinheim.
187. Wang, J.-T., Wasmus, S., and Savinell, R. F. 1996, J. Electrochem. Soc., 143,
1239.
188. Hickner, M., Ghassemi, H., Kim, Y. S., Einsla, B. R., McGrath, J. E. 2004, Chem.
Rev., 104, 4587.
189. Silva, V. S., Schirmer, J., Reissner, R., Ruffman, B., Silva, H., Mendes, A.,
Maderia, L. M., Nunes, S. P. 2005, J. Power Sources, 140, 41.
41
190. Kerres, J., Zhang, W., Jrissen, L., Gogel, V. 2002, J. New Mater. Electrochem.
Syst., 5, 97.
191. Mikhailenko, S. D., Zaidi, S. M. J., and Kaliaguine, S. 2001, Catal. Today, 67, 225.
192. Kreuer, K. A. 2001, J. Membr. Sci., 185, 3.
193. Zaidi, S. M. J., Mikailenko, S. D., Robertson, G. P., Guiver, M. D., and
Kaliaguine, S. 2000, J. Membr. Sci. 173, 17.
194. Wang, J.-T.,Wainright, J. S., Savinell, R. F., and Litt, M. 1996, J. Appl.
Electrochem., 26, 751.
195. Pu, C., Huang, W., Ley, K. L., and Smotkin, E. S. 1995, J. Electrochem. Soc., 142,
119.
196. Ponce, M. L., Prado, L., Ruffmann, B., Richau, K., Mohr, R., and Nunes, S. P.
2003, J. Membr. Sci., 217, 5.
197. Manea, C., and Mulder, M. 2002, J. Membr. Sci., 206, 443.
198. Roziere, J., and Jones, D. J. 2003, Annu. Rev. Mater. Res., 33, 503.
199. Schulster, M. F. H., and Meyer, W. H. 2003, Annu. Rev. Mater. Res., 33, 233.
200. Savadogo, O. 1998, J. New Mater. Electrochem. Syst., 1, 47.
201. Paddison, S. J. 2003, Annu. Rev. Mater. Res., 33, 289.
202. Alberti, G., and Casciola, M. 2003, Annu. Rev. Mater. Res., 33, 129.
203. Li, Q., He, R., Jensen, J. O., and Bjerrum, N. J. 2003, Chem. Mater., 15, 4896.
204. Ruffmann, B., Silva, H., Schulte, B., and Nunes, S. P. 2003, Solid State Ionics,
162163, 269.
205. Nunes, S. P., Ruffmann, B., Rikowsky, E., Vetter, S., and Richau, K. 2002, J.
Membr. Sci., 203, 215.
206. Manea, C., and Mulder, M. 2002, J. Membr. Sci., 206, 443.
207. Dimitrova, P., Friedrich, K. A., Vogt, B., and Stimming, U. 2002, J. Electroanal.
Chem. 532, 75.
208. Li, L., Zhang, J., and Wang, Y. 2003, J. Membr. Sci., 226, 159.
209. Li, L., Xu, L., and Wang, Y. X. 2003, Mater. Lett., 57, 1406.
210. Silva, V., Ruffman, B., Silva, H., Mendes, A., Maderia, M., and Nunes, S. 2004,
Mater. Sci. Forum, 455456, 587.
211. Bauer, B., Jones, D. J., Roziere, J., Tchicaya, L., Alberti, G., Massinelli, M.,
Peraio, A., Besse, S., and Ramunni, E. 2000, J. New Mater. Electrochem. Syst., 3,
93.
212. Jin, X., Bishop, M. T., Ellis, T. S., and Karasz, F. E. 1985, Br. Polymer J., 17, 4.
213. Shibuya, N., and Porter, R. S. 1992, Macromolecules, 25, 6495.
214. Trotta, F., Drioli, E., Moraglio, G., and Poma, E. B. 1998, J. Polym. Sci., 1998, 70,
477.
215. Ise, M., Kreuer, and K. D., Maier, J. 1999, Solid State Ionics, 125, 213.
216. Kreuer, K. D. 1997, Solid State Ionics, 97, 1.
217. Kreuer, K. D. 2001, J. Membr. Sci., 185, 29.
218. Rikukawa, M., and Sanui, K. 2000, Prog. Polym. Sci., 25, 1463.
219. Kerres, J., Ullrich, A., Hring, T., Baldauf, M., Gebhardt, U., and Pridel, W. 2000,
J. New Mater. Electrochem. Syst., 3, 229.
220. Kerres, J., Cui, W., and Junginger, M. 1998, J. Membr. Sci., 139, 227.
221. Kerres, J., Ullrich, A., Meier, F., and Hring, T. 1999, Solid State Ionics, 125, 243.
222. Kerres, J., Tang, C.-M., and Graf, C. 2004, Ind. Eng. Chem. Res., 43, 4571.
42
223. Bailly, C., Williams, D. J., Karasz, F. E., and MacKnight, W. J. 1987, Polymers,
28, 1009.
224. Wang, J. T., Wasmus, S., and Savinell, R. F. 1996, J. Electrochem. Soc., 143,
1233.
225. Wainright, J. S., Wang, J.-T., Weng, D., Savinell, R. F., and Litt, M. H. 1995, J.
Electrochem. Soc., 142, L121.
226. Bouchet, R., and Siebert, E. 1999, 118, 287.
227. Roziere, J., Jones, D. J., Marrony, M., Glipa, X., and Mula, B. 2000, Solid State
Ionics, 145, 61.
228. Xing, B., and Savadogo, O. 2000, Electrochem. Commun., 2, 697.
229. He, R., Li, Q., Xiao, G., and Bjerrum, N. J. 2003, J. Membr. Sci., 226, 169.
230. Blonsky, P. M., Shriver, D. F., Austin, P., and Allock, H. R. 1984, J. Am. Chem.
Soc., 106, 6854.
231. Tang, H., Pintauro, P. N., Guo, Q., and Connor, S. 1999, J. Appl. Polym. Sci., 71,
387.
232. Wycisk, R., and Pintauro, P. N. 1996, J. Membr. Sci., 119, 155.
233. Guo, Q., Pintauro, P. N., Tang, H., and Connor, S. 1999, J. Membr. Sci., 154,
175.
234. Honma, I., Hirakawa, S., Yamada, K., and Bae, J. M. 1998, Solid State Ionics, 118,
29.
235. Honma, I., Takeda, Y., and Bae, J. M. 1999, Solid State Ionics, 120, 255.
236. Honma, I., Nomura, S., and Nakajima, H. 2001, J. Membr. Sci., 185, 83.
237. Nakajima, H., Nomura, S., Sugimoto, T., Nishikawa, S., and Honma, I. 2002, J.
238. Honma, I., Nakajima, H., Nishikawa, O., Sugimoto, T., and Nomura, S. 2002, J.
239. Staiti, P., and Minutoli, M. 2001, J. Power Sources, 94, 9.
240. Staiti, P., Minutoli, M., and Hocevar, S. 2000, J. Power Sources, 90, 231.
241. Baradie, B., Poinsignon, C., Sanchez, J. Y., Piffard, Y., Vitter, G., Bestauoi, N.,
Foscallo, D., Denoyelle, A., Delabouglise, D., and Vaujany, M. 1998, J. Power
Sources, 74, 8.
242. Genova-Dimitrova, P., Baradie, B., Foscallo, D., Poinsignon, C., and Sanchez, J.
Y. 2001, J. Membr. Sci., 185, 59.
243. Samms, S. R., Wasmus, S., and Savinell, R. F. 1996, J. Electrochem. Soc., 143,
1498.
244. Nunes, S. P., Ruffmann, B., Rikowski, E., Vetter, S., and Richau, K. 2002, J.
Membr. Sci., 203, 215.
245. Ponce, M. L., de A. Prado, L. A. S., Silva, V., and Nunes, S. P. 2004, Desalination,
162, 383.
246. Chang, H. Y., and Lin, C. W. 2003, J. Membr. Sci., 218, 295.
247. Chang, H. Y., Thangamuthu, R., and Lin, C. W. 2004, J. Membr. Sci., 228, 217.
248. Thangamuthu, R., and Lin, C. W. 2005, Solid State Ionics, 176, 531.
249. Lin, C. W., Thangamuthu, R., and Yang, C. J. 2005, J. Membr. Sci., 253, 23.
250. Li, L., Xu, L., and Wang, Y. 2003, Mat. Lett., 57, 1406.
251. Xu, W., Liu, C., Xue, X., Su, Y., Lv, Y., Xing, W., and Lu, T. 2004, Solid State
Ionics, 171, 121.
43
252. Kim, D. S., Park, H. B., Rhim, J. W., and Lee, Y. M. 2005, Solid State Ionics, 171,
117.
253. Lin, C. W., Thangamuthu, R., and Chang, P. H. 2005, J. Membr. Sci., (In press).
254. Shen, M., Roy, S., Kuhlmann, J. W., Scott, K., Lovell, K., and Horsfall, J. A.
2005, J. Membr. Sci., 251, 121.
255. Choi, K.-Y., Eom, J.-Y., Jung, H.-Y., Choi, N.-S., Lee, Y.-M., Park, J.-K., Choi,
J.-H., Park, K.-W., and Sung, Y.-E. 2004, Electrochim. Acta, 50, 583.
256. Rao, N., Anderson, T. P., and Ge, P. 1994, Solid State Ionics, 72, 334.
257. Kjaer, J., Yde-Anderson, S., Knudsen, N. A., Skou, E. 1991, Solid State Ionics, 46,
169.
258. Hamlen, R. P. 1999, U. S. Patent 5849428.
259. Poltrazewski, Z., Wieczorek, W., Przyluski, J., Antonucci, V. 1999, Solid State
Ionics, 119, 301.
260. Tung, S.-P., and Hwang, B.-J. 2004, J. Membr. Sci., 241, 315.
261. Tung, S.-P., and Hwang, B.-J. 2005, J. Mat. Chem., (Communicated for
publication).
262. Fontanella, J.-J., Wintersgill, M.-C., Chen, R.-S., Wu, Y., and Greenbaum, S.-G.
1995, Electrochim. Acta, 40, 2321.

Advances in Fuel Cells - Chapter 2

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Advances in Fuel Cells - Chapter 2

Enviado por

Direitos autorais:

Formatos disponíveis

Research Signpost

37/661 (2), Fort P.O., Trivandrum-695 023, Kerala, India

Advances in Fuel Cells, 2005:

Privileged materials for direct

Loka Subramanyam Sarma & Bing Joe Hwang

Privileged materials for direct methanol fuel cells

the two principle reactions in DMFCs such as methanol oxidation reaction

2. Principle reactions in DMFCS

Protons generated at the anode pass through the proton exchange

The free energy (G) of overall reaction at 25 oC and 1 atm is 686

Loka Subramanyam Sarma & Bing Joe Hwang

2.1. Methanol oxidation reaction (MOR)

At potentials of technical interest for DMFCs (<0.6 V vs. RHE) the

Privileged materials for direct methanol fuel cells

During methanol oxidation the efficient catalyst must allow a complete

2.2. Oxygen reduction reaction (ORR)

Loka Subramanyam Sarma & Bing Joe Hwang

O2 + 4 H+ + 4 e 2 H2O (E0 = 1.23 V vs. SHE)

O2 + 2 H+ + 2 e H2O2 (E0 = 0.67 V vs. SHE)

The adsorbed peroxide in equation 14b can be electrochemically reduced to

Privileged materials for direct methanol fuel cells

Pt(OHOH)ads + H+ + e Pt(OH) + H2O

or catalytically decomposed on the electrode surface, or can be desorbed into

3. Privileged materials for DMFCS

3.1. Carbon supports

Loka Subramanyam Sarma & Bing Joe Hwang

finding innovative carbon materials capable of accommodating high metal

3.1.1. Carbon nanotubes (CNTs)

Privileged materials for direct methanol fuel cells

Loka Subramanyam Sarma & Bing Joe Hwang

3.1.2. Graphite carbon nanofibers (GCNFs)

Privileged materials for direct methanol fuel cells

and (d) the attainment of a preferred crystallographic orientation by the

3.1.3. Carbon nanocoils (CNCs)

3.1.4. Porous carbon nanostructures

Loka Subramanyam Sarma & Bing Joe Hwang

carbon nanotubule supported Pt electrodes have been studied for oxygen

Privileged materials for direct methanol fuel cells

Loka Subramanyam Sarma & Bing Joe Hwang

3.2.1.1. Binary Pt-based alloy electrocatalysts

Privileged materials for direct methanol fuel cells

dehydrogenation of methanol and it would facilitate the CO desorption,

Loka Subramanyam Sarma & Bing Joe Hwang

Privileged materials for direct methanol fuel cells

whereas the nanocomposite with 50 wt% shows higher performance when

Loka Subramanyam Sarma & Bing Joe Hwang

FTIR data on PtRu samples shows a CO stretching frequency shift to

Privileged materials for direct methanol fuel cells

reduction in the overpotential by 170260 mV. Out of this total only 40 mV is

Loka Subramanyam Sarma & Bing Joe Hwang

Privileged materials for direct methanol fuel cells

3.2.1.2. Binary Pt-based alloy electrocatalysts other than PtRu

Loka Subramanyam Sarma & Bing Joe Hwang

experimental conditions, the latter effect may stimulate a catalytic activity of

3.2.1.3. Ternary Pt-based electrocatalysts

Privileged materials for direct methanol fuel cells

properties towards methanol oxidation, however methods describing the role of

3.2.2. Electrocatalysts for oxygen reduction reaction

Loka Subramanyam Sarma & Bing Joe Hwang

namely, PtCr/C [153155], PtFe/C [156, 157], PtNi/C [158], PtCo/C

Privileged materials for direct methanol fuel cells

Particle size effects need to be studied carefully. The majority of

Loka Subramanyam Sarma & Bing Joe Hwang

Table 3. Summary of oxygen reduction reaction catalysts under development.