i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 4 1 5 e3 4 2 4

Available online at www.sciencedirect.com

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Durability of different carbon nanomaterial supports

with PtRu catalyst in a direct methanol fuel cell
Annukka Santasalo-Aarnio a, Maryam Borghei b, Ilya V. Anoshkin b, Albert G. Nasibulin b,
Esko I. Kauppinen b, Virginia Ruiz b,c, Tanja Kallio a,*
a

Research Group of Fuel Cells, Department of Chemistry, Aalto University, P.O. Box 16100, 00076 Aalto, Finland
Nanomaterials Group, Department of Applied Physics, Aalto University, P.O. Box 16100, 00076 Aalto, Finland
c
CIDETEC-IK4 (Centre for Electrochemical Technologies), Paseo Miramon 196, 20009 Donostia-San Sebastian, Spain
b

article info

abstract

Article history:

PtRu catalysts with similar particle size and composition were deposited on three different

Received 4 July 2011

carbon supports: Vulcan, graphitized carbon nanofibers (GNF) and few-walled carbon

Received in revised form

nanotubes (FWCNT) and their performance for methanol oxidation was studied in an

11 October 2011

electrochemical cell and in a single cell DMFC. The electrochemical results indicate that

Accepted 1 November 2011

with PtRu/GNF and PtRu/FWCNT higher current densities are obtained and oxidation

Available online 9 December 2011

intermediates deactivate the surface less compared to the same catalyst on Vulcan
support. Conversely, PtRu/Vulcan provided the highest open circuit voltage OCV and

Keywords:

current densities in DMFC experiments due to a well-optimized electrode layer structure.

Carbon nanotubes

Because stability is a key requirement for fuel cell commercialization, 6-day-long fuel cell

Carbon nanofibers

stability tests were carried out, showing that PtRu/Vulcan degraded significantly. This was

Methanol oxidation

due to the collapse of the secondary structure of the electrode layer revealed by post

Direct methanol fuel cell (DMFC)

characterization of the membrane electrode assembly (MEA) with SEM and TEM. PtRu/GNF
exhibited slightly poorer initial performance but better stability because the structure of
the anode layer was maintained. PtRu/FWCNT showed the worst initial performance and
long-term stability. The good stability of non-optimized PtRu/GNF MEAs shows the
potential of these novel nanocarbon supported catalysts as stable fuel cell components
after proper MEA optimization.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

Fuel cells running on liquid fuels such as direct methanol fuel

cells (DMFCs) are very promising energy sources for low power
electronic applications but improvements in performance and
design, as well as cost reduction are still necessary [1]. In
particular, developing more efficient and durable electrocatalysts for methanol oxidation is crucial for achieving
enhanced performance and increasing the lifetime of DMFCs.

With the aim of reducing costs associated with the precious

metal, nanosized mono and bimetallic catalysts deposited on
conducting carbons with high surface area are typically used.
Along with the nature of the catalysts, the search for better
and more stable anode material has comprised evaluating the
influence of the carbon support on the catalytic activity. A
good catalyst support should have high surface area and
conductivity, exhibit good permeability to reactants and have
electrochemical stability under fuel cell operating conditions.

* Corresponding author. Tel.: 358 9470 22583; fax: 358 9470 22580.
E-mail address: tanja.kallio@tkk.fi (T. Kallio).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.11.009

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In this regard, many types of carbon nanostructures have

been investigated as supports for anode electrocatalysts in
DMFCs such as single-walled carbon nanotubes (SWCNTs),
multi-walled carbon nanotubes (MWCNTs), graphitized carbon nanofibers (GNFs), fullerenes and carbon nanohorns, due
to their appealing properties such as high surface area, electronic conductivity as well as chemical and mechanical
stability [2e16]. Most reports have demonstrated the superior
performance of highly porous tubular nanocarbons and
compared them to carbon black in terms of catalyst utilization
and dispersion. Thus, 2-fold enhancements of the catalytic
activity have been observed for MWCNT-supported Pt [6] or
PtRu [7,8] and for SWCNT-supported PtRu [9] and up to a 4-fold
increase for GNF-supported Pt [10,11] with respect to the
carbon black-supported catalysts. PtRu colloids on GNFs also
have 64% higher activities than the unsupported catalysts [17].
On the other hand, there are comparatively few systematic
studies where the performance of electrocatalysts deposited
in the same fashion on several carbon supports and from
various commercial sources is compared [17e20]. These
studies revealed notable differences in the activity trends as
well as in the enhancement factors (with respect to carbon
black) for the different carbon supports, with CNT-supported
catalysts either outperforming [18,21] or exhibiting poorer/
comparable activity [19,22,23] to carbon black. These contrasting results highlight the importance of conducting
further studies to gain more insight into the role of the catalyst support. Furthermore, most of the reports on the improved activities of CNT or GNF-supported catalysts do not
address the crucial issue of the long-term stability and when
they do, conclusions on the stability of novel catalyst supports
are inferred from chronoamperometry or voltammetry tests
in electrochemical cells [8,10,19e21,23]. However, the catalyst
environment in the DMFC membrane electrode assembly
(MEA) differs considerably from that in a half-cell electrochemical set-up, which has motivated the current study
where activity and stability of PtRu catalysts on different
carbon supports have been compared in both scenarios.
Specifically, we have investigated both the catalytic
activity and long-term stability of PtRu catalysts deposited
following the same protocol on a series of carbon supports,
namely GNFs, few-walled CNTs (FWCNTs) and Vulcan. Metal
loadings, MEA preparation and DMFC testing were comparable for the different electrocatalysts. In other reports where
the influence of the catalyst support was evaluated, catalyst
particle differed considerably for each support [17], which
makes more difficult to assess separately the effect of the
support. Here special effort has been done to achieve
comparable catalyst size and composition on the different
carbon supports to minimize differences arising from the
catalyst. We will show that the stability trends for catalysts on
different supports observed in chronoamperometry do not
necessarily correlate with long-term stability tests in DMFC
MEAs. Activities from chronoamperometric tests decrease in
the trend FWCNTs > GNFs > Vulcan, whereas the activities
observed in DMFC tests followed the opposite trend:
Vulcan > GNFs > FWCNTs. Therefore, caution is advised when
attributing enhanced catalytic performance to novel electrocatalysts based solely on electrochemical measurements.
Moreover, this also addresses the question of different MEA

preparation methods that need to be optimized also for the

high surface area catalyst supports.

2.

Experimental methods

2.1.

Catalyst material preparation

Vapour grown carbon nanofibres were kindly supplied by

Showa Denko (product reference VGNF). These are highly
graphitized nanofibers with a diameter of w150 nm and
a length of w10 mm. Prior to catalyst deposition, GNFs were
subject to oxidative surface functionalization by refluxing
them in a 1:1 (vol/vol%) mixture of HNO3 2 M and H2SO4 1 M at
120  C for 6 h. Few-walled carbon nanotubes (FWCNT) with
2e5 walls (<6 nm diameter, w 1 mm length) were obtained by
catalytic pyrolysis of CH4 diluted with 80% H2 at 950  C
according to a method reported elsewhere [24]. The catalyst is
a mixture of CoeMo oxides (5 at.%) supported on MgO. After
the synthesis, residual catalyst was removed (<1% w.) from
the FWCNTs by washing in HCl, followed by rinsing with
deionized water and drying in vacuum. Prior to PtRu deposition, FWCNTs were acid treated to introduce surface functional groups by refluxing them in a 1:1 mixture of HNO3 2 M
and H2SO4 1 M at 120  C for 4 h. Vulcan XC72R powdered
carbon black with 96.11 kg m3 bulk density (Cabot Corporation) was used as received for catalyst deposition.

2.2.

Deposition of PtRu on Vulcan, FWCNTs and GNFs

Ru-Pt catalysts (w25% total metallic loading, Pt:Ru 1:1 atomic

ratio) were deposited on the different carbon supports by
reduction of the corresponding metal precursors, RuCl3 and
K2PtCl6, with NaBH4 according to a previously reported
procedure [25]. Briefly, the carbon supports were ultrasonicated in a solution containing ethylene glycol and water
for 20 min and then the required amount of the metal
precursors (with Pt:Ru atomic ratio of 1:1 and PtRu:C weight
ratio of 1:3) was added and ultrasonicated for 20 min. After
that, a solution of 0.04 M NaBH4 and 0.4 M NaOH was added
dropwise and the resulting suspension was kept under ultrasonication at 60  C for 2 h for complete reduction. Finally the
suspension was filtered and the solid product was collected,
washed thoroughly with water and acetone and dried in
vacuum at 60  C overnight.

2.3.

Physical characterization of the materials

Scanning electron microscopy (SEM) was performed on a JEOL

JSM-7500FA field emission scanning electron microscope
equipped with an energy-dispersive X-rays spectrometer
(EDXS) for evaluation of catalyst metal loadings. For crosssection imaging, MEAs were frozen in liquid nitrogen and
cut. Transmission electron microscopy (TEM) was done with
a Tecnai 12 Bio Twin transmission electron microscope with
LaB6 gun at 120 kV. As-prepared pristine catalyst powder and
degraded catalysts, scratched from the MEA anode, were
dispersed in isopropanol by short ultasonication and a drop
cast on TEM grids. Powder X-ray diffraction spectra were obtained by a Bruker D8 Advance X-ray diffractometer using Cu

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 4 1 5 e3 4 2 4

Ka radiation and a Lynx Eye fast detector with scan conditions

of 2s/0.03 . The BET surface area was determined with N2
adsorption/desorption at 77 K temperature with a FlowSorb
2300 II instrument by Micromeritics. A four-probe method was
used for measuring the electrical conductivities of the MEA
anodes.

2.4.

Electrochemical characterization of the materials

The aim of the electrochemical characterization was to

reproduce the conditions in a fuel cell anode as closely as
possible and therefore, a similar ink as used for fuel cell MEA
was prepared with 5 mg of the studied catalyst material,
Nafion solution (5 wt % Aldrich) and isopropanol (Merck,
p.a.). The ink was mixed carefully with a magnetic stirrer and
an ultrasonic bath. 5-ml droplet of the ink was placed onto
a glassy carbon electrode which was cleaned and polished
with alumina solution and an ultrasonic bath. The ink was
dried in air over night. An electrochemical cell was assembled
with this glassy carbon electrode as a working, a platinum coil
as a counter electrode and standard calomel electrode (SCE) as
a reference; nevertheless, all the potentials mentioned are
referred to the reversible hydrogen electrode (RHE). All the
glassware was carefully boiled in MQ water (0.04 mS cm1,
Millipore) and rinsed various times prior to the measurements. 0.1 M HClO4 (Merck, 70 wt %) was freshly prepared and
used as an electrolyte in order to ensure that no significant
anion adsorption from the electrolyte occurs on the PtRu
surface [26].
The surface potential of the working electrode was
controlled all the time when the electrode was in the electrolyte that was de-aerated prior to the experiments. The
experiments were performed with a potentiostat/galvanostat
PGSTAT100 Autolab system. Firstly, a cyclic voltammogram
(20 mV s1) was obtained to ensure that the electrode preparation had succeeded. The catalyst surface cleaning was done
with CO adsorption/oxidation method because cycling to high
potentials would have caused ruthenium dissolution [27]. The
electrolyte was purged with CO gas (99.99%) for 2 h while the
electrode was kept in 0.1 V vs. RHE potential and rotated at
300 rpm to ensure easy diffusion to the catalyst surface. While
the potential was still held the gas was changed to N2 and
purged for 30 min to remove the CO from the electrolyte.
Subsequently, a cyclic voltammogram with three scans was
obtained at 10 mV s1 to show the CO oxidation peak behaviour. After this cleaning cycle voltammograms of the catalyst
surface were performed at 20 mV s1. In this report, all the
currents are presented normalized by the catalyst loading on
the working electrode and all voltammograms refer to the
features in the third cycle, where steady-state response was
attained.
After the measurements in pure electrolyte, the solution
was changed to one containing the same electrolyte and 1 M
methanol. To prevent changes in methanol concentration, the
gas inlet was first directed into a bubbler bottle containing the
same solution as the cell and methanol saturated gas was
directed to the experimental cell. Cyclic voltammograms were
recorded with a rotating disc electrode (RDE) at 10 mV s1 rate
with and without 1800 rpm rotation (Pine instruments). To
further
study
the
catalyst
poisoning
additional

3417

chronoamperometric measurements for 1 h were obtained at

0.7 V vs. RHE potential.

2.5.

Fuel cell experiments

Prior to the fuel cell experiments a membrane electrode

assembly (MEA) with each of the studied catalyst materials
was made. The catalyst ink was prepared as a mixture of
catalyst (60 wt % of Pt on Vulcan (Alfa Aesar) for cathode and
the investigated PtRu catalyst for anode), Nafion solution and
isopropanol solvent. The ink was first stirred with a magnetic
stirrer for several hours and the Vulcan catalyst was sonicated
with an ultrasonic bath. The slurry was painted onto the
membrane materials with an airbrush and dried in a vacuum
oven for 2 h. The metal loading of the cathode was
2  0.2 mg cm2 and for the anode 1  0.2 mg cm2. The reason
for using cathodes with higher catalyst loading and same
Nafion loading at the anode was to ensure that the differences
seen in the fuel cell results were purely dependent on the
anode catalyst supporting material. When both electrodes
were painted onto the membrane, the MEA was heat pressed
at 130  C, with 50 kN pressure for 120 s. The fuel cell was
assembled with Teflon insulators, gas diffusion layers (carbon
cloths) and a MEA, closed and tightened evenly with 10 kN
force.
The fuel cell experiments were performed in a single cell
DMFC with surface area of 7.29 cm2. 1 M methanol (Merck,
p.a.) fuel was fed to the anode with 1.5 ml min1 rate and dried
oxygen gas (5.0 Aga) to the cathode at 300 ml min1. The
temperature of the cell was controlled to be 70  C  1  C. The
cell was stabilized over night with the studied methanol fuel
(0.2 ml min1) and oxygen with 30 ml min1 and normalized
2 h prior to the polarization experiments with higher flow
rates. The polarization curves were measured with a PGSTAT
20 instrument with an Ecochemie 10 A current booster
BSTR10A and a GPES software from the open circuit voltage
(OCV) to 0.05 V at the rate of 0.5 mV s1. In addition, long-term
stability test for the MEAs at 70  1  C was performed after
measuring the polarisation curves. The flow rates of the fuels
were lowered to 0.5 ml/min for the methanol and 90 ml min1
for oxygen and stabilized for 2 h. The potential control was
applied and kept at constant 0.4 V for 137 h while the current
was observed as a function of time. After the measurement
the polarisation curve was obtained by the same method
described above. Finally, the degraded MEAs were removed
from the cell and the cross-sections were imaged with SEM
and catalyst material scratched from the MEA anode was
analysed by TEM.

3.

Results and discussion

3.1.

Structural characterization of the materials

As indicated above, special effort has been devoted to

obtaining catalysts with comparable metal loading, Pt:Ru
atomic ratio and particle size (Table 1) on the different carbon
supports with clearly different BET surface areas increasing in
order GNF < Vulcan < FWCNT. Metallic content and Pt:Ru
atomic ratios are determined from the pristine catalyst

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Table 1 e Characterization data for PtRu-carbon

nanomaterials. The fresh catalyst diameter has been
determined from the pristine catalyst powder and the
degraded one from the MEA anode after fuel cell
experiments.
PtRu-Vulcan
Metal w%
Pt:Ru atomic ratio
(EDXS)
PtRu diameter
(TEM, nm)
fresh/degraded
PtRu diameter
(XRD, nm) fresh

22.6
1.0

PtRu-GNF
23.5
1.1

PtRu-FWCNT
26.0
1.1

3.3/4.5

3.2/3.5

2.8/3.3

3.01

3.47

3.34

powder as the average from multiple spot EDXS analysis of Pt

and Ru emission intensities. TEM images and histograms
(Fig. 1) indicate that all powder catalysts exhibit good particle
dispersion and narrow particle size distribution, with more
aggregates observed on GNFs and FWCNTs than on Vulcan.
Mean particle sizes, which are summarized in Table 1, do not
differ considerably for the different as-prepared catalysts.
Fig. 2 presents XRD patterns of as-prepared catalysts,
which clearly show the diffraction peaks of PtRu alloy crystal
faces (111), (200), (220) and (311) at around 40.2 , 46.8 , 68.3 ,
82.3 , respectively, characteristic of a face-centered cubic (fcc)
structure with a cell constant of 3.88 for all catalyst samples.
The average particle size was estimated from the Pt (111)
diffraction peak according to the Scherrer formula for the

Fig. 1 e TEM images of as-prepared PtRu catalysts on Vulcan (a), GNF (b) and FWCNT (c) and after 137 h stability tests in
DMFC (def).

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 4 1 5 e3 4 2 4

Fig. 2 e XRD patterns of as-prepared catalyst powders.

different catalysts (Table 1), which is in good agreement with

the values calculated from the TEM images. Hexagonal carbon
peak C(002) at around 26 is dominant but the other characteristic peaks C(100) around 42 and C(101) at 45 overlap with
the PtRu diffraction pattern and consequently are not well
resolved. Moreover, graphite peaks C(004) around 54 and
C(110) around 78 can be observed only for the GNF support
showing highest intensities. The comparable structure achieved for the PtRu nanoparticles in the three catalyst materials
enables assessing separately the influence of the type of
carbon support on the observed catalytic properties of the
ensemble.

3.2.

Electrochemical characterization of the materials

The prepared PtRu catalyst materials on different supports

have been studied in an electrochemical cell to determine
their activity for methanol oxidation. The catalyst materials
have been cleaned with a CO adsorption/oxidation procedure
and not by cycling to high voltages to avoid the dissolution of
ruthenium from the alloy [27]. This is also the reason why all
the experiments are performed only up to 0.7 V. Electrochemical surface areas calculated from the CO adsorption/
oxidation experiments result in similar values in range of
12e14 m2 g1 for carbon supported alloy catalyst materials.
This is expected as special effort was done to synthetize
materials with similar particle size and distribution. However,
these values have not been used to normalize the currents
because details of CO adsorption on ruthenium surface are
unknown; instead the current are normalized with catalyst
loading.
The voltammograms obtained in 0.1 M HClO4 are presented
in Fig. 3. All three catalysts exhibit the typical features of PtRu
nanoparticle catalysts in HClO4 electrolyte [28,29]: a clear
electrosorption of hydrogen on platinum is observed at
potentials between 0.05 and 0.1 V. Shortly after this the
ruthenium oxide formation initiates at 0.2 V [28]. This poorly
resolved hydrogen adsorption region is the reason why

3419

Fig. 3 e Cyclic voltammograms of PtRu catalyst on different

carbon supports in 0.1 M HClO4, scan rate of 20 mV sL1.
PtRu/Vulcan (dashed, black line), PtRu/FWCNT (thin, red
solid line), PtRu/GNF (thick, green solid line). (For
interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this
article.)

hydrogen adsorption/desorption on platinum surface can not

be used for electrochemical surface area determination.
Instead measured currents have been divided by the catalyst
loading on the electrode. For FWCNT support the active
surface area is higher than for the other two supports and
therefore slightly higher currents are obtained. Moreover,
with PtRu/FWCNT an additional peak at the platinum oxide
region is observed around 0.55 V that has been previously
reported in H2SO4 electrolyte at 0.65 V [6,8,30] and might be
due to electroactive surface groups on carbon support [31]
resulting from the oxidative acid treatment of FWCNTs.
Fig. 4A shows the activity of PtRu catalyst on different
supports towards methanol oxidation. The cyclic voltammograms indicate that around four times higher currents are
obtained with PtRu/FWCNT support and even eight times
higher with PtRu/GNF compared to PtRu/Vulcan. These results
are in accordance with the results obtained by other groups
when comparing separately CNT to Vulcan [8,9,19,21e23] or
GNF to Vulcan [10]. On the other hand, there are only few
reports where the performance of MWCNT, SWCNTs from
several suppliers and GNF supports are compared by the same
group [18] observing that all PtRu on CNT supports are more
active for methanol oxidation than PtRu/GNFs.
In general, cyclic voltammetry is not a good method to
model the conditions that catalyst and support material need
to tolerate in the fuel cell, where current is drawn with
constant potential. Therefore, chronoamperometric experiments (Fig. 4B) have also been performed at 0.7 V. As can be
seen from Fig. 4B with all of the supports the current obtained
at 0.7 V in the cyclic voltammogram (Fig. 4A) is not maintained
for a long time due to the platinum catalyst sites poisoning by
methanol oxidation intermediates [29,32]. Especially, the high
current obtained with PtRu catalyst on GNF support decreases
4 times after around 500 s, approaching the value of PtRu/
Vulcan after 1 h. Even if the maximum current density

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Fig. 5 e DMFC polarization curves for different PtRu catalyst

supports at 70  C. On cathode 2 mg cmL2 Pt on Vulcan is
used in each case. PtRu catalyst loading for anode is
around 1 mg cmL2. (a) PtRu/Vulcan (black line), (b) PtRu/
FWCNT (red line), (c) PtRu/GNF (green line). (For
interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this
article.)

Fig. 4 e Methanol oxidation on PtRu catalyst on different

carbon supports in 0.1 M HClO4 and 1 M methanol
solutions. (A) Cyclic voltammograms with 1800 rpm and
10 mV sL1 and (B) chronoamperometric curves at 0.7 V
potential. (a) PtRu/Vulcan (black line), (b) PtRu/FWCNT (red
line), (c) PtRu/GNF (green line). (For interpretation of the
references to colour in this figure legend, the reader is
referred to the web version of this article.)

obtained for PtRu/FWCNT with cyclic voltammetry is almost

half that of PtRu/GNF, the same catalyst on a FWCNT support
seems to be clearly more stable, retaining 69% of the initial
current after 1 h at 0.7 V. This value is considerably high
compared to the 10% reported by Li et al. for the same experiment with PtRu catalyst on CNT [8]. Current drops of 16% [19]
and 78% [23] have been reported for other CNT-supported
catalysts during chronoamperometric measurements at
lower potential (0.4 V). The wide range of the results obtained
by different groups illustrates the relevance of catalyst and
support preparation methods.

3.3.

Fuel cell performance

Direct comparison of results reported by different research

groups on the fuel cell performance of various catalyst
supports is a challenging task due to the variety of experimental protocols used for MEA preparation and fuel cell
operating conditions. To the best of our knowledge no attempt
to evaluate the long-term performance of fuel cell catalysts on

several different nanocarbon supports in the same DMFC setup has been previously done. In Fig. 5 polarization curves of
DMFC with similar catalyst loading and ionomer content but
different anode catalyst supports are presented. All the pristine MEA anodes show electronic resistivity in the range of
1e2 mU m. The open circuit voltage (OCV) depends e.g. on
operating temperature, methanol crossover through the
Nafion membrane, selected catalysts and electrode layer
structure. For the three support materials all the conditions
remain the same except the electrode layer structure. The
OCV value obtained for PtRu/Vulcan MEA (590 mV, Table 2) is
in agreement with previously published data [9,17,33] and
PtRu/GNF MEA has only 20 mV lower OCV. However, a significantly lower OCV (450 mV) has been obtained for the PtRu/
FWCNT MEA compared to the other supports. This trend
agrees with that observed by Liu et al. [9] with higher catalyst
loadings.
PtRu/Vulcan MEA yields high current density (299 mA cm2,
Table 2) even with very low (1 mg cm2) anode loadings. PtRu/
GNF MEA also produces a reasonable current density of
231 mA cm2 whereas the value for PtRu/FWCNT is moderate
(158 mA cm2). SEM images of the MEA cross-sections for the
different catalysts before the experiments (Fig. 6) can help to
explain the differences observed for fuel cell performance and
OCV. Anode thicknesses have also been determined (Table 2)
from the MEA cross-section SEM images. The fresh PtRu/
Vulcan anode layer is considerably thinner than the electrode
layers of the other supports, which are almost 8 times thicker
even for a same catalyst loading. This is due to the higher
surface area of the tubular nanocarbon supports and consequently larger volumes for the same catalyst loading. Also from
the SEM cross-section images it can be seen that PtRu/Vulcan
anodes are optimally structured due to the years of practice in

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Table 2 e The performance of the different MEAs thicknesses the anode electrodes by SEM analysis before and after the
137 h chronoamperometric experiment in a fuel cell.
Support

OCV (initial)
V

Vulcan
FWCNT
GNF

0.59
0.45
0.55

Max. current density

2

mA cm
299
158
231

OCV (after)

Current density

Anode thickness

Decrease
after 137 h

Fresh mm

Degraded
mm

Thickness
change

0.57
0.46
0.54

14%
35%
1%

81
60  9
65  5

27  3
63  8
56  4

2.7%
0.04%
0%

The range of thicknesses and mean value with errors for each electrode is given.

optimizing the MEA preparation conditions. It is important to

keep in mind that MEA fabrication plays a vital role in DMFC
performance. When dealing with supports with totally
different surface area, the optimal solvent and Nafion solution
contents for Vulcan supported-catalyst are not necessary the

best ones for GNF and FWCNT-supported ones. This has been
noticed by us and also by other groups for PEMFC MEAs and
a detailed study of optimizing ink composition for catalysts on
FWCNT and GNF supports will be subject of a further separate
study.

Fig. 6 e Cross-section SEM images of fresh (aec) and degraded (def) MEA anodes with PtRu catalysts on Vulcan (a, d), GNF
(b, e) and FWCNT (c, f).

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Nevertheless, a basic practical requirement for the use of

these materials as cell components in commercial fuel cells is
a good long-term stability. This type of tests are time
consuming and therefore often absent in many reports
assessing the performance of novel catalyst supports. Here
potentiostatic experiments in DMFC for 137 h at 0.4 V were
performed after measuring the polarisation curves in order to
evaluate the durability of the catalyst structure (Fig. 7).
Immediately after this experiment another polarisation curve
was measured and the losses in OCV and maximum current
density are presented in Table 2. To further study the loss and
agglomeration of the catalyst particles, EDXS analysis and
TEM images of the used anode catalyst were taken and are
presented in Fig. 1def along with the catalyst particle size
distribution. EDXS characterization of the catalysts after
stability tests do not reveal significant metal loss in any of the
supports. However, TEM analysis of the degraded catalysts
(Fig. 1) show particle size growth and broader size distributions, the extent of which varies with the catalyst support
(Table 1).
As can be seen from Fig. 7, PtRu/Vulcan produces the
highest current density, as expected from the polarisation
curve (Fig. 5), nevertheless, the current density degradation is
rapid and no steady value seems to be attained even for such
a long experiment. After the 6-day experiment the OCV
decreased only 20 mV (Table 2), however, the 14% loss of the
maximum current density is problematic from the point of
view of applications. This degradation can be explained by
comparing SEM images of the fresh and degraded PtRu on
Vulcan support (Fig. 6a and d). In the fresh anode, the PtRu/
Vulcan layer exhibits a three-dimensional net structure that
allows efficient liquid and gas flow through the whole anode
layer. Conversely, several cross-section SEM images of the 6day used MEA (Fig. 6d) show that the secondary structure of
the anode layer is collapsed, inhibiting the transport of the

fluids through the electrode. Moreover, the anode layer has

swelled in diluted methanol solution and the anode thickness
has increased almost 3.5 times (Table 2). Moreover, the mean
particle size of PtRu catalyst on Vulcan support increases from
3.3 nm to 4.5 nm (Fig. 1d) and the size distribution becomes
clearly broader compared to fresh catalyst material.
A similar phenomenon can also explain the poor stability
of the PtRu/FWCNT MEA during the 6-day test (Fig. 7, Table 2).
As seen in the SEM images, the fresh PtRu/FWCNT anode layer
shows spongy morphology offering pathways for fluid flow
(Fig. 6c) which leads to the high anode thickness (Table 2).
Nevertheless, after the 6-day experiment a dramatic current
drop was observed, which is mainly due to the loss of pathways in the anode layer clearly visible in Fig. 6f. Moreover,
TEM images also reveal the presence of more bundles in the
PtRu/FWCNT anode after the stability test, which together
with the increase in average particle size from 2.8 nm to
3.3 nm and loss of cavities in the anode layer, could contribute
to the highest current drop (35%) noted for the investigated
PtRu MEAs.
Even though PtRu/GNF catalyst shows high activity
towards methanol oxidation in RDE measurements (Fig. 4) it
exhibits poorer performance than PtRu/Vulcan in DMFC
experiments (Fig. 5). These results contrast with those reported by Guo et al. [34] for PtRu catalyst on carbon nanofibers
that showed modest activity for methanol oxidation in electrochemical cell but still slightly higher performance in DMFC
compared to Vulcan. Unfortunately, no detailed information
on MEA preparation process was provided by the authors. In
our study the current density of 231 mA cm2 obtained with
the PtRu/GNF anode (Fig. 5) is surprisingly high even though
the anode thickness is 8 times thicker compared to the PtRu/
Vulcan anode. Interestingly, the current density changes
during the 6-day experiment are almost negligible (Table 2).
The reason for this better stability can be inferred from SEM
characterization of the MEA cross-section (Fig. 6b and e) that
shows how the spongy three-dimensional structure of PtRu/
GNF anode has been preserved during the 6-day measurement, unlike with the other supports. Moreover, the particle
size growth is comparatively less pronounced for PtRu/GNFs
from degraded MEAs, which further explains the remarkable
stability of these catalysts.
As a mechanically and chemically resistant material, GNF
is able to withstand the mechanical and electrochemical
stress induced by the fluid flow, electrochemical reactions and
dimensional changes upon starting and shutting down of the
fuel cell. Thus, we envisage that after suitable optimization of
MEA preparation process for the PtRu/GNF anodes, these
materials could provide higher current densities with better
stability than conventional PtRu/Vulcan anodes.

4.
Fig. 7 e The current density obtained at 0.4 V with different
support materials in a DMFC at 70  C. (a) PtRu/Vulcan (black
line), (b) PtRu/FWCNT (red line), (c) PtRu/GNF (green line).
(For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this
article.)

Conclusions

In this work PtRu catalyst has been deposited on three different

carbon support materials with special effort to obtain comparable particle size and composition in order to evaluate the
effect of the support in the catalytic activity and stability of the
materials in DMFC anodes. Very similar metal loadings,
particle sizes and even distributions were attained for the

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 3 4 1 5 e3 4 2 4

catalysts on the different carbon supports. Electrochemical

experiments show that the highest currents are reached with
PtRu catalyst on GNF support whereas PtRu/FWCNT seems to
be more tolerant to methanol oxidation intermediates. Nevertheless, catalysts on both tubular supports exhibit clearly
higher activity towards methanol oxidation and better tolerance for COads poisoning than the same catalyst on Vulcan
support. When the same catalysts are compared in a DMFC
anode an inverse trend is observed, with PtRu/Vulcan exhibiting the highest OCV and current densities. However, when
subject to the long-term chronoamperometry experiments this
catalyst degrades fast, the three-dimensional layer structure of
the Vulcan anode is lost, resulting in a gradual decrease of
current density that is problematic from the application point
of view. PtRu/FWCNT produced moderate current densities
and suffered more pronounced current density losses and
anode layer structural changes. On the other hand, although
PtRu/GNF provided slightly lower initial current density than
PtRu/Vulcan, negligible current loss was detected during the 6day experiment, indicating a more stable nature of the anode
layer structure. Overall, further optimization of MEA preparation for the novel catalyst supports in view of the MEA structural characterization after the long-term stability tests shall
lead to enhanced performance as DMFC anode catalyst layers.

Acknowledgements
The Academy of Finland (T.K., V.R., M.B. and A.G.N., Academy
Research Fellowship) and the Spanish Ministry of Science and
Innovation (V.R., Prog. Ramon y Cajal) are acknowledged for
financial support. We also thank Dr. Iratxe de Meatza for
helpful discussions and Kati Vilonen for help with the BETarea determination.

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