Electrochimica Acta 128 (2014) 304–310

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Composite anode electrode based on iridium oxide promoter for

direct methanol fuel cells
V. Baglio a,∗ , D. Sebastián a , C. D’Urso a , A. Stassi a , R.S. Amin b , K.M. El-Khatib b , A.S. Aricò a
a
CNR-ITAE Institute, via Salita S. Lucia sopra Contesse, 5, 98126 Messina, Italy
b
Chem. Eng. & Pilot Plant Dept., National Research Center, Dokki, Giza, Egypt

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

Article history: A composite anode was developed to increase the performance of a direct methanol fuel cell (DMFC).
Received 6 July 2013 High surface area IrO2 nanopowder was synthesized by a sulfite complex method and added to a 50%
Received in revised form 9 October 2013 PtRu/C catalyst prepared by the same procedure. A catalytic ink, composed of PtRu/C catalyst, IrO2 and
Accepted 18 October 2013
Nafion ionomer, was deposited on a carbon-cloth-based backing layer and used as composite anode
Available online 1 November 2013
in a DMFC. A significantly higher performance was recorded for the composite electrode-based MEA
compared to a bare one, at 60 ◦ C and 90 ◦ C, confirming that the electrocatalytic activity is related to the
Keywords:
characteristics of water displacement of IrO2 additive, which acts as a co-catalyst for this reaction. The
Direct methanol fuel cell
PtRu catalyst
improvement was significantly higher by using 5 M methanol solution as the fuel. These results evidence
Methanol oxidation that a multifunctional catalyst can operate better than PtRu for methanol oxidation since this multi-step
Water discharging process requires different functionalities to speed up the reaction rate.
IrO2 © 2013 Elsevier Ltd. All rights reserved.

1. Introduction intermediates. The role of Ru is to oxidize CO by means of the facile

Direct methanol fuel cells (DMFCs) are considered as an attrac-
tive option for the efficient and clean conversion of energy in
portable applications or auxiliary power units [1–3]. Pt-Ru catalysts
have shown the highest electro-catalytic activity for the oxidation
of methanol when used at the anode of DMFCs, but the high cost, the
sluggish kinetics and the stability of the bimetallic nanoparticles
are the main drawbacks of these catalysts [4–8]. Yet, it is neces-
sary to further enhance the catalytic activity of the anode catalyst
decreasing the net amount of platinum used in the membrane-
electrode assembly (MEA), and reducing thus the final stack cost.
In this regard, several routes have been pursued to achieve this
goal, e.g. the use of non-precious alloys, core-shell structures, alter-
native supports, ternary and quaternary formulation adding other
metals, etc. [9–24]. However, although some progress is registered
to reduce the amount of platinum used, there is no clear evidence
regarding the increase of performance and stability [25].
Recently, some metal oxides have been investigated as addi-
tives, including TiO2 [26–31], CeO2 [32,33], SnO2 [34], ZrO2
[35], WO3 [36,37], MoO3 [38], etc. These additives have allowed
achieving slightly better performance than Pt-based catalysts.
The methanol oxidation process consists of two main steps,
i.e. the dehydrogenation of methanol and the oxidation of CO
∗ Corresponding author. Tel.: +39 090624237; fax: +39 090624247.
E-mail addresses: baglio@itae.cnr.it, vincenzo.baglio@itae.cnr.it (V. Baglio).
formation of OH species from the water displacement process [39].
This is the rate determining step, especially at high temperature and
high methanol concentration when the methanol dehydrogenation
reaction on Pt is sufficiently fast. There is an important analogy
among the methanol oxidation and oxygen evolution reactions
since both processes require water discharging on the electrode
followed by the adsorption of active oxygen species that give rise
to a surface reaction with adsorbed methanolic residues, in the case
of methanol oxidation, or desorbs as oxygen molecule in the elec-
trolysis mode. Of course these processes occur in a quite different
potential window and water displacement at very low potentials,
as required for the methanol process, is a quite slow step. In this
regard, the addition of oxygen evolution catalysts such as iridium
oxide may be beneficial to provide enhanced methanol oxidation
activity at lower overpotential. IrO2 exhibits an excellent corrosion
resistance in acidic medium, good electrical conductivity and high
electrocatalytic activity toward oxygen evolution [40]. Ir belongs to
platinum group metals (PGM) and is characterized by a high cost
(approximately 40% lower than platinum). However, in contrast
to other metal oxides mentioned herein that are more econom-
ically interesting, IrO2 presents high electronic conductivity and
high resistance in acid media. Chen et al. studied Pt particles elec-
trodeposited on iridium oxide thin film supported on a titanium
substrate for the oxidation of methanol. They obtained a poten-
tial shift for the methanol oxidation reaction of over 0.2 V when
adding iridium oxide to the Ti/Pt electrode, and they correlated it
with a low coverage of CO and a significant CO2 formation at lower

0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.10.141
 V. Baglio et al. / Electrochimica Acta 128 (2014) 304–310
potentials applying in situ FTIR measurements [41]. Nevertheless,
to maximize both platinum and iridium oxide utilization in the
catalytic layer, small nanoparticles are required to obtain as high
surface area as possible and a good interaction between the dif-
ferent phases involved in the oxidation of methanol. In the present
work, an easy method to prepare a composite DMFC anode has been
developed. The electrode is composed of an in-house prepared high
metal surface area 50 wt% PtRu/C catalyst mixed to an in-house
synthesized high surface area IrO2 . This composite electrode was
investigated in a direct methanol single cell and compared to a
bare one. To address the need of reduction of noble metal amount
for cost-effective DMFCs, a Pt loading as low as 0.5 mg cm−2 in the
anode was used in all experiments.
2. Experimental
The in-house made 50 wt% PtRu/C catalyst was prepared as
reported in Ref. [42]. Briefly, sulfite complexes of Pt and Ru, in
appropriate amounts, were decomposed by hydrogen peroxide to
form aqueous colloidal solutions of Pt and Ru oxides. These parti-
cles were adsorbed on carbon black to form a PtRuOx /Vulcan XC-72
catalyst. The amorphous oxides supported on carbon were reduced
in a hydrogen stream to form a metallic alloy.
IrO2 was prepared using, also in this case, the sulfite complex
route [40]. Briefly, Ir chloride salt was used to obtain the iridium
sulfite complex by reaction with sodium dithionite. Afterwards, the
Ir-sulfite complex obtained was decomposed in the presence of
H2 O2 to form a colloidal suspension giving rise to an amorphous
oxide after flocculation that was filtered and dried at 80◦ C. This
amorphous Ir-oxide was subsequently treated in air at 400 ◦ C for
one hour.
X-ray diffraction (XRD) powder patterns for these materials
were obtained on a Philips X’Pert X-ray diffractometer using a
Cu/K␣ source operating at 40 kV and 30 mA. The peak profile of
the (2 2 0) reflection in the face-centered-cubic (fcc) structure of
PtRu alloy was obtained by using the Marquardt algorithm. Instru-
mental broadening was determined by using a standard platinum
sample. X-ray fluorescence (XRF) analysis of the PtRu/C catalysts
was carried out with a Bruker AXS S4 Explorer spectrometer oper-
ating at a power of 1 kW and equipped with a Rh X-ray source, a LiF
220 crystal analyzer and a 0.128 divergence collimator. The Pt/Ru
atomic ratio was determined by using Pt/L␣ and Ru/L␣ emission
lines after appropriate calibration with standard samples. Trans-
mission electron microscopy (TEM) analysis was carried out by first
dispersing the catalyst powder in isopropyl alcohol. A few drops of
these solutions were deposited on carbon film-coated Cu grids and
analyzed with a FEI CM12 microscope.
The electrodes were prepared according to the procedure
described in a previous paper [43]. A slurry composed of catalyst
and water was mixed under sonication at 60 ◦ C for 30 min. Then,
the appropriate amount of IrO2 was added to the anode slurry dur-
ing the treatment under sonication at 60 ◦ C and left for another
30 min. Two composite electrodes were prepared, having an IrO2
content of 20 wt% and 40 wt% with respect to the catalyst (50 wt%
PtRu/C) amount. Afterwards, a 15 wt% of Nafion ionomer (5 wt%,
Ion Power) with respect to the catalyst was added dropwise to the
slurry. The obtained ink was deposited on a commercial GDL from
E-TEK (HT-ELAT). An anode electrode without IrO2 was prepared for
comparison using the same procedure. The anodes were prepared
with a Pt loading of 0.5 mg cm−2 , whereas Pt black powder (Alfa
Aesar) was used for cathode fabrication on a commercial GDL from
E-TEK (LT-ELAT) with a Pt loading of 1 mg cm−2 . A Nafion 117 mem-
brane was used as the electrolyte. Membrane-electrode assemblies
(MEAs) were formed by hot-pressing the electrodes onto the mem-
brane for 90 s, at 130 ◦ C and 20 kg cm−2 , and subsequently installed
305
Pt
IrO2
C
PtRu/C
Intensity / a.u.
IrO 2
Composite: PtRu/C + 40% IrO 2
10 20 30 40 50 60 70 80 90 100
2 theta / degree
Fig. 1. XRD patterns of the 50 wt% PtRu/C catalyst, the IrO2 additive and the com-
posite PtRu/C + 40 wt% IrO2 .
in a fuel cell test fixture of 5 cm2 active area (Fuel Cell Tech., Inc.).
The cell was connected with a DMFC test station from Fuel Cell
Tech., Inc., for the single cell polarization measurements. For these
experiments, preheated aqueous methanol (2 or 5 M) was fed to
the anode chamber of DMFC through a pump; whereas, humidified
oxygen was fed to the cathode. Atmospheric pressure was main-
tained in both compartments for all measurements. Reactant flow
rates were 2 and 100 mL min−1 for methanol/water mixture and
oxygen stream, respectively. Single cell performances were inves-
tigated by steady-state galvanostatic measurements.
3. Results and discussion
3.1. Physico-chemical characterization
Fig. 1 shows the XRD patterns of the 50 wt% PtRu/C catalyst,
the IrO2 additive used for the anode electrode preparation, and the
composite ink. PtRu/C sample presents the typical cubic fcc crys-
tallographic structure of Pt and its alloys. A shift toward higher
Bragg angles with respect to reference Pt (JCPDS card n◦ 40-802) is
observed in the XRD pattern of the 50 wt% PtRu/C catalyst, indicat-
ing that Ru is alloyed within the cubic structure of Pt, as expected
for Ru contents below 70 at%. The physico-chemical properties of
the 50 wt% PtRu/C catalyst are reported in Table 1. The degree
of alloying, calculated according to the relationship described by
Garcia et al. [44], was Pt43 Ru57 , close to the nominal composition
(50:50) and to the XRF bulk composition of Pt49 Ru51 . Moreover, the
PtRu crystallite size, determined by the Debye–Sherrer equation
and considering the (2 2 0) reflection broadening, was 1.6 nm. This
low PtRu crystallite size together with a high alloying degree results
in a very high theoretical surface area of 226 m2 g−1 . The IrO2 pat-
tern shows the presence of broadened peaks corresponding to the
reflection of the tetragonal structure of IrO2 (JCPDS card n◦ 15-870),
indicating small crystallites. This sample was also characterized by
an underlaying amorphous matrix. The composite material based
on the highest content of IrO2 is also included in Fig. 1. Notice
that the diffractogram of the composite material corresponds to
the contribution of the patterns of both PtRu/C and IrO2 , where the
IrO2 -related peaks show low intensity because IrO2 is characterized
by fine crystallites in an amorphous matrix.
TEM image of the pure 50 wt% PtRu/C catalyst is reported in
Fig. 2a, showing a good coverage of the carbon support by the small
PtRu nanoparticles (1.6 nm), well-dispersed on the carbon black
particles of about 30 nm size. Whereas, Fig. 2b shows a TEM image
of the IrO2 nanoparticles, with an average size of 2.6 nm. Assuming
spherical nanoparticles and a density of IrO2 of 11.66 g cm−3 , the
306 V. Baglio et al. / Electrochimica Acta 128 (2014) 304–310

Table 1
Physico-chemical characteristics of the PtRu catalyst.

Peak position (2 deg) Lattice parameter Pt in alloy Ru in alloy Density PtRu PtRu particle size MSA
(2 2 0 reflection) (nm) (%) (%) alloy (g cm−3 ) (XRD) (nm) (m2 g−1 )

50% PtRu/C 68.836 0.385 43 57 16.4 1.6 226

Fig. 2. TEM images of (a) the 50 wt% PtRu/C catalyst, (b) the IrO2 nanoparticles, (c) composite PtRu/C + IrO2 , and (d) detail at high magnification of composite PtRu/C + IrO2 .

theoretical surface area results in 198 m2 g−1 , comparable to the 0.8

Anode: PtRu/C 2M MeOH, 60ºC
0.06
mass surface area calculated for PtRu nanoparticles (226 m2 g−1 ).
0.7 2M MeOH, 90ºC
Yu et al. [27] found that even bigger nanoparticles of TiO2 (10 nm) 0.05
5M MeOH, 60ºC
can be allocated in the catalyst structure by ultrasonically mixing 0.6
-2

5M MeOH, 90ºC
Power density / W cm

process. Accordingly, it is expected that our preparation proce- 0.04

Cell potential / V

dure may lead to a high density of PtRu-IrO2 interfaces within 0.5

the electrode architecture. This is clearly visible in Fig. 2c and d,
0.4 0.03
which show the composite material. The presence of both PtRu/C
and IrO2 nanoparticles agglomerates are distinguished. Notice that 0.3
0.02
supported PtRu nanoparticles appear closely connected with IrO2
agglomerates. Fig. 2d shows in detail the interface between the 0.2

catalyst and the promoter surfaces. 0.01

0.1

0.0 0.00
3.2. Electrochemical characterization 0.0 0.1 0.2 0.3 0.4 0.5
-2
Current density / A cm
The bare PtRu/C catalyst was investigated in a single cell at
60 ◦ C and 90 ◦ C, both for portable and APU applications, under Fig. 3. DMFC polarization and power density curves at 60 ◦ C and 90 ◦ C for the MEA
atmospheric pressure, feeding a 2 M or a 5 M methanol solu- equipped with the pure 50 wt% PtRu/C catalyst at the anode (anode: 2 M or 5 M
methanol; cathode: oxygen feed, atmospheric pressure).
tion at the anode. The polarization and power density curves
are reported in Fig. 3. A significant increase in performance was
 V. Baglio et al. / Electrochimica Acta 128 (2014) 304–310
0.8
Anode: 2M MeOH, 60ºC
0.7 PtRu/C + 20%IrO 2 2M MeOH, 90ºC
5M MeOH, 60ºC
0.6
5M MeOH, 90ºC
Cell potential / V
0.5
0.4
0.3
0.2
0.1
0.0
0.0 0.1 0.2 0.3 0.4
-2
Current density / A cm
Fig. 4. DMFC polarization and power density curves at 60 ◦ C and 90 ◦ C for the assem-
bly equipped with the composite 50 wt% PtRu/C + 20 wt% IrO2 at the anode (anode:
2 M or 5 M methanol; cathode: oxygen feed, atmospheric pressure).
observed passing from 60 ◦ C to 90 ◦ C, due to the enhanced methanol
oxidation and oxygen reduction kinetics. The maximum power
density reached values of 13 mW cm−2 at 60 ◦ C and 38 mW cm−2
at 90 ◦ C. Also the open circuit potential (OCP) slightly increased
at higher temperature (about 20 mV). However, a remarkable
decrease of performance was observed at 90 ◦ C with 5 M methanol
with respect to 2 M methanol. This loss of performance is attributed
to the effect of methanol cross-over. An increase of methanol con-
centration at the anode compartment causes a higher rate of fuel
diffusion through the polymeric membrane, reaching the cathode
compartment and creating a mixed potential, which reduces the
cell potential and efficiency. This is also evidenced by the decrease
of OCP of 40 mV at 60 ◦ C and 55 mV at 90 ◦ C. It is pointed out that
low Pt loading was used for these experiments (0.5 mg cm−2 at the
anode and 1 mg cm−2 at the cathode); this makes difficult to do
a comparison with previous results reported in the literature in
which higher loadings are generally employed [45]. Furthermore,
the use of PtRu catalysts with very small crystallite particles (in
the present case 1.6 nm) was reported to be not the best option
for intermediate and high temperature DMFC operation [44]. Most
of the studies carried out on methanol oxidation, especially those
dealing with Pt-Ru, have been focused on the optimization of the
composition, e.g. the Pt/M atomic ratio and on a better understand-
ing of the role of alloy and oxides on the promoting mechanism. In
this regard, the effect of lattice parameter, oxidation states, parti-
cle size and dispersion for PtRu have been investigated [39,44]. It
is emphasized in several reports the need of an alloy formation to
allow for an atomic mixing of the active catalytic sites but also the
need to have specific crystallographic planes on the surface. From
the studies carried out in the last three decades, the unsupported or
carbon supported Pt-Ru alloy with equimolar composition seems to
provide the best performance and today this represents the bench-
mark anode catalyst for DMFCs [39,46,47]. In order to increase the
performance of this anode catalyst, it is thought that the addition of
IrO2 , which has been demonstrated to be one of the most active and
stable catalysts for the oxygen evolution reaction in PEM electrolyz-
ers [40], could help to accelerate the water discharging process,
which is one of the intermediate steps of the methanol oxidation
reaction. The water displacement process, i.e. the rate determining
step in the oxidation of methanol, is essentially addressed by Ru in
a conventional Pt-Ru anode catalyst [39]. However, in this regard,
it is interesting to understand if there could be a synergistic role of
IrO2 and if this oxide may affect the extension of the reaction zone
inside the catalytic layer.
307
0.06 0.8 0.06
Anode: 2M MeOH, 60ºC
0.7 PtRu/C + 40%IrO 2
0.05
2M MeOH, 90ºC 0.05
0.6
5M MeOH, 60ºC
-2
-2
5M MeOH, 90ºC
Power density / W cm
Power density / W cm
0.04 0.04
Cell potential / V
0.5
0.03 0.4 0.03
0.3
0.02 0.02
0.2
0.01 0.01
0.1
0.00 0.0 0.00
0.5 0.0 0.1 0.2 0.3 0.4 0.5
-2
Current density / A cm
Fig. 5. DMFC polarization and power density curves at 60 ◦ C and 90 ◦ C for the assem-
bly equipped with the composite 50 wt% PtRu/C + 40 wt% IrO2 at the anode (anode:
2 M or 5 M methanol; cathode: oxygen feed, atmospheric pressure).
In Fig. 4, the use of a composite formulation (PtRu/C + 20% IrO2 )
was investigated at the anode under the same conditions of those
used to test the bare PtRu/C catalyst reported in Fig. 3. The max-
imum power density obtained with this composite-based anode
is of 20 mW cm−2 at 60 ◦ C and 44 mW cm−2 at 90 ◦ C, highlighting
the important effect of operating temperature. A slight increase in
the OCP, maximum power density and short circuit current density
was observed for the composite catalyst-based cell with respect
to the bare PtRu/C anode. In contrast to the results obtained in
Fig. 3, the detrimental effect of methanol cross-over at high temper-
ature affects in a lesser extent the performance of this cell. Notice
that at 90 ◦ C and 5 M methanol, the maximum power density is
only 7% lower than that obtained at the same temperature and 2 M
methanol. Whereas, the bare PtRu/C based cell suffers a 37% max-
imum power density decay under the same conditions. This is an
important achievement taking into account the possibility to oper-
ate at high energy density with high methanol concentration. This
means longer operation for electronic devices powered by DMFCs.
With the purpose of further investigating the effect of IrO2 on
the anode behavior, a composite formulation with a higher content
of additive (PtRu/C + 40% IrO2 ) was investigated. The polarization
and power density curves are reported in Fig. 5. The maximum
power density values achieved with the highest concentration of
IrO2 tested are 23 mW cm−2 at 60 ◦ C and 31 mW cm−2 at 90 ◦ C.
The OCP values obtained with this composite anode decrease sig-
nificantly when passing from 60 ◦ C to 90 ◦ C, about 20 mV at 2 M
methanol and 95 mV at 5 M methanol. This decay indicates a poor
performance for the 40% IrO2 based anode at high temperature in
comparison with the other two anode formulations. Nevertheless,
at low temperature (60 ◦ C) the presence of a higher amount of IrO2
appears to favor the process.
Fig. 6 shows a comparison between the performance recorded
for the bare PtRu/C catalyst (empty symbols) and the two composite
anodes (20% IrO2 and 40% IrO2 , full symbols) with 2 M methanol
solution, at 60 ◦ C (Fig. 6a) and at 90 ◦ C (Fig. 6b). In the activation
region (low current densities) the overpotential is decreased and
efficiency is considerably improved with the addition of IrO2 , as also
evidenced by the increase of the OCP up to 50 mV (PtRu/C + 40% IrO2
at 60 ◦ C, Fig. 6a). Only in the case of 40% IrO2 at 90 ◦ C, mass transfer
constraints lead to lower performance. In general terms we can
assume a positive influence of IrO2 on the oxidation of methanol.
Similar comparison at higher methanol concentration (5 M) is
reported in Fig. 7. Notice that at 60 ◦ C there is a lower overpoten-
tial in the activation region that is reflected in all the polarization
curve. Also in this case higher OCP values are recorded (up to 50 mV
308 V. Baglio et al. / Electrochimica Acta 128 (2014) 304–310

(a) 0.8 60ºC, MeOH 2M PtRu/C 60ºC, MeOH 5M PtRu/C

0.030 (a) 0.8 0.030
PtRu/C + 20% IrO 2 PtRu/C + 20% IrO2
0.7 0.7
PtRu/C + 40% IrO 2 0.025 PtRu/C + 40% IrO2 0.025

-2

-2
0.6 0.6

Power density / W cm

Power density / W cm
0.020 0.020
Cell potential / V

Cell potential / V
0.5 0.5

0.4 0.015 0.4 0.015

0.3 0.3
0.010 0.010
0.2 0.2
0.005 0.005
0.1 0.1

0.0 0.000 0.0 0.000

0.00 0.05 0.10 0.15 0.20 0.25 0.00 0.05 0.10 0.15 0.20 0.25
-2 -2
Current density / A cm Current density / A cm

90ºC, MeOH 2M PtRu/C 90ºC, MeOH 5M PtRu/C

(b) 0.8 0.06 (b) 0.8 0.06
PtRu/C + 20% IrO 2 PtRu/C + 20% IrO2
0.7 0.7
PtRu/C + 40% IrO 2 0.05 -2 PtRu/C + 40% IrO2 0.05

-2
0.6 0.6
Power density / W cm

Power density / W cm
0.04
Cell potential / V

0.04

Cell potential / V
0.5 0.5

0.4 0.03 0.4 0.03

0.3 0.3
0.02 0.02
0.2 0.2
0.01 0.01
0.1 0.1

0.0 0.00 0.0 0.00

0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5
-2 -2
Current density / A cm Current density / A cm

Fig. 6. DMFC polarization and power density curves: comparison of anode formu- Fig. 7. DMFC polarization and power density curves: comparison of anode formu-
lations (PtRu/C, PtRu/C + 20 wt% IrO2 , PtRu/C + 40 wt% IrO2 ); anode: 2 M methanol; lations (PtRu/C, PtRu/C + 20 wt% IrO2 , PtRu/C + 40 wt% IrO2 ); anode: 5 M methanol;
cathode: oxygen feed; atmospheric pressure (a) at 60 ◦ C and (b) at 90 ◦ C. cathode: oxygen feed; atmospheric pressure (a) at 60 ◦ C and (b) at 90 ◦ C.

with respect to those obtained with the bare PtRu/C catalyst). The work, we have analyzed three anode compositions, which can be
behavior analyzed in Figs. 6 and 7 indicates that the PtRu/C is more expressed as milligrams of equivalent platinum (in terms of cost,
prompt to be poisoned by adsorbed CO intermediates compared mgPt-eq ) as follows: 0% IrO2 corresponds to 0.50 mgPt-eq cm−2 , 20%
to the composite electrode. Thus, the methanol conversion to CO2 IrO2 corresponds to 0.66 mgPt-eq cm−2 (i.e. an increase of +32%) and
is lower for the PtRu/C catalyst compared to the composite elec- 40% IrO2 corresponds to 0.82 mgPt-eq cm−2 (i.e. an increase of +64%).
trode, where the presence of IrO2 may enhance the kinetics of water Consequently, to be economically interesting in terms of $ W−1 ,
discharging process. This also produces a lower methanol con- the increase of performance must be higher than the increase of
centration at the interface, limiting the methanol cross-over rate anode cost. Fig. 8 reports the percentage of performance increase
through the membrane, as can be also envisaged from the highest
OCP for the cell based on the composite electrode. Possibly another
contribution should be taken into account since the presence of a
high content of additive may hinder the access of methanol to the
active PtRu sites.
The dependence of the maximum power density on the content
of iridium oxide (Fig. 8) confirms this interpretation. At low tem-
perature, it is remarkable that the higher the content of IrO2 the
higher the maximum power density, independently of methanol
concentration. Whereas at high temperature, the achievement of
a maximum power is found to be related to a certain amount of
IrO2 content, which may be found around 20%. More experiments
are necessary to further optimize anode structure and stability [48],
but these results confirm that the electrocatalytic activity is related
to the characteristics of water displacement of IrO2 additive, which
acts as a co-catalyst for this reaction. It is pointed out that to opti-
mize the anode composition, the cost of the anode components
together with their performance should be taken into consider-
Fig. 8. Effect of additive content (IrO2 ) in the anode on the maximum power density
ation. The current cost of iridium is about 40% lower than the cost at different DMFC operating conditions. Percentages on the bars indicate the relative
of platinum, according to Johnson Matthey [49]. In the present increase of power density with respect to the 0% IrO2 .
 V. Baglio et al. / Electrochimica Acta 128 (2014) 304–310
with respect to the bare PtRu/C anode for each tested condition.
Notice that for 5 M methanol concentration and the composite
anode based on 20% IrO2 , the increase of performance (+54% at 60 ◦ C
and + 75% at 90 ◦ C) significantly compensates the cost increase due
to the presence of iridium (+32%).
To summarize, the results evidence that a multifunctional cata-
lyst can operate better than PtRu for methanol oxidation since this
multistep process requires different functionalities to speed up the
reaction rate.
Another important evidence is the possibility to establish a par-
allelism between methanol oxidation and oxygen evolution. Since
both processes are widely investigated but from different points
of view, sharing the different knowledge may allow to increase
the probability to find better formulations for methanol electro-
oxidation.
4. Conclusions
The addition of high-surface-area IrO2 nanoparticles to a PtRu/C
catalyst produced an increase of performance for the cell equipped
with this composite anode electrode due to the enhanced kinetics
for the water discharging process, which is one of the intermediate
steps of the methanol oxidation reaction. The improved electro-
catalytic activity was thus attributed to the characteristics of water
displacement of IrO2 , which are known from the oxygen evolu-
tion process. Such a parallelism may provide new routes to design
multifunctional catalysts where Pt-alloys can be combined with
oxide promoters to accelerate the multiple steps of the methanol
oxidation process.
Acknowledgements
CNR-ITAE authors acknowledge the financial support of PRIN
2010-11 project “Advanced nanocomposite membranes and inno-
vative electrocatalysts for durable polymer electrolyte membrane
fuel cells’ (NAMED-PEM). Furthermore, the research leading to
these results has received funding from the European Community’s
Seventh Framework Programme (FP7/2011-2014) for the Fuel Cells
and Hydrogen Joint Technology Initiative under grant agreement
DURAMET no. 278054.
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