Electrochemical investigation of electrocatalysts for the

oxygen evolution reaction in PEM water electrolyzers

Shidong Song
a,b,
*, Huamin Zhang
a,
*, Xiaoping Ma
a
, Zhigang Shao
a
,
Richard T. Baker
c
, Baolian Yi
a
a
Proton Exchange Membrane Fuel Cell Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, 457 Zhongshanlu Road, Dalian, Liaoning 116023, PR China
b
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
c
School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
a r t i c l e i n f o
Article history:
Received 4 August 2007
Received in revised form
29 March 2008
Accepted 21 June 2008
Available online 9 September 2008
Keywords:
Water electrolysis
Regenerative fuel cell
Oxygen evolution reaction
Anode electrocatalyst
Catalyst coated membrane
a b s t r a c t
To develop the proton exchange membrane water electrolyzer (PEMWE) with satisfactory
performance and durability for application in a regenerative fuel cell (RFC) system, anode
electrocatalysts of Ir, Ru and their oxides were prepared and incorporated into the catalyst
coated membranes (CCM) of the PEMWE. Repetitive cyclic voltammetry of the Naon
bonded electrodes, steady state polarization curves and stability testing of the single
PEMWE cells were performed to investigate the performance and stability of these elec-
trocatalysts. The structure and specic surface areas of the electrocatalysts were charac-
terized by XRD and BET. IrO
2
exhibited a slightly lower performance but a markedly higher
stability than the other electrocatalysts. By modifying the preparation process via
a colloidal iridium hydroxide hydrate precursor, which permitted a lower heat treatment
temperature, its performance was enhanced, corresponding to a terminal voltage of 1.63 V
at 1 A/cm
2
.
2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
The electrolysis of water using cells with a proton exchange
membrane (PEM) is an attractive and efcient method for
producing hydrogenand oxygenat lowtemperature. Recently,
it has been considered to be a very promising technology for
future large scale hydrogen production and on-board gener-
ation of oxygen in space applications [1].
However, the development of proton exchange membrane
water electrolyzer (PEMWE) systems has beenheld back by the
cost of components such as the PEM and the precious metal
electrocatalysts. Since there are still no non-noble metal
electrocatalysts with satisfactory activities yet developed, it
becomes vital to reduce production costs by improving the
specic performance and durability of those noble metal
electrocatalysts. On the hydrogen side of the cell, platinum
provides the best performance and is commonly used for the
PEMWE cathode [2,3]. Most of the overpotential losses are
related to the electrochemical processes at the anode, where
the oxygen evolution reaction (OER) takes place [4]. Therefore,
the development and optimization of anode electrocatalysts is
of great importance for PEMWE technology. Because of the
acidic environment and high anode potential during water
electrolysis, non-noble catalytic metals like Ni and Co cannot
* Corresponding authors. Dalian Institute of Chemical Physics, Proton Exchange Membrane Fuel Cell Key Materials and Technology
Laboratory, 457 Zhongshanlu Road, Dalian, Liaoning 116023, PR China. Fax: 86 411 84665057.
E-mail addresses: songshidong@dicp.ac.cn (S. Song), zhanghm@dicp.ac.cn (H. Zhang).
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ he
0360-3199/$ see front matter 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.06.039
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1
be used due to corrosion [5]. In noble metal electrocatalysts, Pt
forms a poorly conducting oxide lm and shows a high over-
potential for OER. However, electrocatalysts consisting of Ir,
Ru, or their oxides (which are reported to have the rutile
structure and to be very good conductors (metallic type,
w10
4
U
1
cm
1
[6])) have been shown to possess very high
electrocatalytic activities for OER [7]. Tseung and Jasem[8] and
Trasatti [9] put forward guidelines for the choice of oxide
electrocatalysts for OER. They emphasized that oxygen
evolution can only proceed when the electrode potential is
higher than the potential of the metal/metal oxide couple or
the lower metal oxide/higher metal oxide couple, which
indicates that OER is governed by surface electrochemistry.
After Beer [10] discovered the dimensionally stable anodes
(DSAs), oxides of Ir and Ru have been used as catalysts on
titaniumsubstrates inDSAs for a varietyof electrode processes
such as water electrolysis and the chlor-alkali process. Many
researchers have studied the use of IrO
2
and RuO
2
in DSAs for
the OER in acid electrolyte solutions [1113]. The following
reaction cycle was generally proposed as the mechanism for
the OER on these anode electrocatalysts [1416].
S H
2
O/S--OH
ads
H

(1)
S--OH
ads
/S--O
ads
H

(2)
S--O
ads
S--O
ads
/2S O
2
(3)
Here S represents the oxide electrocatalyst. OH
ads
and O
ads
represent adsorbed hydroxyl species and adsorbed oxygen
atoms, respectively.
Nevertheless, DSAs are unsuitable for use in PEMWEs due
to the difculty in obtaining good contact between the elec-
trocatalyst layer and the PEM electrolyte [17]. Inspired by the
proton exchange membrane fuel cell (PEMFC) techniques, the
electrocatalyst layer is preferably fabricated on the membrane
directly forming the catalyst coated membranes (CCMs) rather
than on the titanium substrate [17,18]. Although very
comprehensive studies of Ir or Ru DSA oxides have been
carried out, to date, work regarding the electrochemical
investigations of anode electrocatalysts in polymer electro-
lytes, especially with respect to their potential application in
PEMWEs in RFC systems, are scarce. The RFC is a promising
energy storage and conversion system which consists of
a PEMWE and a PEMFC subsystem. It can be applied not only
for space applications but also in on-site energy storage
systems. These systems have the advantages of being free
from self-discharge and of giving theoretically higher energy
densities compared to secondary batteries. However, existing
secondary battery systems have a clear advantage over RFC
when roundtrip efciency is considered. The roundtrip ef-
ciency of charging and discharging secondary batteries is
about 80%, but the practically achievable roundtrip efciency
of RFCs (electricity to hydrogen and hydrogen back to elec-
tricity) is generally around 40%. Despite this, such RFC
systems may be applicable for use with renewable energy
sources, such as photovoltaic, wind and hydroelectric energy.
One of the benets of a PEMWE is the wide range of power
loadings and very rapid power-up/power-downrates, whichis
compatible withrenewable energy sources, whichare variable
by nature. The evaluation of electrocatalysts, especially the
stability of anodic electrocatalysts under variable input energy
conditions, should, therefore, be of interest. However, to the
best of our knowledge, most of the stability tests of electro-
catalysts are carried out potentiostatically or galvanostatically
in a single cell, as for secondary batteries.
In our previous work, we achieved a very high performance
of water electrolysis operation with IrO
2
/Pt anode electro-
catalysts [1922]. The cell voltage required was only about 1.6
and 1.8 V at current densities of 1 and 2 A/cm
2
, respectively
[19]. In the present work, electrocatalysts of Ir, Ru and their
oxides were prepared and incorporated into the Naon
bonded electrodes and the CCMs of PEMWEs. Repetitive cyclic
voltammetry of the Naon bonded electrodes, steady state
polarization curves and galvanostatic stability testing of the
single PEMWE cells were performed in order to investigate the
performance and stability of these electrocatalysts. XRD and
BET techniques were also employed to examine the structure
and specic surface areas of the electrocatalysts.
2. Experimental
2.1. Preparation of anode electrocatalysts
Ru and Ir catalysts were prepared by the reduction of their
chloride solution with NaBH
4
[23]. After reaction, the reduced
and precipitated slurry was washed repeatedly with distilled
water until no Cl

was detected. Finally, the electrocatalysts

were obtained after centrifugation and drying.
RuO
2
, IrO
2
, and Ru
0.5
Ir
0.5
O
2
electrocatalysts were made by
proprietary modication of the Adams-type fusion of the
iridiumsalt in a nitrate ux [19,24]. The metal precursor (RuCl
3
or H
2
IrCl
6
$nH
2
O) was added in ethanol/isopropanol (volume
ratio 1:1), followed by the addition of NaNO
3
. The mixture was
heated at 60

C until dry. The salt mixture was further dried in
an oven at 80

C for 30 min. The dry salt mixture was nely
ground and then sintered at 500

C for 30 min to obtain the
salt-oxide mixture. Finally, the mixture was washed with
deionized water until no Cl

was detected to obtain the oxide

product.
In addition, IrO
2
was prepared by a colloid method [25]
which permitted a lower heat treatment temperature.
H
2
IrCl
6
$nH
2
O was dissolved in an NaOH solution. Under the
protection of N
2
at 40

C, the mixture was stirred for 4 h, and
200 mg ascorbic acid was added to the solution, which was
maintained at 5

C. After adjusting the pH to 8 with HClO
4
, a
light yellow precipitate was obtained after 30 h. This resulting
iridium hydroxide hydrate precursor was thermally treated at
400

C for 30 min, forming the oxide material. The IrO
2
sample
prepared by the Adams method was named IrO
2
(A), and that
prepared by the colloid method was named IrO
2
(C).
2.2. Preparation of electrodes for PEMWEs
Ru, Ir, RuO
2
, IrO
2
, and Ru
0.5
Ir
0.5
O
2
were used as anode elec-
trocatalysts. A commercial Pt/C catalyst (28.4 wt%, T.K.K.
Corp.) was used as the cathode electrocatalyst.
To prepare a CCM, a homogeneous ink composed of elec-
trocatalyst, Naon solution (5 wt%, DuPont) and isopropanol
was sprayed directly onto each side of a Naon 112
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1 4956
membrane. The electrocatalyst loading was 0.5 mg/cm
2
for Pt/
C and 3 mg/cm
2
for the anode electrocatalysts.
The CCM was sandwiched between two diffusion layers
and the assembly was hot-pressed at 140

C and 10 MPa to
form the electrode for the PEMWE. The diffusion layers were
prepared using wet-proofed carbon paper (TGP-H-060, Toray)
[17]. A single PEMWE cell using IrO
2
as the anode electro-
catalyst was prepared for a stability test by a similar process
with the exception that a corrosion-resistant diffusion layer,
prepared as in our previous work [19], was applied to the
anode side.
2.3. Physico-chemical characterization
The physical phase and structure of the oxides were probed
using X-ray diffraction (XRD) analysis. Diffraction patterns
were collected on a D/MAX-2400 type diffractometer using Cu-
Ka radiation and equipped with a nickel lter.
The BET method was used to evaluate the specic surface
areas of catalysts by the N
2
absorption method (ASAP2010
Micromeritics Instrument). The BET specic surface areas give
information on the dispersion of particles of a sample in
general, but this is not always directly related to the extent of
the electrochemically active areas of the material. This
information was generally evaluated by the voltammetric
charge from CV voltammograms.
2.4. Preparation of Naon bonded electrodes and
repetitive CV measurements
The working electrode was a thin layer of Naon bonded
catalyst cast on a Pt disk electrode (2 mm in diameter). The Pt
electrode was polished with 0.05 mm alumina slurries. After
polishing, the electrode was washed with ethanol in an
ultrasonic bath and dried under vacuum. The thin lm on the
Pt electrode was prepared as follows: 10 mg electrocatalyst,
1.0 ml ethanol and 80 mL Naon solution (5 wt%, DuPont) were
mixed and ultrasonicated for 30 min to form a black catalyst
ink. A 25-mL portion of the ink was cast on the Pt electrode
surface. The coating was dried at room temperature in air for
1 h. Before measurement, the working electrode surface was
washed carefully with triple distilled water.
The performance and stability investigations of electro-
catalysts were carried out by repetitive CV in a three-electrode
test cell at room temperature. A platinum plate was used as
the counter electrode and a KCl-saturated calomel electrode
(SCE) as the reference. The CV experiments were conducted
between 0 and 1.2 V vs. SCE with a scan rate of 50 mV/s using
a Potentiostat (EG&G 263A) in 0.5 M H
2
SO
4
solution, while
nitrogen was bubbled through the solution.
2.5. Single cell tests on PEMWEs
Steady state polarization and stability test were performed at
80

C in galvanostatic mode using a constant current supply
and a single PEMWE cell with an active area of 5 cm
2
, as
described in a previous paper [21]. Deionized water was
pumped into the anode from the water reservoir and was
maintained at 80

C and atmospheric pressure. The stability
test was conducted at a current density of 300 mAcm
2
for
a period of 20 h.
3. Results and discussion
3.1. Physico-chemical characterization of
electrocatalysts
XRD results of oxide electrocatalyst are presented in Fig. 1. All
peaks match a rutile structure for all the samples. Broad peaks
were observed for IrO
2
samples and Ir doped RuO
2
. This was
consistent with the RuO
2
having crystallized at lower
temperatures than the IrO
2
[26]. Both RuO
2
and IrO
2
have the
rutile crystal structure, which implies that RuO
2
IrO
2
solid
solutions should be easily formed. It is known that the mixed
oxide system of RuO
2
and IrO
2
can form a stable solid solution
within quite wide composition ranges [27,28]. Some diffrac-
tion peaks of RuO
2
disappear and shift towards those of IrO
2
in
the XRD pattern of Ru
0.5
Ir
0.5
O
2
, which possibly indicates the
formation of RuO
2
IrO
2
solid solution. The diffraction peaks
are more clearly discernible for IrO
2
(C) samples than for
IrO
2
(A), indicating that the former possessed a slightly higher
crystallinity though it was calcined at a lower temperature.
The average size of individual crystallites both of IrO
2
(A) and
IrO
2
(C) are about 5.5 nm, as calculated from the Scherrer
equation. The activity of the specic crystal surface planes of
the oxides has been investigated. The authors identied that
the (111) and (101) surface planes, at 34.7

and 40.3

, respec-
tively, had the lowest overpotential for OER [29]. As seen in
Fig. 1, the (101) reection of IrO
2
is signicantly weaker than
that of Ru-based catalysts indicating that the former may
possess a lower electrocatalytic activity for the OER.
The BET specic surface areas of the electrocatalysts are
given in Table 1. The values for the oxides are higher than
Fig. 1 XRD patterns of the oxide electrocatalysts.
Table 1 The BET specic surface area of electrocatalysts
Ir Ru RuO
2
Ru
0.5
Ir
0.5
O
2
IrO
2
(A) IrO
2
(C)
BET (m
2
/g) 7.79 20.9 101 130 120 203
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1 4957
those of the metal electrocatalysts, and IrO
2
(C) exhibited
a much higher specic surface area than IrO
2
(A), indicating
better IrO
2
dispersion. Because the electrocatalyst samples
were dispersed in alcohol in an ultrasonic bath which is
a very similar treatment to the preparation process of Naon
bonded electrodes and CCMs we believe that the dispersion
of the electrocatalysts in the polymer electrolyte may be
similar to that of the samples studied here.
3.2. Repetitive cyclic voltammetry
Fig. 2 ae shows repetitive cyclic voltammograms obtained on
Ru, Ir, RuO
2
, IrO
2
, and Ru
0.5
Ir
0.5
O
2
in 0.5 M H
2
SO
4
solution.
Repetitive potential cycling was applied as a rapid and
convenient method to investigate the ageing properties of the
electrocatalysts under variable transient conditions, with
a viewto their potential application as energy storage systems
connected to intermittent renewable energy sources. The
activity and stability of the electrocatalysts were evaluated
and compared using the initial potential of the OER and the
changes in the shape of the voltammograms before and after
hundreds of scan cycles. In the rst scan cycle, the initial
potentials of OER can be observed. These were lower indi-
cating that the OER could take place more easily for the
metal electrocatalysts. The voltammetric capacitances of all
the electrocatalysts decreased signicantly or appreciably
with increasing number of scan cycles. This might be related
to electrocatalyst erosion and/or dissolution. The dissolution
of RuO
2
and IrO
2
electrocatalysts has been found in some
accelerated lifetime tests [30,31].
The shape of the voltammogram for the Ru electrocatalyst
changed dramatically by the 400th scan cycle compared with
Fig. 2 Cyclic voltammograms of electrocatalysts (a) Ru, (b) Ir, (c) RuO
2
, (d) IrO
2
, and (e) Ru
0.5
Ir
0.5
O
2
during repetitive potential
cycles.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1 4958
the rst one, as shown in Fig. 2a, but became relatively
consistent in the subsequent cycles. The initial potential of
OER moved towards a higher anodic potential and the anodic
current peak decreased signicantly. In the rst cycle, two
pairs of broad peaks localized around 0.4 and 0.8 V vs. SCE
have been attributed to the Ru(III)/Ru(IV) and Ru(IV)/Ru(V)
redox surface transition [32,33], however, they cannot be
observed clearly after 400 scan cycles. It is generally believed
in the study of DSA electrodes that the stability of Ru or RuO
2
electrocatalysts is unacceptably low because of the easy
conversion to a non-conductive and soluble RuO
4
oxide at
high anodic potential [34,35]. After 400 scan cycles for the Ru
electrocatalyst, the anodic current peak for the OER continued
decreasing gradually, indicating a continuous performance
loss. Fig. 2b shows the voltammogramof the Ir electrocatalyst.
As for the Ru electrocatalyst, both the initial potential of the
OER and the shape of the voltammograms changed with
number of scans. However, the anodic current peak for the
OER did not change as much as for Ru over 1000 scan cycles.
After 400 scan cycles Ir achieved a very stable activity, indi-
cating that the Ir can be considered to be more stable an
electrocatalyst than the Ru. Two pairs of broad peaks were
observed in the rst scan cycle at around 0.65 and 0.95 V vs.
SCE. These were attributed to the Ir(III)/Ir(IV) and Ir(IV)/Ir(V)
redox couples, respectively [36]. After 400 scan cycles, the
anodic current peak corresponding to the Ir(III)/Ir(IV) redox
couple had decreased, while that of the oxidation from Ir(IV)
to Ir(V) was enlarged. According to the mechanism of the OER
(see Eqs. (1)(3)), the surface electrochemistry for the OER is
governed by the Ir(III)/Ir(IV) redox couple [37,38]. It is sug-
gested that the activity of Ir for the OER was degraded as the
number of active sites for the Ir(III)/Ir(IV) couple decreased and
the number of those for the Ir(IV)/Ir(V) couple increased. The
voltammogram of RuO
2
, as shown in Fig. 2c, is similar to that
for the Ru electrocatalyst. Both the activity and stability for
the OER were decreased with cycling. This was ascribed to
the conversion of RuO
2
to RuO
4
at high anodic potential. The
voltammogram for RuO
2
did not change as dramatically as
that of Ru, indicating that it is more stable than the Ru elec-
trocatalyst. In Fig. 2d, the voltammogram of the IrO
2
electro-
catalyst was not changed obviously after 1000 cycles, although
a small decrease in current was observed. The stability of IrO
2
was, therefore, markedly higher under repetitive potential
cycling than the other electrocatalyst compositions. Peaks
associated with the redox couples, Ir(III)/Ir(IV) and Ir(IV)/Ir(V),
were not clearly observed because of a much higher capaci-
tance charging current.
The catalytic activity of OER electrodes can be evaluated
by comparing with the double-layer capacitance which is
proportional to the number of surface active sites and calcu-
lated from CV voltammograms at potentials in the double
layer region (generally between 0 and 1.4 V vs. RHE) [9,13,
3941]. However, the voltammetric capacitance of Ir or Ru
oxide contained contributions from both a double-layer
capacitance and a pseudocapacitance. The pseudocapaci-
tance is believed to be caused by the Ru or Ir sites involved in
the faradaic process, while the double-layer capacitance is
related to the number of surface active sites, i.e. in a non-
faradaic process. During long polarization times, the number
of Ru or Ir sites involved in the faradaic process would be
expected to increase, and the pseudocapacitance would be
likely to increase with number of cycles. Therefore, it is
speculated that the decrease of charge storage features in
Fig. 2ae indicates a decrease in the double-layer capacitance
and in the number of active surface sites. By comparing the
corresponding voltammetric capacitances, the CV curves
reveal that the active sites were more numerous on the oxide
electrocatalysts than on the metal electrocatalysts. The trends
in the changes of the shape of the voltammograms also
showed that the oxides possessed a more stable real active
surface area than the metals. Furthermore, the stability in
number of active sites was best for IrO
2
.
Fig. 2e shows the voltammogram of the Ru
0.5
Ir
0.5
O
2
elec-
trocatalyst. As for Ru and RuO
2
, both the activity and stability
for the OER decreased with repetitive potential cycling, but the
change in the shape of the CV curves is obviously less within
the rst 400 scan cycles, in contrast to the behaviour of the
RuO
2
electrocatalyst. This indicates that doping with Ir can
improve the stability of RuO
2
to some extent. From the above
analysis, it is concluded that the IrO
2
electrocatalyst possesses
an acceptable stability under repetitive potential cycling,
which may meet the potential application requirements for
variable power loads. Repetitive CV measurement is found to
be a fast, convenient and effective method for the screening of
different electrocatalysts.
3.3. Single cell performance of PEMWEs
Fig. 3 shows the steady state polarization curves of PEMWE
cells constructed using different anode electrocatalysts. The
potentials are not corrected for IR drops. Ru exhibited the
highest performance at low current density. However, it
degraded dramatically at high current density, which implies
an irreversible conversion of RuO
2
to RuO
4
and a large
increased resistance of the electrode under high anodic
polarization conditions. Ir exhibited the lowest performance
which is consistent with the very low anodic current for the
OER and the relatively small number of active surface sites
deduced from the voltammetric capacitance in the CV curves.
Fig. 3 Steady state polarization curves of PEMWE cells
using different anode electrocatalysts.
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1 4959
The oxide electrocatalysts were relatively close in perfor-
mance. At low current densities the PEMWE using the RuO
2
electrocatalyst showed the lowest terminal voltage, while at
high current densities, it increased signicantly. The PEMWE
using an IrO
2
(C) electrocatalyst showed an obviously better
performance than that using IrO
2
(A), especially at high
current densities, corresponding to the lowest terminal
voltage of 1.63 V at 1 A/cm
2
, which gives a better measure of
the performance under real operating conditions than at low
current densities. This result is probably related to the better
dispersion of the electrocatalyst in the polymer electrolyte
and to the higher conductivity of the electrocatalyst with
higher crystallinity [18]. The activities of the electrocatalysts
deduced from CV analysis are expected to be in a good
agreement with those derived from cell performance tests
because the preparation of the Naon-based CCMs is similar
in both cases. The inset in Fig. 3 is the plot of the steady state
polarization curve of a PEMWE fabricated by the same prep-
aration process as used for the other electrocatalysts, but
using Pt black (T.K.K. Corp.), at the same loading, as the anodic
electrocatalyst. This showed quite a poor performance in
comparison with the other anodic electrocatalysts considered
here.
Although extensive research and development on elec-
trocatalysts for the OER has been performed since the DSA
technique was developed by Beer [10], the applicable electro-
catalysts are still limited to Ir or Ru noble metals and their
oxides. In general, from the previous studies on DSA elec-
trodes, RuO
2
is known as a highly active electrocatalyst for
OER but suffers from instability. IrO
2
is preferred because of
the higher stability but its activity must be improved further to
lower the specic electric power consumption. Hence, there
seem two routes to address the cost saving issue besides the
development of new non-noble electrocatalysts. One route is
to dope RuO
2
with IrO
2
, and perhaps also mix with inert
components like Ta
2
O
5
, to obtain an electrocatalyst with both
high activity and high stability so that the anode electro-
catalyst loading can be reduced. More recently, Marshall et al.
developed Ir
x
Ru
y
Ta
z
O
2
as the anode electrocatalysts for the
PEMWE [26]. The lowest cell voltage, of only 1.567 V at
1 Acm
2
, was achieved with an anode electrocatalyst loading
of 2 mg cm
2
. This may be the best result available in the
published literature. The second route is to reduce the elec-
trocatalyst loading by a physical method. Slavcheva et al.
deposited a thin lm of IrO
2
by magnetron sputtering to form
the anode electrocatalyst layer for PEMWE [42]. The best
performance a cell potential of 1.55 V at 0.3 Acm
2
was
achieved using a 500 nm electrocatalyst layer containing an
anode electrocatalyst loading of only 0.2 mg cm
2
. The results
of the present work show that the activity of IrO
2
can be
improved by modifying the preparation process. If deposition
is onto a cheap, corrosion-resistant and highly conductive
substrate, the catalyst loading can be reduced without
a signicant loss of performance [43]. However, little work on
this has been published to the best of our knowledge. Further
work is therefore required to modify the preparation process
of CCMs and to develop the electrocatalyst substrate.
A stability test using IrO
2
as the anode electrocatalyst was
performed in galvanostatic mode at 300 mAcm
2
for 20 h and
the results are shown in Fig. 4. The potential is relatively
constant throughout the test, indicating the stability of the
IrO
2
electrocatalyst.
Compared with steady state techniques, the transient state
technique is rapid and effective for testing the stability of
electrocatalysts. Furthermore, considering the variable nature
of renewable energy, investigating the electrocatalyst under
transient state conditions may be preferable for meeting the
requirements of RFC applications.
4. Conclusions
The electrochemical performance and stability of Ru, Ir, RuO
2
,
IrO
2
, and Ru
0.5
Ir
0.5
O
2
electrocatalysts were studied by repeti-
tive CV, steady state polarization curves and stability tests.
IrO
2
exhibited a markedly higher stability in repetitive CV
measurements and the single cell stability test. By modifying
the preparation process using a colloidal iridium hydroxide
hydrate precursor, which permitted a lower heat treatment
temperature, its performance was enhanced further. The
results revealed that repetitive cyclic voltammograms is
a rapid and effective method for investigating the activity and
stability of anode electrocatalysts and may be the method of
choice when considering their potential application in
PEMWEs for RFC systems.
Acknowledgement
This work is partly supported by the Knowledge Innovation
Program of the Chinese Academy of Sciences (Grant No.
DICPR200502).
Appendix A
Supplementary data
Supplementary data associated with this article can be found
in the online version, at doi: 10.1016/j.ijhydene.2008.06.039.
Fig. 4 Stability test of PEMWE with IrO
2
as the anode
electrocatalyst at 300 mAcm
L2
and 80 8C.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1 4960
r e f e r e n c e s
[1] McElroy JF. Recent advances in SPE water electrolyzer. J
Power Sources 1994;47(3):36975.
[2] Millet P, Alleau T, Durand R. Characterization of membrane
electrode assemblies for solid polymer electrolyte water
electrolysis. J Appl Electrochem 1993;23(4):32231.
[3] Ioroi T, Kitazawa N, Yasuda K, Yamamoto Y, Takenaka H.
Iridium oxide/platinum electrocatalysts for unitized
regenerative polymer electrolyte fuel cells. J Electrochem Soc
2000;147(6):201822.
[4] Bockris JOM. Hydrogen economy in the future. Int J Hydrogen
Energy 1999;24(1):115.
[5] Millet P. Water electrolysis using eme technology: electric
potential distribution inside a Naon membrane during
electrolysis. Electrochim Acta 1994;39(17):25016.
[6] Trasatti S. Electrodes of conductive metallic oxides (part A).
Amsterdam: Elsevier; 1981.
[7] Krusin-Elbaum L, Wittmer M. Conducting transition metal
oxides: possibilities for RuO
2
in VLSI metallization. J
Electrochem Soc 1988;135(10):26104.
[8] Tseung ACC, Jasem S. Oxygen evolution on semiconducting
oxides. Electrochim Acta 1977;22(1):314.
[9] Trasatti S. Physical electrochemistry of ceramic oxides.
Electrochim Acta 1991;36(2):22541.
[10] H.B. Beer. US patent, 710, 551 (1958); 3,711,385(1971); 3,632,498
(1972).
[11] Lassali TAF, De Castro SC, Boodts JF. Structural,
morphological and surface properties as a function of
composition of Ru Ti Pt mixed-oxide electrodes.
Electrochim Acta 1998;43(1617):251525.
[12] Krysa J, Maixner J, Mraz R, Rousar I. Effect of coating
thickness on the properties of IrO
2
Ta
2
O
5
anodes. J Appl
Electrochem 1998;28(3):36972.
[13] da Silva LA, Alves VA, da Silva MAP, Trasatti S, Boodts JFC.
Oxygen evolution in acid solution on IrO
2
TiO
2
ceramic
lms. A study by impedance, voltammetry and SEM.
Electrochim Acta 1997;42(2):27181.
[14] De Faria LA, Boodts JFC, Trasatti S. Electrocatalytic properties
of ternary oxide mixtures of composition Ru
0.3
Ti
(0.7x)
Ce
x
O
2
:
oxygen evolution from acidic solution. J Appl Electrochem
1996;26(11):11959.
[15] Kota R, Lewerenz HJ, Bruesch P, Stucki S. Oxygen evolution
on Ru and Ir electrodes: XPS-studies. J Electroanal Chem
1983;150(12):20916.
[16] Savinell RF, Zeller III RL. Electrochemically active surface
area. J Electrochem Soc 1990;137(2):48994.
[17] Marshall A, Brresen B, Hagen G, Tsypkin M, Tunold R.
Electrochemical characterisation of Ir
x
Sn
1x
O
2
powders as
oxygen evolution electrocatalysts. Electrochim Acta 2006;
51(15):31617.
[18] Rasten E, Hagen G, Tunold R. Electrocatalysis in water
electrolysis with solid polymer electrolyte. Electrochim Acta
2003;48(2526):394552.
[19] Song SD, Zhang HM, Ma XP, Shao ZG, Zhang YN, Yi BL.
Bifunctional oxygen electrode with corrosion-resistive gas
diffusion layer for unitized regenerative fuel cell.
Electrochem Comm 2006;8(3):399405.
[20] Song SD, Zhang HM, Liu B, Zhao P, Zhang YN, Yi BL. An
improved catalyst-coated membrane structure for PEM
water electrolyzer. Electrochem Solid State Lett 2007;10(8):
B1225.
[21] Shao ZG, Yi BL, Han M. Bifunctional electrodes with a thin
catalyst layer for unitized proton exchange membrane
regenerative fuel cell. J Power Sources 1999;79(1):825.
[22] Liu H, Yi BL, Hou M, Wu JF, Hou ZJ, Zhang HM. Composite
electrode for unitozed regenerative proton exchange
membrane fuel cell with improved cycle life. Electrochem
Solid State Lett 2004;7(3):A569.
[23] Brown HC, Brown CA. A new convenient technique for the
hydrogenation of unsaturated compounds. J Am Chem Soc
1962;84(8):14935.
[24] Adams R, Shriner RL. Platinum oxide as a catalyst in the
reduction of organic compounds. III preparation and
properties of chloroplatinic acid with sodium nitrate. J Am
Chem Soc 1923;45(9):21719.
[25] Marshall A, Brresen B, HagenmG, Tsypkin M, Tunold R.
Preparation and characterisation of nanocrystalline Ir
x
Sn
1x
O
2
electrocatalyticpowders. Mater ChemPhys2005;94(23):22632.
[26] Marshall AT, Sunde S, Tsypkin M, Tunold R. Performance of
a PEM water electrolysis cell using Ir
x
Ru
y
Ta
z
O
2
electrocatalysts for the oxygen evolution electrode. Int J
Hydrogen Energy 2007;32:23204.
[27] Arikawa T, Takasu Y, Murakami Y, Asakura K, Iwasawa Y.
Characterization of the structure of RuO
2
IrO
2
/Ti electrodes
by EXAFS. J Phys Chem B 1998;102(19):373641.
[28] Kameyama K, Tsukada K, Yahikozawa K, Takasu Y. Surface
characterization of RuO
2
IrO
2
TiO
2
coated titanium
electrodes. J Electrochem Soc 1994;141(3):6437.
[29] Trasatti S. Electrodes of conductive metallic oxides (part B).
Amsterdam: Elsevier; 1981.
[30] Da Silva LA, Alves VA, Trasatti S, Boodts JFC. Surface and
electrocatalytic properties of ternary oxides Ir
0.3
Ti
(0.7x)
Pt
x
O
2
.
Oxygen evolution from acidic solution. J Electroanal Chem
1997;427(12):97104.
[31] Krysa J, Kule L, Mraz R, Rousar I. Effect of coating thickness
and surface treatment of titanium on the properties of IrO
2

Ta
2
O
5
anodes. J Appl Electrochem 1996;26(10):9991005.
[32] Mattos-Costa FI, de Lima-Neto P, Machadoa SAS, Avacaa LA.
Characterisation of surfaces modied by sol-gel derived
Ru
x
Ir
1x
O
2
coatings for oxygen evolution in acid medium.
Electrochim Acta 1998;44(89):151523.
[33] Stucki S, Kotz R. Oxygen evolution and corrosion on
rutheniumiridiumalloys. J ElectrochemSoc 1985;132(1):1037.
[34] Louc ka T. The reason for the loss of activity of titanium
anodes coated with a layer of RuO
2
and TiO
2
. J Appl
Electrochem 1977;7(3):2114.
[35] Kotz R, Stucki S. In-situ identication of RuO
4
as the
corrosion product during oxygen evolution on ruthenium in
acid media. J Electroanal Chem 1984;172(12):2119.
[36] ArdizzoneS, Carugeti A. Propertiesof thermallypreparediridium
dioxide electrodes. J Electroanal Chem 1981;126(13):28792.
[37] De Pauli CP, Trasatti S. Electrochemical surface
characterization of IrO
2
SnO
2
mixed oxide electrocatalysts.
J Electroanal Chem 1995;396(12):1618.
[38] De Farla LA, Boodts JFC, Tasatti S. Physico-chemical and
electrochemical characterization of Ru-based ternary oxides
containing Ti and Ce. Electrochim Acta 1992;37(13):25118.
[39] Nanni L, Polizzi S, Benedetti A, De Battistia A. Morphology,
microstructure, and electrocatalytic properties of RuO
2
SnO
2
thin lms. J Electrochem Soc 1999;146(1):2205.
[40] Ito M, Murakami Y, kaju Hayato, Yahikozawa K, Takasu Y.
Surface characterization of RuO
2
SnO
2
coated titanium
electrodes. J Electrochem Soc 1996;143(1):326.
[41] Benedetti A, Riello P, Battaglin G, De Battisti A, Barbieri A.
Physicochemical properties of thermally prepared Ti-
supported IrO
2
ZrO
2
electrocatalysts. J Electroanal Chem
1994;376(12):195202.
[42] Slavcheva E, Radev I, Bliznakov S, Topalov G, Andreev P,
Budevski E. Sputtered iridium oxide lms as electrocatalysts
for water splitting via PEM electrolysis. Electrochim Acta
2007;52:388994.
[43] Chen G, Bare SR, Mallouka TE. Development of supported
bifunctional electrocatalysts for unitized regenerative fuel
cells. J Electrochem Soc 2002;149(8):A10929.
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 3 ( 2 0 0 8 ) 4 9 5 5 4 9 6 1 4961