DOI: 10.1002/cphc.

201100984

Electrocatalysis Using Porous Nanostructured Materials

Nadine Menzel,* Erik Ortel, Ralph Kraehnert, and Peter Strasser[a]

The performance of electrochemical reactions depends strong-
ly on the morphology and structure of the employed catalytic
electrodes. Nanostructuring of the electrode surface represents
a powerful tool to increase the electrochemically active surface
area of the electrodes. Moreover, it can also facilitate faster dif-
fusive mass transport inside three-dimensional electrodes. This
minireview describes recent trends in the development of syn-
thesis routes for porous nanostructured electrode materials
and discusses the respective important electrocatalytic applica-
tions. The use of structure-directing agents will play a decisive
role in the design and synthesis of improved catalysts.

1. Introduction

Electrochemistry is enjoying growing interest in science and of all individual steps that contribute to an electrocatalytic pro-
technology. In addition to established electrolysis processes cess.
such as the evolution of halogens, for example, chlorine,[1, 2] Scheme 1 illustrates an example of a porous electrode and
galvanic elements such as fuel cells, photoelectrochemical cells the sequence of coupled physicochemical steps that constitute
(PEC), or batteries have come to the fore in recent years. In an electrocatalytic process. The chemical transformation of re-
particular, low-temperature fuel
cells, such as polymer electrolyte
membrane fuel cells (PEMFC)[3–5]
or direct methanol fuel cells
(DMFC),[6–8] enable efficient and
direct electrochemical conver-
sion of hydrogen or methanol
into electricity. Hence, they rep-
resent key technology for the
future production of electricity
from renewable, clean, and sus-
tainable resources. The wide-
spread practical use of this tech-
nology requires the develop-
ment of more efficient processes
and, in particular, new efficient
electrocatalysts. Moreover, a
deeper understanding of the re-
action mechanisms and kinetics Scheme 1. Schematic representation of the individual physicochemical steps that constitute an electrocatalytic
process. The process is illustrated for the example of a porous electrode applied to an oxidation reaction.
is also important to improve the
electrocatalytic performance.
The efficiency of an electroca-
talytic reaction is expressed as the overpotential, h (sum of actants occurs in the reaction layer near the surface of the
losses of electric potential), that is, the difference between a electrode. The catalytic reaction itself proceeds at the interface
theoretical potential required for a catalytic reaction and the between (accessible) the electrode surface and electrolyte. It
potential required in the practical experiment. These losses consists of adsorption, reaction, and desorption. However,
result from different physicochemical phenomena, for example, these catalytic steps are often preceded by diffusive transport
kinetic reaction overpotentials and ohmic overpotentials.
Ohmic overpotentials are a consequence of electric resistance [a] N. Menzel, E. Ortel, Dr. R. Kraehnert, Prof. Dr. P. Strasser
of the electrolyte, transport limitations of charged reactant The Electrochemical Energy, Catalysis, and Materials Science Laboratory
species, and conductor and contact resistances. Minimizing Department of Chemistry, Chemical Engineering Division
Technical University Berlin
these overpotentials is one of the main challenges for electro-
Straße des 17. Juni 124, 10623 Berlin (Germany)
chemists in the development of efficient electrocatalysts. How- Fax: (+ 49) (0)30 314-22261
ever, such optimization requires a fundamental understanding E-mail: nadine.menzel@tu-berlin.de

ChemPhysChem 2012, 13, 1385 – 1394  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1385

Nadine Menzel received her Engineer-
ing Diploma in 2008 at the Technical
University Berlin, Germany, in chemical
engineering. She is currently working
on her doctoral thesis at the same uni-
versity in the group of Prof. P. Strasser.
Her research is focused on the funda-
mental understanding of mechanistic
aspects of the electrochemical chlorine
evolution which also includes synthesis
of electrocatalysts and electrochemical
measurements.
Erik Ortel received his M.Sc. in 2008 at
the Technical University of Applied Sci-
ences Berlin, Germany, in pharmaceuti-
cal and chemical engineering. He is
currently a Ph.D. student at the Techni-
cal University of Berlin in the Junior
Research Group DEPOKATnm of Dr.-Ing.
Ralph Kraehnert. His research is mainly
focused on the synthesis of mesopo-
rous oxide films for catalytic applica-
tions.
Ralph Kraehnert was awarded a
degree as Dr.-Ing. in 2005. His work on
Pt-catalyzed oxidation of ammonia
was carried out at the Institute of Ap-
plied Chemistry Berlin under the guid-
ance of Prof. M. Baerns. Since 2007 he
has led an independent Junior Re-
search Group financed by the NANO-
FUTUR program of BMBF. He develops
methods for a rational design of cata-
lysts and the synthesis of porous
oxides, colloidal nanoparticles and cat-
alysts with controllable nanostructure.
Peter Strasser is a full professor in the
Chemical Engineering Division of the
Department of Chemistry at the Tech-
nical University of Berlin. Prior to his
appointment, he was an Assistant Pro-
fessor at the Department of Chemical
and Biomolecular Engineering at the
University of Houston and prior to that
he served as a senior member of staff
at Symyx Technologies, Inc. In 1999,
Peter Strasser obtained his doctoral
degree in physical chemistry and elec-
trochemistry from the Fritz-Haber Institute of the Max-Planck Soci-
ety, Berlin, under the direction of Professor Gerhard Ertl. He studied
chemistry at Stanford University, USA, the University of Tuebingen,
Germany, and the University of Pisa, Italy, and received his diploma
degree (M.S.) in chemistry in 1995.
1386 www.chemphyschem.org
N. Menzel et al.
of reactants to the electrode interface, chemical reactions oc-
curring in the electrolyte, and mass transport from the bulk of
the electrolyte to the reaction layer. Moreover, the products of
the electrocatalytic surface reaction are also the subject of sim-
ilar reaction and transport steps. The chemical and geometrical
configuration of the catalytic electrode provides control over
all of these individual steps.
Optimized catalytic electrodes show a low intrinsic overpo-
tential for the desired reaction path and a high overpotential
for undesired side reactions. Moreover, they provide high elec-
trical conductivity and good mechanical, chemical, and electro-
chemical stability. To maximize the number of active sites, they
also possess a high active surface with good accessibility to
the reactants. The intrinsic catalytic properties are controlled
by the choice of the local composition of the electrodes. In
contrast, surface area and transport properties can be opti-
mized by nanostructuring of the electrode material.
In general, electrodes consist of a current collector and a
substrate that is coated with the electrocatalyst. This catalyst is
formed either completely of the active material or by a catalyst
support onto which active particles are deposited. The shape
of the electrodes can be flat, rough, or 3D porous. Flat or
rough electrodes are often made from a solid bulk metal. How-
ever, due to their low surface-to-volume ratio they are only
useful when highly active and cheap materials are used. In
contrast, porous structures provide a higher specific (active)
surface area, but at the expanse of increasing manufacturing
effort. Porous electrodes exist for both bulk and supported cat-
alysts. In the latter, pores are introduced into the support ma-
terial. The porosity of the catalyst material, that is, its nano-
structure, controls not only the active surface area, but also
the transport of reactants and products. These can exist in
either liquid or gas phases (e.g. gas evolution reactions). While
small pores provide a higher surface area, they can also de-
crease the rate of mass transport. The synthesis of porous cata-
lysts therefore requires control over the obtained pore size.
Porous electrocatalysts have been synthesized in many dif-
ferent ways. Synthesis methods include chemical reduction or
electrochemical deposition from metal salt solutions, deposi-
tion by sputtering or precursor evaporation, sol–gel synthesis,
powder technology, or spraying and dip-coating methods.
However, the degree of porosity and control over the electro-
catalyst nanostructure varies significantly between the different
synthesis methods.
This minireview focuses on synthesis methods that enable
direct control over the catalyst nanostructure through physical
synthesis parameters or with auxiliary structure-directing
agents. Synthesis options for porous catalysts and porous cata-
lyst supports are described in Section 2. Moreover, the role of
the nanostructure in improving the performance of the elec-
trocatalysts is discussed for three selected reactions in Sec-
tion 3.
 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2012, 13, 1385 – 1394
Porous Nanostructured Materials
2. Synthesis of Porous Nanostructured
Electrocatalysts
The synthesis of porous nanostructured electrocatalysts can be
realized by nanostructuring of either the conductive support
(mostly carbon) or the electrocatalytically active material
(mostly metals or metal oxides). Possible synthesis routes for
nanostructured electrocatalysts described below are 1) nano-
casting by using templates, 2) dealloying of alloys, and 3) elec-
troassisted deposition or dissolution.
2.1. Nanocasting with Templates
Nanocasting is the process in which a template with a length
scale of nanometers is surrounded or filled with the material
(or a precursor for it) to be cast. The initial template is re-
moved thereafter from the stabilized precursor phase, thereby
a material with open porosity can be obtained. Different tem-
plates allow precise control over the synthesized porous struc-
ture.[9, 10] In a review from 2010, Walcarius highlighted recent
trends for template-directed porous electrodes in the field of
electroanalysis.[11] The following part only focuses on the main
nanocasting synthesis strategies that lead to porous templated
electroactive catalysts and are highlighted by a few examples.
Figure 1 illustrates the nanocasting concept of using mi-
celles of amphiphilic polymer molecules as soft templates.
Upon deposition, the micelles assemble into well-defined peri-
odic mesostructures, such as hexagonal or cubic phases, in
which the voids between the micelles are filled with the pre-
cursor (Figure 1I). Subsequent treatment of the composite re-
moves the template (typically by template extraction or heat
treatments) and results in mesoporous materials (Figure 1II).[12]
The general concept allows the synthesis of both mesoporous
carbon and metal oxides. The precursor used (organic precur-
sors for carbon and metal alkoxides or metal salts for metal
oxides) and synthesis conditions permit the synthesis of meso-
porous bulk catalysts (Figure 1II; e.g. Pt,[13] Pt/Ru,[13] RuO2,[14]
IrO2[15]) or mesoporous catalyst supports with incorporated
active species (Figure 1IIa; e.g. Pt in carbon,[16] Pt–Pb in
carbon/Nb2O5[17]). The mesoporous material (Figure 1II) result-
ing from soft templating can itself be replicated again; this
material then acts as a “hard template” (Figure 1III). The hard
template, for example, mesoporous silica SBA-15, is infiltrated
with a precursor. After template removal (by HF in the case of
silica), a negative mesoporous replicate (Figure 1III) is obtained,
which resembles the initial structure of the soft templates (Fig-
ure 1I).[18] In analogy to the soft-templated route, mesoporous
electrocatalytic active materials (Figure 1III; Pt–Ru[19]) or meso-
porous supports (Figure 1IIIa) can be achieved. Such mesopo-
rous supports obtained by the hard-templating pathway (Fig-
ure 1IIIa) are, for example, OMCs,[20] which are widespread in
the field of nanostructured electrocatalysts (see Sections 3.1
and 3.2). Nevertheless, carbon-free, hard-templated mesopo-
rous WO3 was also successfully used as a nanostructured elec-
trode catalyst support.[21]
Examples of materials obtained by the nanocasting ap-
proach are given in Figure 1 for both the synthesis of bulk cat-
ChemPhysChem 2012, 13, 1385 – 1394  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 1. An illustration of the nanocasting pathway by soft (I) and hard (II)
templates. TEM images of representative electrocatalysts based on mesopo-
rous supports and mesoporous materials as “active” phases are presented.
A) Poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide) (PEO-b-PB-
b-PEO) soft-templated IrO2 (reprinted with permission from[15]), B) Pt–Pb in-
corporated in poly(isoprene-block-ethylene oxide) (PI-b-PEO) soft-templated
carbon–Nb2O5 composite (reprinted with permission from ref. [17]), C) meso-
porous silica SBA-12hard-templated Pt–Ru (reprinted with permission from
ref. [19]), and D) Pt incorporated in ordered mesoporous carbon (OMC; re-
printed with permission from ref. [6]).
alysts (A, B) and support materials with incorporated active
components (C, D). Figure 1 A illustrates a TEM image of a mes-
oporous iridium oxide film prepared by the soft-templated
preparation pathway (Figure 1II). The iridium oxide film was
obtained by dip-coating through deposition of iridium acetate
precursor and PEO-b-PB-b-PEO polymer templates[22] on titani-
um electrodes. After heat treatment at 300 8C, the soft-tem-
plate decomposed and iridium oxide with a cubic mesostruc-
ture with pore sizes of 16 nm and a specific surface area of
248 m2 g1 (Kr-BET) was obtained.[15] The catalytic performance
of templated versus untemplated IrO2 catalyst in the oxygen
evolution reaction (OER) is discussed in Section 3.3.
Figure 1 B shows a TEM image of Pt–Pb nanoparticles incor-
porated into the pores of a mesoporous niobium oxide–
carbon composite support. The synthesis procedure reported
by Orilall et al.[17] is based on the self-assembly of PI-b-PEO
block copolymer templates with NbCl5/Nb(OEt)5 and noble-
metal precursors [(dimethylcyclooctadiene)platinumand triphe-
nyl(phenylethynyl)lead]. After heat treatments (700 8C under
argon and subsequently 875 8C under reductive atmosphere), a
crystalline, hexagonally arranged, cylindrical, mesoporous
niobium oxide–carbon composite with Pt–Pb nanoparticles in-
corporated into the mesopores was obtained. The materials
synthesized in one pot show pores with an average diameter
of around 25 nm and specific surface areas (N2-BET) between
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 N. Menzel et al.

137 and 217 m2 g1. These electrocatalysts show promising

electrochemical activity toward formic acid oxidation.
The TEM image in Figure 1 C presents a nanostructured
Pt–Ru electrocatalyst synthesized through the hard-templating
approach (Figure 1III), reported by Jiang and Kucernak.[19] First,
they synthesized hexagonal mesoporous SBA-12 silica using
nonionic surfactant Brij 76 as the soft template and tetraeth-
oxysilane (TEOS) as the silica source. After calcination a meso-
porous silica hard-template was obtained. Subsequently,
H2PtCl6 and RuCl3 were impregnated into the silica template
Figure 2. Electron microscopy images of hard-templated electrocatalysts.
and heat-treated at 300 8C. Thereafter, the silica template was A) AAO-templated Pt–Ru nanowires (reprinted with permission from
removed by using a solution of 10 wt % HF at room tempera- ref. [24]), B) Ag nanowire templated Pt nanotubes (reprinted with permission
ture. The retained nanostructured Pt–Ru material with meso- from ref. [8]).
pores of about 3 nm in diameter demonstrates high activity to-
wards the electrochemical oxidation of methanol.
Figure 1 D shows a TEM image of an OMC film with incorpo- ethylene glycol reduction of silver nitrate. Figure 2 B shows a
rated Pt nanoparticles (synthesis path IIIa). Here, Su et al.[6] first TEM image of the respective templated electrocatalysts.
prepared hexagonal mesoporous silica SBA-15 with the surfac- In the case of a nanostructured electrocatalyst with regular
tant P123 and a SiO2 precursor. The calcined mesoporous SBA- pore sizes above 50 nm, spherical latex templates (e.g. polymer
15 hard template was impregnated with benzene (carbon or silica spheres) can be employed.[26] These spheres are assem-
source) by chemical vapor deposition (CVD). After carboniza- bled into colloidal crystals with highly uniform 3D structures
tion at 900 8C the silica hard template was then removed with and are then infiltrated with a carbon or metal oxide precursor.
HF solution. Platinum nanoparticles were then deposited on Alternatively, the spheres and the precursor are codeposited.
the prepared mesoporous carbon by the borohydride reduc- Thereafter, the template is usually removed by calcination
tion method. The enhanced activity of this material in electro- (polymer) or HF etching (SiO2) to produce porous catalysts or
chemical methanol oxidation is described in Section 3.2. carbon supports. Chai et al.[27] synthesized ordered, uniform,
In addition to templating routes that start with amphiphilic porous carbon frameworks with pore sizes in the range of 10
molecules, porous anodic aluminum oxide (AAO)[23] hard tem- to 1000 nm by infiltration of colloidal SiO2 templates with
plates can also be used for the preparation of nanostructured phenol and formaldehyde (carbon source) followed by poly-
electrocatalysts. For example, Zhao et al.[24] used AAO tem- merization and carbonization of the carbon precursor. The
plates for the synthesis of Pt–Ru and Pt nanowire array electro- porous carbons were used as supports for Pt–Ru alloy nano-
des on Ti/Si substrate. This catalyst synthesis started with the particles in methanol fuel cell catalysts. Figure 3 A shows a TEM
preparation of the AAO template by anodization of a thin Al
film on a conductive Ti/Si substrate in oxalic acid solution at
20 V (see also Section 2.3). The resulting AAO template con-
tained uniform cylindrical pores that were aligned perpendicu-
lar to the substrate surface. The pores were then filled with a
metal by electrodeposition from an electrolyte solution con-
taining, for example, H2PtCl6 and RuCl3. A platinum plate was
used as a counter electrode and the AAO/Ti/Si structure was
the working electrode. The as-prepared composites were im-
mersed in a solution of NaOH to remove the AAO template.
The brush-shaped Pt–Ru nanowires obtained were about
30 nm in diameter and 1 mm in length. They were tested for Figure 3. TEM images of A) Pt–Ru incorporated in macroporous carbon (re-
methanol electro-oxidation. Figure 2 A shows a SEM image of printed with permission from ref. [27]) and B) hollow carbon spheres with in-
corporated Pt (reprinted with permission from ref. [28]).
the surface morphology of the prepared Pt–Ru nanowires. In a
similar way, Liu et al.[25] used AAO hard templates to synthesize
multisegment Pt–Ni nanorods as methanol electro-oxidation image of this catalyst. Furthermore, Su et al.[28] synthesized
catalysts by sequential electrodeposition of Pt and Ni into polystyrene-templated macroporous silica as a hard template
nanoporous anodic alumina membranes. to deposit carbon on the surface of this inverse silica opal. The
Moreover, Alia et al.[8] used silver nanowires as hard tem- carbon deposition was carried out by using a CVD method
plates to synthesize porous platinum nanotubes for oxygen re- with benzene vapor as the carbon precursor. Then, carbon/
duction and methanol oxidation reactions. The porous plati- silica composite was immersed in HF solution to remove the
num nanotubes, with a thickness of 5 nm, an outer diameter silica. The macroporous carbon was used as a support for plati-
of 60 nm, and a length of 5–20 mm, were synthesized by gal- num nanoparticles and showed strong performance improve-
vanic displacement of silver nanowires, which were formed by ments in the methanol oxidation reaction due to nanostructur-
ing of the catalyst support (see Section 3.2). Figure 3 B shows a

1388 www.chemphyschem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2012, 13, 1385 – 1394
Porous Nanostructured Materials
TEM image of the hollow carbon spheres with a diameter of
around 200 nm with incorporated platinum nanoparticles.
It is clear that, in contrast to the soft-templated synthesis
route, the hard-templating approach demands more prepara-
tion steps. However, hard templates are often more stable
against the precursor system and a precise negative replica of
the template can be created more easily than with soft tem-
plates. In general, nanocasting of templates is one of the most
promising synthesis strategies to precisely control the porous
structure of nanostructured electrocatalysts.
2.2. Nanoporous Materials Made by Dealloying
Another important synthetic process to obtain 3D highly
porous electrocatalytic electrodes is chemical dealloying[29]
(CD). In this synthesis single-phase, multicomponent bulk
alloys are formed by melting. From this alloy, the less-noble
metal is selectively dissolved by an etching process in
acids,[30, 31] alkalis,[32, 33] or electrochemically.[34, 35] The removal of
the less-noble metal can result in mesopores being formed in
the remaining metal. The synthesis of mesoporous electrocata-
lysts by chemical or electrochemical dealloying has, for exam-
ple, been reported for Au from an Ag–Au alloy,[36–41] Pt from
Cu–Pt[34, 42] or Si–Pt,[42] Cu from Mn–Cu,[35, 43] and Al–Cu[32] and
Ag from Al–Ag.[31, 33] Control over the size of the mesopores
during electrochemical or chemical dealloying results from
varying the starting alloy composition,[36] the electrochemical
potential driving dissolution,[36] the electrolyte temperature,[34]
the dealloying/etching time,[35] or employing thermal annealing
after dealloying.[36] A potential drawback of the synthetic
method is the fact that complete removal of the alloying com-
pound cannot be guaranteed; hence, the second metal might
also affect the electrochemical performance of the resulting
catalysts.
Typical electron microscopy images of nanoporous gold
films made by dealloying from different Ag–Au alloys are pre-
sented in Figure 4.Figure 4 a depicts a cross-sectional SEM
Figure 4. SEM images of nanoporous Au made by selective dissolution of Ag
from an Ag–Au alloy. a) Cross-section of dealloyed Au32 atm %Ag68 atm %.
b) Planar view of dealloyed Au26 atm %Ag74 atm %. (reprinted with permission
from ref. [36]).
image of dealloyed Au32 atm %Ag68 atm %, which shows an open
porosity in the whole film. The planar view of a dealloyed
Au26 atm %Ag74 atm % film (Figure 4 b) indicates ligament spacings
in the order of 10 nm.
The dealloying method described can also serve for the syn-
thesis of a support such as porous gold. When compared with
typical carbon supports, the deposition of an atomically thin
ChemPhysChem 2012, 13, 1385 – 1394  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
layer of platinum on gold can improve the catalyst/substrate
binding while providing a high dispersion of the active plati-
num phase.[30] Furthermore, it is possible to use the dealloyed
porous material as a hard template for the nanostructuring of
platinum-based electrocatalysts formed by epitaxial casting.[44]
An epitaxial skin of a second material is coated on a mold that
is subsequently dissolved away. In this case platinum is grown
epitaxially onto the nanoporous gold by an electroless plating
process described by Ding et al.[30] This is a simple strategy to
synthesize free-standing noble-metal membranes with a hier-
archical bicontinuous porous architecture.
With dealloying it is possible to synthesize porous 3D cata-
lysts in a simpler and faster way than with the templating
techniques described in Section 2.1. However, the synthesis of
ordered nanopore structures by dealloying has not been re-
ported so far.
2.3. Electrochemical Deposition and Dissolution
For some electrode compositions, material-specific synthetic
routes for nanostructures exist. This includes, in the case of ti-
tania, the electrochemical dissolution of titanium to create TiO2
nanorods; metals such as platinum can also be nanostructured
by electrochemical deposition in the presence of structure-di-
recting agents.
Schmuki et al. synthesized highly ordered, self-organized
TiO2 nanotubes by electrochemical anodization of titani-
um.[45–47] This synthetic route represents a simple electrochemi-
cal oxidation reaction of a metallic titanium substrate under
specific conditions, such as a sufficient anodic voltage and
acidic fluoride (0.05–0.5 m) containing electrolytes. However,
oxide nanotubes with well-defined lengths and diameters and
vertical alignment relative to the substrate are obtained. The
defined nanostructure results from varying the pH of the elec-
trolyte[48, 49] (influences the thickness of the tube walls), the
voltage[50, 51] (diameter of the tubes), or anodization time[47, 51]
(tube length). Figure 5 shows one example of TiO2 tubes ob-
Figure 5. Electron microscopy images of TiO2 nanotubes made by anodiza-
tion of Ti. a) Plan view and b) cross-section of the TiO2 nanotubes (reprinted
with permission from ref. [46]).
tained by electrochemical anodization of a titanium foil in
0.135 m HF in ethylene glycol electrolyte at 30 V for 5 h. After
anodization the sample was annealed in air for 1 h at 450 8C.
Macak et al.[45] demonstrated the influence of TiO2 nanotubes
as supports for Pt/Ru nanoparticles in the methanol oxidation
reaction.
Electrochemical and hydrothermal methods can be com-
bined to synthesize porous platinum electrodes. In the hydro-
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 N. Menzel et al.

thermal-assisted seed growth method,[52] platinum particles are H 2 O 2 þ 2 H þ þ 2 e ! 2 H 2 O ð3Þ

first deposited electrochemically on titanium substrates with-
out structure-directing agents. Thereafter, porous platinum
Platinum-based materials are the most commonly used cata-
structures were reported to grow by hydrothermal treatment
lysts for ORR,[4, 5, 59] often in the form of unsupported large crys-
of these substrate for 10 h at 100 8C using autoclaves contain-
talline platinum black particles.[60]
ing ethylene glycol, a platinum salt (H2PtCl6), and HCl, for ex-
A decrease in the platinum loading was achieved by the in-
ample.[53]
troduction of carbon black as a catalyst support (commercial
Nanostructured (mesoporous) electrodes of metals such as
Pt/C).[61, 62] Due to the high surface area of carbon black, better
Pt[54, 55] and Au[56, 57] can also be synthesized by electrochemical
spatial distribution and utilization of the active platinum parti-
deposition through electroreduction of a metal salt in the pres-
cles were achieved. However, the ORR activity of a catalyst also
ence of hard or soft templates, such as silica colloids,[56, 57] poly-
depends significantly on the size of the platinum particles and
styrene (PS) particles,[57] or micelles of octaethylene glycol
the spatial distribution of these particles over the support.[63]
monohexadecyl ether (C16EO8)[54, 55] (see Section 2.1). Moreover,
Despite the high surface area of carbon black, two main disad-
ruthenium oxide[58] was synthesized in a similar way; however,
vantages exist: Due to its dense structure carbon black sup-
in this case, the structure-directing agent was polystyrene.
ports show significant mass-transfer limitations. Moreover, they
Methanol oxidation on porous platinum catalysts was studied
also undergo thermal degradation at high fuel-cell working
by Garcia et al.[55]
temperatures.[64, 65]
In many syntheses it is necessary to use a templating
A significant improvement in the ORR performance can be
method before the electrochemical deposition of the electro-
achieved by using nanostructured carbon supports, as sum-
catalytic active material can be carried out. Therefore, numer-
marized in a review by Antolini.[62] In particular, OMC[62, 66–70] at-
ous preparation steps are needed; however, precise control of
tracted great attention as a catalytic support material for ORR
the pore diameters and layer thickness is possible. In the case
due to their controllable pore sizes and high surface areas (see
of anodization, only a 1D structure could be synthesized. Ad-
Section 2.1). Higher spatial distribution of the active nanoparti-
vantages of this method are the precisely tunable tube lengths
cles and more facile diffusion of reactants and products due to
and diameters and also direct electrical connectivity between
the mesoporous structure led to an increase in the catalytic
the substrate and support or catalytically active material due
performance. Figure 6 demonstrates the activity increase of
to direct growth of the tubes from the substrate.

3. Applications as Electrocatalysts
A complete overview of all reported applications of nanostruc-
tured electrocatalysts is beyond the scope of this minireview.
However, we focus on three selected electrochemical reactions,
namely, oxygen reduction, methanol oxidation, and oxygen
evolution, to illustrate the advantages of the nanostructured
electrodes. Two of these examples employ supported catalysts,
namely, the oxygen reduction reaction (Section 3.1) and meth-
anol oxidation (Section 3.2), whereas the oxygen evolution re-
action uses the unsupported catalyst IrO2 (Section 3.3).

3.1. Oxygen Reduction Reaction on Carbon-Supported

Platinum
One of the most serious challenges in the development of
proton-exchange membrane fuel cells (PEMFC) is the oxygen
reduction reaction (ORR). ORR is a complex electrode reaction
due to it irreversibility and the very slow kinetics. Two possible
reaction pathways for the ORR exist: the direct 4-electron re-
duction pathway [Eq. (1):
O 2 þ 4 H þ þ 4 e ! 2 H 2 O ð1Þ
and the two-electron reduction pathway with hydrogen perox-
ide as an intermediate [Eqs. (2) and (3)]:
O 2 þ 2 H þ þ 2 e ! H 2 O 2 ð2Þ
Figure 6. Potential–current density plots for oxygen reduction on Pt cata-
lysts in 0.5 m H2SO4 at room temperature on gas diffusion electrodes made
of Pt/OMC with Pt particle sizes of 40 ( ! ) and 4 nm (~), and commercial
Pt/C with a Pt particle size of 2 nm (*) at loadings of 0.6 mg per cm2 of Pt.
Potentials are given versus a saturated calomel electrode (SCE; reprinted
with permission from ref. [67]).
ORR on OMC supports. The OMC support was synthesized by
hard templating with SBA-15 mesoporous silica. Sucrose was
used as the carbon source. At an identical Pt loading and com-
parable Pt particle size, the OMC-supported Pt catalyst clearly
shows enhanced ORR activity compared with the standard
Pt/C catalyst. At a potential of about 0.55 V versus SCE [
 0.31 V vs. a reversible hydrogen electrode (RHE)] the current

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Porous Nanostructured Materials

density (per cm2 of electrode) of a Pt/OMC catalyst is twice as

high as the activity of a commercial Pt/C electrocatalyst.
Furthermore, Yamada et al.[68] reported that OMC facilitated
better spatial distribution of small Pt particles (  5 nm) and
promoted improved electrolyte transportation; this resulted in
a 2.5 higher limiting current density at a potential of 0.4 V
versus RHE. Hayashi et al.[69] and Vengatesan et al.[70] also con-
firmed such an improvement of the catalytic performance due
to better spatial distribution of the platinum nanoparticles in
the ordered mesoporous structure and better mass transport
of the reactants and products in and at the electrocatalyst. Fur-
ther information on the use of unsupported porous catalysts
in fuel cells can be found in a recent review by Antolini and
Perez.[71]
Figure 7. Typical cyclic voltammograms for the electro-oxidation of metha-
nol at platinum catalysts in 0.5 m H2SO4 + 1 m CH3OH at room temperature.
3.2. Methanol Oxidation on Carbon-Supported Platinum Pt/XC-72 is a commercial catalyst and Pt/CMK-5-xxx-60 are synthesized or-
dered porous carbons, in which the last number denotes the graphitization
DMFCs are promising highly efficient and clean energy sources
time and the second number is the graphitization temperature. Potentials
for applications in electric vehicles and portable devices. The are given versus SCE (reprinted with permission from ref. [16]).
oxidation of methanol is an important reaction for the design
of DMFCs. The total oxidation process of the methanol oxida-
tion can be written as shown in Equation (4): comparison of different catalysts. Lower onset potentials corre-
spond to better catalysts.
CH3 OH þ H2 O ! CO2 þ 6 Hþ þ 6 e ð4Þ Much effort has been made to enhance the performance of
methanol oxidation. One method was the improvement of
This total oxidation process can be divided in the three con- electrocatalytic activity and minimization of CO poisoning due
ventional reactions for a platinum catalyst shown in Equa- to the use of Pt–Ru[19, 27] alloys or other metals or metal
tions (5), (6), and (7):.[72] alloys.[73–75] Furthermore, great work has been made to improve
access to large areas of the catalytic material, as well as facili-
Pt þ CH3 OH ! Pt-CO þ 4 Hþ þ 4 e ð5Þ tate electron transfer and mass transport due to structuring
Pt þ H2 O ! Pt-OH þ Hþ þ e ð6Þ and well-developed porosity of the support.
The standard catalytic activities of platinum catalysts on
þ 
Pt-CO þ Pt-OH ! 2 Pt þ CO2 þ H þ e ð7Þ carbon black (Pt/C) were determined by different
groups.[6, 8, 76, 77] Results given in Table 1 show that specific cur-
A typical cyclic voltammogram for the oxidation of methanol rent densities with relation to the electrochemical surface area
on platinum is shown in Figure 7. (ECSA) are between 0.1 and 0.4 mA per cm2 of Pt at 0.7 V
The cyclic voltammetry profiles show that, at a potential of versus RHE for standard Pt/C catalysts. The onset potential is
around 0.2 V versus SCE, methanol molecules adsorb at the around 0.6 V versus RHE.
platinum surface [Eq. (5)]. Water is oxidized at a potential of For catalysts with an OMC support, the onset potential is
about 0.4–0.45 V vs. SCE [Eq. (6)]. If both species are adsorbed slightly lower (  0.1 V) and the specific current density is
on the surface, then the formation of CO2 can occur [Eq. (7)], around 0.4 mA per cm of Pt, which is higher than the values
as indicated in the cyclic voltammogram by the increase in the for a commercial catalyst (Table 1). Su et al.[6, 28] demonstrated
potential in the forward scan at this point (see Figure 7). Due that catalysts with ordered meso- and macroporous carbon
to formation of PtOH or PtO,
the current density reaches a
maximum value and decrease Table 1. Catalytic activity of methanol oxidation for Pt (20 wt %) on OMC supports and commercial carbon at
room temperature.
thereafter (  0.6–0.7 V vs. SCE).
MeOH decomposition and CO Synthesis procedure of Pt20 wt %/C and Pt20 wt %/OMC Onset poten- j [mA per cm2 of Pt] cMeOH Ref.
removal do not proceed effi- tial [V] vs. RHE at 0.7 V vs. RHE [mol L1]
ciently on PtO surfaces. In the commercial Pt/C (E-TEK)  0.5  0.15 1 [28]

[6]
backward scan, CO desorption commercial Pt/C (E-TEK)  0.6  0.1 1
[28]
starts at a potential of about hard templating with silica opal, CVD for 2 h at  0.45  0.4 1
1000 8C
0.7 V vs. SCE and reaches a maxi- hard templating with SBA-15, CVD for 1 h at 900 8C  0.55  0.3 1 [6]

mum current density at around hard templating with SBA-15, CVD for 60 min at  0.55  0.63 1 [16]

0.4 V vs. SCE. The onset potential
and current density at a selected
potential are important for the
500 8C and graphitization at 850 8C
[7, 20]
hard templating with SBA-15, wet impregnation,  0.6 0.5
functionalization in 2 m HNO3 for 0.5 h

ChemPhysChem 2012, 13, 1385 – 1394  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 1391
 N. Menzel et al.

supports (pore size:  3.5[6] and  70 nm,[28] respectively) had a methods with polymer micelles, as described in Section 2.1.
higher electrocatalytic activity towards methanol oxidation Soft templating created mesopores of about 16 nm in diame-
than standard catalysts. This results from better mass transport ter, as shown in Figure 1 A.
of the reactants and products due to higher spatial distribution Figure 8 A provides information about the active surface
of platinum particles on the mesoporous material. Lei et al.[16] area of the film, which was determined electrochemically in a
also showed that the electrocatalytic activity of Pt supported potential window between 0.4 and 1.4 V versus RHE.[15] The
on OMC (pore size  3–4.7 nm) was higher than that of stan-
dard catalysts. Moreover, Calvillo and co-workers reported that
functionalization with HNO3 to create oxygen groups at the
surface of OMC improved the performance of methanol oxida-
tion due to better spatial distribution and anchoring of the
platinum particles on the support.[7, 20]
This short summary of OMCs as one example of a porous
nanostructured catalyst support for methanol oxidation shows
that the characteristics of the carbon support for platinum cat-
alysts have great impact on electrochemical properties in
methanol oxidation. The OMCs offer a larger accessible surface
area than that of standard carbon blacks; this results in better
spatial distribution of the platinum particles on the support
and enhances catalytic activity. Furthermore, the area of the
electrode/electrolyte interface increases, which enhances
charge and mass transport through the porous Pt/OMC cata-
lyst and decreases the diffusion distance of electrolyte ions.

3.3. OER on Unsupported IrO2

OER is the anodic half-cell reaction of the water-splitting pro-
cess. The efficient oxidation of water is a great challenge in the
development of viable, cost-effective, durable technologies for
the conversation of light into storable fuels. The electrochemi-
cal water-splitting reaction is divided into two half-cell reac-
tions. The hydrogen evolution reaction (HER) proceeds at the
cathode and the OER at the anode. The oxidation process is
shown in Equation (8):

2 H 2 O ! O 2 þ 4 H þ þ 4 e ð8Þ

OER is a very complex process with several surface-adsorbed

intermediates and the mechanism of OER on these different
electrodes is still a matter of discussion. More detailed informa-
tion about the water-splitting reaction and it half-cell reactions
can be found in a recent review by Dau et al.[78]
Among numerous catalytic materials, such as binary and ter-
nary ruthenium metal alloys,[79, 80] ruthenium oxides, or rutheni-
um mixed metal oxides,[81–84] iridium oxide is regarded as one
of the most stable and active catalysts for the OER.[15, 85–89]
Recent studies on the synthesis of colloidal iridium oxide nano-
particles[85, 87, 90] reported an increase in the electrochemically
active surface area and a reducing OER overpotential. Iridium
particles were deposited on the electrode support. The over-
potential for the OER, determined at a current density of
0.5 A cm2, was around 0.25 V versus RHE, as reported by Naka-
gawa et al.[87] However, synthetic method did not provide
access to controlled pore structure and crystallinity of the
layers. Recently, we highlighted a soft-templated synthesis of
nanocrystalline mesoporous IrO2 catalyst layers. The mesopo-
rous IrO2 catalyst layers were synthesized by soft-templating
Figure 8. A) Cyclic voltammograms of a) templated and b) untemplated IrO2
films in a potential window between 0.4 and 1.4 V versus RHE and a scan
rate of 50 mV s1. B) Cyclic voltammograms for the OER in a potential
window between 1 and 1.6 V versus RHE recorded with a scan rate of
6 mV s1 on a) templated and b) untemplated IrO2 films. The current density,
j, is normalized to the geometric surface area of the working electrode (re-
printed with permission from ref. [15]). Insets show SEM images of a) tem-
plated and b) untemplated IrO2 films calcined at 450 8C.
templated mesoporous (Figure 8 A, a) film exhibits a signifi-
cantly larger active surface area than the untemplated IrO2
sample (Figure 8 A, b). Figure 8 B shows cyclic voltammograms
of the OER recorded on IrO2 films with and without templated
mesoporosity. These voltammograms were recorded under
quasi-steady-state voltammetric responses (scan rate 6 mV s1).
Both catalysts are active for OER; however, the templated mes-
oporous catalyst clearly shows a higher catalytic activity per
geometric surface area of the planar electrode (see Figure 8 B).
Therefore, the improved performance of the templated meso-

1392 www.chemphyschem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2012, 13, 1385 – 1394
Porous Nanostructured Materials
porous catalyst in Figure 8 B originates from an increase in the
accessible surface area.
4. Summary and Outlook
Nanostructured conductive porous materials are attractive can-
didates as supports or active components of catalytic electro-
des. The porous nanostructure significantly increases the cata-
lytically active surface area and accelerates mass transport;
hence, porous electrodes are particularly beneficial for gas re-
actions in gas diffusion electrodes. Beyond the examples dis-
cussed herein, porous electrodes are also suited for gas reac-
tions such as hydrogen evolution and reduction, formic acid
formation,[91] CO and glucose oxidation, or the chlorine evolu-
tion reaction. In most cases, the intrinsic catalytic activity is not
influenced by the structuring of the electrode support or the
catalytic species.
Depending on the detailed nature of the reacting molecules,
mass transport and diffusion rates, optimum pore diameters,
wall thicknesses, and catalyst or support morphologies may
differ significantly. Hence, individual optimization of the elec-
trode material is required for each application. We have em-
phasized three different synthetic routes that are applicable for
the synthesis of well-ordered, porous, nanostructured elec-
trode materials. Close collaboration between material scientists
and electrochemists will promote new promising develop-
ments in the field of porous nanostructured materials as highly
active electrocatalysts.
Acknowledgements
We thank Tobias Reier, Mehtap Oezaslan, and Frdric Hasch for
assistance and aid in obtaining information about the topic. In
addition, we thank the German Cluster of Excellence in Catalysis
(UNICAT) funded by the German National Science Foundation
(DFG) managed by the Technical University Berlin for financial
support. E.O. and R.K. acknowledge generous funding from BMBF
within the frame of the Nanofutur program (FKZ 03X5517A).
Keywords: carbon · electrochemistry · mesoporous materials ·
nanostructures · oxygen
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Received: December 9, 2011
Published online on February 14, 2012

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