DOI: 10.1002/fuce.
201200069
Pd-RuSe/C as ORR Specific Catalyst in
Alkaline Solution Containing Methanol
S. Maheswari1, P. Sridhar1*, S. Pitchumani1
1
CSIR-Central Electrochemical Research Institute-Madras Unit, CSIR Complex, Chennai 600 113, India
Received May 07, 2012; accepted September 04, 2012
Abstract
Carbon supported RuSe (RuSe/C) catalyst in varying atomic
ratios of Ru to Se, namely, 1:1, 2:1, and 3:1 were prepared
and their performances were compared with carbon sup-
ported Ru (Ru/C). Based on the performance, Palladium
was incorporated into as prepared RuSe(2:1)/C and heat
treated HTRuSe(2:1)/C. Ru/C, RuSe/C, and Pd-RuSe/C
were characterized by X-ray diffraction (XRD) and transmis-
sion electron microscopy techniques. The XRD analyses of
Ru/C, RuSe/C and Pd-HTRuSe/C show the formation of
the hcp structure of Ru particles and the mean particle size
was obtained from Ru(101) peak. The electrochemical char-
1 Introduction
Direct methanol fuel cells (DMFCs) are alternative to the
hydrogen fuel cells and are often referred to as the sixth fuel
cell type. However, the full potential of the DMFCs has not
been realized due to kinetic constraints associated with anode
reaction and the permeation of methanol through the poly-
mer membrane to the cathode, which results in a depolariz-
ing oxidation reaction on the cathode (parasitic current). The
rate of methanol permeation is particularly high due to elec-
tro-osmotic drag associated with proton conduction mecha-
nism, i.e. from anode to cathode. Due to methanol cross over,
100 mV potential and 25% efficiency losses occur at cathode
in DMFCs even while using Pt as catalyst [1].
Unlike in acidic media, the kinetics of both methanol oxi-
dation reaction and oxygen reduction reaction (ORR) in alka-
line media is much faster allowing the use of non-precious
metal catalysts to reduce the cost of the fuel cell. Prabhuram
et al. [2] reported that the polarization characteristic of metha-
nol oxidation on platinum black in alkaline solution is super-
ior by one order of magnitude in current at a given potential
to that in acidic media. On platinum, the bonding of chemi-
sorbed intermediates, such as formic acid, formaldehyde and
CO appears weaker than in acidic media leading to more effi-
cient electro-oxidation.
Similar to the use of proton-exchange membrane in acid
fuel cells, the use of an anion-exchange membrane (AEM)
instead of a caustic alkaline liquid electrolyte in an alkaline
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ORIGINAL RESEARCH PAPER
acterizations of Ru/C, RuSe/C, Pd-HTRuSe(2:1)/C and Pd-
RuSe(2:1)/C were conducted by cyclic voltammetry. Linear
Sweep Voltammetric studies showed that incorporation of
Pd in HTRu-Se(2:1)/C resulted in better catalytic activity
toward oxygen reduction with resistance to methanol oxida-
tion. The quantity of hydrogen peroxide produced was
obtained from rotating ring disk electrode studies.
Keywords: Alkaline Direct Methanol Fuel Cell (ADMFC);
Electrocatalyst; Methanol Tolerance; Oxygen Reduction
Reaction; Ru-Se
fuel cell can solve problems, such as electrolyte leakage and
precipitation of carbonate salts. The advantage of alkaline
direct methanol fuel cells (ADMFC) over DMFCs is that in
the former OH– ions diffuse through the membrane and form
water at the anode due to the reactions given below resulting
in reduced methanol cross over from the anode to the cath-
ode.
Anodic reaction
CH3 OH ‡ 6OH → 5H2 O ‡ CO2 ‡ 6e E0a ˆ 0:81 V (1†
Cathodic reaction
3=2O2 ‡ 3H2 O ‡ 6e → 6OH E0c ˆ 0:40 V (2†
Net reaction
CH3 OH ‡ 3=2O2 → 2H2 O ‡ CO2 E0cell ˆ 1:21 V (3†
where, E0 represents the standard electrode potential of an
electrochemical reaction.
For further development of ADMFCs, efforts are being
expended to develop efficient electrocatalysts for the anode
and the cathode, which requires methanol-tolerant and oxy-
gen specific ones. There are three ways to obtain higher
methanol tolerance (i) Methanol adsorption reduction that
decreases both the mixed potential and CO poisoning, (ii)
–
[*] Corresponding author, psridhar@csircmc.res.in
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 Maheswari et al.: Pd-RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol
ORIGINAL RESEARCH PAPER
Lowering of CO oxidation, which reduces the mixed potential
but does not reduce CO poisoning and (iii) CO oxidation
enhancement that reduces CO poisoning but increases the
mixed potential [3]. The most effective way is through
reduced methanol adsorption, the so-called “ensemble
effect”, which is dilution of the active component with cataly-
tically inert metals by alloying and affecting the distribution
of active sites.
Non-noble metal catalysts for methanol tolerance reported
in the literature are macrocyclic derivatives such as porphyr-
ins and phthalocyanines of transition-metal compounds like
Co and Fe and chalcogenide materials. Ruthenium based
chalcogenides showed higher methanol tolerance compared
with macrocyclic derivatives [4]. These electrocatalysts have
shown nearly the same activity for ORR in the absence as well
as in the presence of methanol but have shown poor electro-
catalytic activity in relation to dispersed Pt in methanol free
electrolytes.
A number of Ru-based chalcogenides (RuxZy; Z = S, Se,
and Te) have been synthesized as cathode catalysts and tested
for ORR in alkaline and acidic medium [5, 6]. Among these,
Ru-based chalcogenide catalysts, RuSex, have attracted much
attention because of their activity for oxygen reduction com-
bined with their complete inactivity for methanol oxidation
[4, 6–8], which makes them interesting for use as cathode
material in the ADMFC. The activity enhancement provided
by the Se atoms is related to an interfacial effect resulting
from the binary structure of the catalysts. In these systems,
Ru atoms act as electrochemically active sites for ORR; Se
atoms play a role in chemically stabilizing the Ru centres
against oxidation, leading to improved catalytic activity and
stability [6]. However, with and without methanol, these cata-
lysts did not match the catalytic activity of carbon supported
Palladium for ORR. Unlike in acid media, ORR and methanol
oxidation activity of Pd in alkaline media is remarkably high-
er than that of Pt [9–11].
Ternary electro-catalysts may be more active than their ori-
ginal mono and bimetallic counterparts, as the addition of a
third component may modify the bifunctional, electronic or
structural characteristics of the mono and bimetallic catalyst
surface [12, 13].
Prakash and Joachin [14] reported that oxygen reduction
on ruthenium electrode proceeds primarily by a direct 4-elec-
tron reduction pathway without producing significant
amounts of solution phase peroxide in alkaline medium.
Anastasijevic et al. [15] explained that the reaction kinetics
and mechanism were found to depend on the oxidation state
of the ruthenium surface and the kinetics was slower on a Ru
surface with a thicker oxide layer. Ramaswamy et al. [5] first
time investigated Ru based chalcogenides for ORR in alkaline
medium and have shown Ru-Se/C as a better ORR catalyst
compared with other Ru-based chalcogenides (Ru-S and Ru-
Te/C). So far there is no report on RuSe/C catalyst for metha-
nol tolerance in alkaline medium.
In the present study, catalysts containing Ru and Se in
varying atomic ratio namely, 1:1, 2:1, and 3:1 were prepared,
964 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
heat treated and evaluated for ORR in presence of methanol
and the ratio was optimized. Subsequently, Pd was incorpo-
rated into as prepared and heat treated RuSe(2:1)/C to evalu-
ate the ORR in presence and absence of methanol. In the fol-
lowing text, Pd incorporated into as prepared and heat
treated RuSe(2:1)/C will be referred to as Pd-RuSe(2:1)/C
and Pd-HTRuSe(2:1)/C, respectively. The prepared catalysts
were characterized by XRD, transmission electron microscope
(TEM), and ORR. The prepared catalysts were also evaluated
in Fuel Cell mode.
2 Experimental Section
2.1 Preparation of Catalyst
Single-step borohydride reduction method was followed
for catalyst preparation and the reactions were carried out at
80 °C. Selenium modified Ruthenium catalysts were synthe-
sized following a procedure reported in the literature [16]. To
prepare Ru-Se (1:1)/C catalyst, 1.026 g of RuCl3 and 0.219 g
of SeO2 were wetted with IPA and dissolved in 150 ml of
double distilled water. The resulting solution was added to
0.6 g of well dispersed carbon (Vulcan XC 72 R) under stir-
ring condition followed by heating to 80 °C for 30 min. After
cooling to the room temperature, alkaline NaBH4 was added
to reduce the metal ions. NaOH allows the stabilization of
borohydride in water; otherwise it is reduced by H+ to H2
and boron derivatives, with the precipitation of the Ru and Se
hydroxides. These hydroxides are then reduced to their
respective metallic forms by the addition of NaBH4 [17]. The
reaction mixture was heated at 80 °C under stirring for an
hour to complete the reaction process, followed by cooling to
room temperature. The mixture was filtered and washed with
double distilled water and dried at 60 °C overnight under
vacuum. The RuSe/C obtained was transferred into a porce-
lain boat and heat treated at 500 °C for 2 h under nitrogen
atmosphere. To prepare Ru/C, the above procedure without
the addition of SeO2 was followed. To prepare Pd-RuSe(2:1)/
C and Pd-HTRuSe(2:1)/C, 333.0 mg of PdCl2, corresponding
to 20% of Pd in the final catalyst, dissolved in 50 ml. of IPA
was added to the suspension containing as-prepared RuSe/C
or heat treated RuSe/C under constant stirring followed by
the addition of aqueous alkaline solution containing 0.1 M
sodium borohydride, heated to 80 °C, cooled to room temper-
ature and filtered. The solid obtained was dried at 80 °C.
2.2 Physical Characterization
Powder X-ray diffraction (XRD) studies were conducted to
analyze the crystallinity of carbon-supported Ru/C, RuSe/C,
Pd-HTRuSe(2:1)/C and Pd-RuSe(2:1)/C nano catalysts. For
this purpose, powder XRD patterns were obtained on a Phi-
lips PanAnalytical X-ray Diffractometer using CuKa radiation
(k = 1.5406 Å) between 10° and 90° in reflection geometry in
steps of 5° min-1.
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Maheswari et al.: Pd-RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol
TEM was used to determine the average particle size and
dispersion of carbon supported Ru, RuSe and Pd-
HTRuSe(2:1) catalysts. For this purpose, the microscopic fea-
tures of the samples were examined by using TECNAI 20 G2
TEM (200 kV). For TEM characterization, a carbon film
deposited onto a mica sheet was placed onto the copper grid.
Catalyst was suspended in isopropyl alcohol and cast by
dropping the suspension onto a carbon-coated copper grid
followed by solvent evaporation in vacuum at room tempera-
ture (≈25 °C).
The surface atomic compositions of Pd-HTRuSe/C and
Pd-RuSe/C catalysts were obtained using energy dispersive
X-ray analysis (EDAX) facility provided with a scanning elec-
tron microscope (TESCAN).
2.3 Electrochemical Characterization
All the catalysts were electrochemically characterized
using cyclic voltammetry and ORR was evaluated based on
the linear-sweep voltammetry (LSV) measurements. The elec-
trochemical setup consisted of a computer-controlled electro-
chemical analyzer (Autolab PGSTAT-30), a radiometer speed
control unit from Pine Instrument Company and a rotating
ring disk electrode (glassy carbon (GC) disk of 5 mm diam-
eter and platinum as the ring). A conventional three-electrode
cell consisting of GC disk with a geometric area of 0.196 cm2
was used as the working electrode. Before each test, the elec-
trodes were polished with 0.06 lm alumina on a polishing
cloth to obtain a mirror-like finish followed by rinsing with
double-distilled water in an ultrasonic bath. For ink prep-
aration, 14 mg of catalyst and 28 mg of 5 wt.% of Nafion
ionomer were ultrasonically dispersed with 4 ml of water for
30 min to obtain a homogeneous solution. In this case, Nafion
helps to attach the catalyst particles on the GC electrode [18].
To prepare the working electrode, catalyst (Ru/C, RuSe(1:1)/
C, RuSe(2:1)/C, RuSe(3:1)/C, Pd-HTRuSe(2:1)/C, Pd-
RuSe(2:1)/C, and Pd/C) suspension was quantitatively trans-
ferred to the surface of the polished GC disk. The electrode
was dried at room temperature. A pre-calibrated mercury
mercuric oxide (MMO, 0.165 V vs. standard hydrogen elec-
trode) electrode and a platinized Pt foil were used as the ref-
erence and counter electrodes, respectively, in the three-elec-
trode configuration. All electrochemical experiments were
carried out at room temperature (≈25 °C).
Hydrogen peroxide produced in O2 saturated 0.1 M KOH
electrolyte was monitored using polycrystalline platinum
ring biased at 0.5 V versus MMO, in RRDE configuration.
Collection efficiency of the Pt ring electrode is N = Iring/
Idisk = 0.35.
In order to clean and activate the working electrode, it was
cycled between –1 and 0.5 V with respect to MMO at a sweep
rate of 50 mV s–1 in high pure nitrogen purged 0.1 M KOH
with and without 0.1 M CH3OH until stable and reproducible
voltammograms were obtained. The cyclic voltammograms
were recorded once the working electrode was well equili-
brated. LSV experiments were performed using RRDE in oxy-
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ORIGINAL RESEARCH PAPER
gen saturated 0.1 M KOH with and without 0.1 M CH3OH.
LSV data were recorded in the cathodic-sweep direction from
0.2 to –0.5 V versus MMO over a range of rotations (400–
2400 rpm) at a scan rate of 3 mV s–1.
2.4 Fuel Cell Studies
2.4.1 Customizing the Electrolyte
Ammonium-type AEM (AHA-Neosepta) was modified
from Cl– to OH– form as follows. The AHA membrane com-
prises tetra-alkyl ammonium groups as fixed cation groups
bonded to a polyolefin backbone chain. The Cl– form mem-
brane was rinsed several times with de-ionized water, and
then immersed in 4 mol dm–3 KOH aqueous solution at room
temperature for overnight for the replacement of Cl– with
OH–. The membranes were again washed several times with
de-ionized water at room temperature.
2.4.2 Fabrication of Membrane Electrode Assembly (MEA)
MEA preparation for ADMFCs was adopted with some
modification of the procedure described elsewhere [9]. In
brief, both electrodes comprised backing layer, gas diffusion
layer (GDL) and catalyst layer. For backing layer, carbon
paper (Toray TGP-H-120) of 0.35 mm thickness was teflo-
nized with 15 wt.% of polytetrafluroethylene emulsion and
sintered at 350 °C for 1 h. The GDL was coated with a homo-
geneous suspension of high surface area carbon (Vulcan
XC72 R) with 1.5 mg cm–2 loading over the teflonized Toray
sheet, which was then sintered at 350 °C for half-an-hour.
2.4.2.1 Preparation of Catalyst Layer
Catalysts were suspended in IPA and the mixture was agi-
tated in an ultrasonic water bath. 1.5 wt.% of anion conduct-
ing ionomer FAA 003 was dissolved in N-methyl pyrrolidone
and added to the catalyst slurry. The mixture was treated
ultrasonically for at least 10 min and then coated on GDL.
Both anode and cathode contained Pt-Ru/C and Pd/
PdRuSe/PdHTRuSe, respectively with a metal (Pt/Pd) load-
ing of 1 mg cm–2, which was kept identical in all the MEAs.
MEAs were obtained by pressing the cathode and anode on
either side of the AEM under a compaction pressure of
60 kg cm–2 at room temperature for 5 min.
2.4.3 Cell Polarization Studies
The performance of MEAs was evaluated using a conven-
tional 4 cm2 fuel cell fixture with a parallel serpentine flow
field machined on graphite plates (Schunk Kohlenstofftech-
nik GmbH, Germany). After equilibration, the single cells
were tested at room temperature (30 °C) with 2M methanol
with 6M KOH and humidified oxygen at anode and cathode,
respectively at a flow rate of 0.5 L min–1 at atmospheric pres-
sure. Measurements of cell potential as a function of current
density were conducted potentiostatically using a LCN10-40
electronic load procured from Bitrode Corporation.
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 965
 Maheswari et al.: Pd-RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol

3 Results and Discussion

ORIGINAL RESEARCH PAPER

Figure 1a–d shows the XRD patterns of Ru/C and RuSe/C

containing Ru and Se in varying atomic ratio namely, 1:1, 2:1,
and 3:1, respectively. The crystallite size is calculated from
the Debye-Scherrer equation using Ru(101) diffraction peak.
Ru/C catalyst exists in hexagonal close packed (hcp) struc-
ture with a lattice constant of a = b = 2.722 Å and
c = 4.3016 Å, which is in good agreement with JCPDS data.
No oxide peaks of ruthenium are observed. XRD patterns of
RuSe/C catalyst show all the peaks corresponding to that of
Ru/C. Lattice constant of Ru(101) in RuSe/C is less compared
with that in Ru/C due to lattice contraction because of the
presence of Se. Crystallite size of RuSe/C is lesser than Ru/C,
which indicates that Se prevents the agglomeration and
forms the pyrite structure. Crystallite size decreases with
increasing Se content. [i.e. Ru/C (7.6 nm) > RuSe(3:1)/C
(4.8 nm) > RuSe(2:1)/C (4.5 nm) > RuSe(1:1)/C) (4.1 nm)].
This trend is in good agreement with the literature. [19].
Se is considered to be an important element to increase the
stability and prevent oxidation of Ru. Here, Se is firmly
bonded to ruthenium atoms at the surface and also p-type
semiconductor of Se in elemental form becomes metallic
when interacting with Ru in Ru-Se catalysts, due to charge
transfer from Ru to Se [20]. Figure 2a–e shows XRD patterns
Fig. 2 XRD patterns of (a) Pd/C (b) HTRuSe(2:1)/C (c) Pd-HTRuSe(2:1)/C
of Pd/C, HTRuSe(2:1)/C, Pd-HTRuSe(2:1)/C, RuSe(2:1)/C,
(d) RuSe(2:1)/C and (e)Pd- RuSe(2:1)/C.
and Pd-RuSe(2:1)/C. Pd-HTRuSe(2:1)/C shows mixed peaks
of Pd/C and HTRuSe(2:1)/C while Pd-RuSe(2:1)/C shows indicating that Ru and Se may be present in amorphous form,
peaks corresponding to that of Pd/C alone. Hence, in both which is also confirmed by the XRD patterns of RuSe/C as
the cases palladium alloy formation is unlikely. In the former shown in Figure 2d. It is interesting to note that comparison
case Pd and RuSe/C may be present together as a composite. of XRD patterns of RuSe/C and HTRuSe/C as shown in Fig-
In the latter case, there is no peak corresponding to RuSe/C ure 2b and d, respectively suggests that on heat treatment the
crystallinity changed from amorphous to crystalline. Similar
observation has been reported [8].
TEM images of HTRu/C, HTRuSe(2:1)/C and Pd-
HTRuSe(2:1)/C are shown in Figure 3. Ru/C heat treated at
500 °C shows bigger particle size compared with RuSe/C
and Pd-HTRuSe(2:1)/C. It confirms that Se hinders the parti-
cle size growth of Ru. The composition of Pd-HTRuSe(2:1)/C
and Pd-RuSe(2:1)/C were confirmed by the EDAX.
Cyclic voltammograms of Ru/C and RuSe/C catalysts
comprising Ru and Se in varying ratio in 0.1 M KOH in pres-
ence of 0.1 M methanol under deaerated atmosphere at a scan
rate of 50 mV s–1 are shown in Figure 4. To clean and acti-
vate, the working electrode was cycled between –1 and 0.5 V
versus MMO at a sweep rate of 50 mV s–1 in high pure nitro-
gen purged 0.1 M KOH until stable and reproducible voltam-
mograms were obtained. Peaks corresponding to oxidation of
methanol and adsorbed intermediates in the forward and
reverse scans, respectively are not observed which revealed
the inactivities of Ru/C and RuSe/C catalysts towards
methanol oxidation.
Figure 5 shows the linear sweep voltammograms on the
Ru and RuSe/C catalysts in 0.1 M KOH containing 0.1 M
Fig. 1 XRD patterns of (a) Ru/C (b) RuSe(1:1)/C (c) RuSe(2:1)/C and (d) methanol under oxygen atmosphere at a rotation rate of 1600
RuSe(3:1)/C. rpm and at a scan rate of 3 mV s–1. LSV obtained for Ru/C

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Maheswari et al.: Pd-RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol
Fig. 3 TEM images for (a) Ru/C, (b) HTRuSe(2:1)/C, and (c) Pd-
HTRuSe(2:1)/C.
Fig. 4 Cyclic Voltammograms of Ru/C, RuSe(1:1)/C, RuSe(2:1)/C, and
RuSe(3:1)/C in deareated 0.1 M KOH in presence of 0.1 M CH3OH solu-
tion at a sweep rate of 50 mV s–1.
matches well with that reported in the literature [14, 15]. On
modification of Ru surface by Se, the kinetic region shifted to
more positive potential. RuSe (2:1)/C shows reduction in
onset potential by 50 mV compared with Ru/C and exhibits
higher catalytic activity than catalysts of other compositions.
This positive shift indicates that Se is promoting the catalytic
activity of Ru and stabilizes the Ru surface toward adsorbed
oxide/hydroxide formation, in other words, Se modification
of Ru/C catalyst decreases the inhibiting effect of oxy-species
adsorption on Ru [4, 21, 22]. According to Stolbov, Se atoms
become negatively charged due to ionic Se–Ru bonding. Since
O and OH also become negatively charged upon adsorption,
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ORIGINAL RESEARCH PAPER
Current density / mA cm-2
Potential / V, vs. MMO
Current density / mA cm-2
Potential / V, vs. MMO
Fig. 5 (a) Linear sweep voltammograms of Ru/C, RuSe(1:1)/C,
RuSe(2:1)/C and RuSe(3:1)/C in oxygen saturated 0.1 M KOH in pres-
ence of 0.1 M CH3OH solution at 1600 rpm. (b) Ring current measured
during ORR at 1600 rpm.
Se and these intermediates repel each other electrostatically.
This repulsion increases the total energy of the system and
thus reduces the binding energies of oxy-species [23].
However, RuSe(3:1)/C and RuSe(1:1)/C catalysts show
lesser catalytic activity than RuSe (2:1)/C, which could be
due to insufficient Se for inhibiting formation of oxy-species
on Ru in RuSe(3:1)/C and blocking of Ru active sites by Se in
RuSe(1:1)/C. These catalysts show nearly the same catalytic
activity for ORR in the presence and absence of 0.1 M metha-
nol and no methanol oxidation peak is observed in 0.1 M
KOH solution containing 0.1 M methanol. Though Se modi-
fied Ru shows better ORR activity than Ru/C but is still lower
than that on Pd/C.For Ru/C catalyst, the H2O2 formation
yields are highest at low overpotentials (at –0.1 V), which is
associated with blocking of Ru surface by hydroxide or oxide
species. For RuSe/C catalysts, the formation of H2O2
decreases significantly in comparison with Ru/C at the corre-
sponding potentials revealing the preference for O2 reduction
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 967
 Maheswari et al.: Pd-RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol
ORIGINAL RESEARCH PAPER
to water rather than H2O2 formation. It is interesting to note
that H2O2 formation on RuSe(2:1)/C is the lowest coinciding
with its maximum ORR activity as revealed by LSV. The
increased ORR activity with increasing Se content can be due
to either the suppression of oxy/hydroxide electrosorption
on Ru sites, thus providing OH-ad free Ru sites for the ORR
or the formation of a new active RuSe phase [22]. With higher
Se content as in (RuSe(1:1)/C), the H2O2 yield increases again
due to reduced availability of two neighboring free sites on
Ru for dissociative adsorption of oxygen, which is required
for the complete reduction to water [4, 22].
In Figure 6, log ik is plotted versus potential that gives the
Tafel plot. From the plot, the Tafel slope is calculated. In the
higher potential region, i.e. < 0.05 V, the slope calculated is
88 mV dec–1 and it can be explained by a mechanism of oxy-
gen reduction in which the reaction involves an initial fast
charge-transfer step followed by a chemical step, which is the
rate-determining step [24]. The Tafel slope value remains
unchanged in the presence and absence of methanol, suggest-
ing that methanol does not affect the kinetics of oxygen
reduction on RuSe(2:1)/C.
Figure 7 shows the LSV of RuSe(2:1)/C, Pd/C, Pd-
HTRuSe(2:1)/C, and Pd-RuSe(2:1)/C in 0.1 M KOH in pres-
ence of 0.1 M methanol under an oxygen atmosphere at a
rotation rate of 1600 rpm and at a scan rate of 3 mV s–1. The
onset potential and E1/2 values are given in Table 1. Pd-
HTRuSe(2:1)/C shows enhanced ORR activity than
HTRuSe(2:1)/C and nearly the same onset potential as that
for Pd/C. But methanol oxidation current is lower by
200 mA cm-2 than Pd/C. It is very interesting to note that Pd-
RuSe (2:1)/C shows more positive onset potential than
HTRuSe(2:1)/C but less positive onset potential than that of
Pd-HTRuSe(2:1)/C, while there is very little methanol oxida-
tion current. Improved ORR activity of Pd-HTRuSe(2:1) com-
pared with Pd-RuSe(2:1) could be due to the fact that without
heat treatment Ru could be present predominantly in oxi-
dized form as reported by Bron et al. [25]. Further investiga-
Fig. 6 Tafel plots of HTRuSe(2:1)/C with and without methanol.
968 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Current density / mA cm-2
Potential / V, vs. MMO
Fig. 7 Linear sweep voltammograms of HTRuSe(2:1)/C, PdRuSe(2:1)/C,
Pd/C and Pd-HTRuSe(2:1)/C in oxygen saturated 0.1 M KOH in presence
of 0.1 M CH3OH solution at 1600 rpm.
Table 1 Data from half-cell measurements
Catalysts HTRuSe(2:1)/C Pd/C Pd-HTRuSe(2:1)/C Pd-RuSe(2:1)/C
On-set –50 16 16 –24
Potential (mV)
Half-wave –197 –70 –75 –103
potential (mV)
tion is being pursued to understand the behavior of methanol
oxidation on Pd-RuSe(2:1)/C and Pd-HTRuSe(2:1)/C.
ORR activity of Pd-HTRuSe(2:1)/C in absence of methanol
is compared with that in presence of methanol as shown in
Figure 8a. Onset and half-wave potentials for ORR in pres-
ence of methanol are more positive compared with that in
absence of methanol while the trend is reversed in the case of
Pd/C as can be seen in Figure 8b. The catalytic activity for
ORR on Pd/C and Pd-HTRuSe(2:1)/C without methanol is
nearly the same as revealed in Figure 8a and b. However, in
case of Pd-HTRuSe(2:1)/C, influence of methanol oxidation
current on ORR current is significantly less compared with
that in case of Pd/C.
Steady state polarization studies are conducted for
ADMFCs comprising 20% Pd/C, Pd-RuSe(2:1)/C, and Pd-
HTRuSe(2:1)/C as cathode catalyst and 40% Pt-Ru/C as
anode catalyst at room temperature. Figure 9 shows steady-
state performance curves for ADMFCs with aqueous 6 M
KOH containing 2 M methanol and oxygen as fuel and oxi-
dant, respectively. Among the various ADMFCs, the cell
comprising Pd-HTRuSe(2:1)/C shows the highest peak
power density of 13.7 mW cm–2 in relation to Pd/C and Pd-
RuSe(2:1)/C with a power density of 11.5 and 13.3 mW cm–2,
respectively matching the trend observed in the kinetic stud-
ies.
www.fuelcells.wiley-vch.de FUEL CELLS 12, 2012, No. 6, 963–970
Maheswari et al.: Pd-RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol

4 Conclusion

ORIGINAL RESEARCH PAPER

Pd-RuSe/C is prepared in two steps (i) preparation and
Current density / mA cm-2

heat treatment of RuSe/C at 500 °C in the first step and (ii)

incorporation of Pd nanoparticles by reducing PdCl2 salt
using sodium borohydride. The Tafel slope value
(88 mV dec–1) of RuSe(2:1)/C is almost the same with and
without methanol. Linear polarization measurements reveal
that in the presence of methanol, E1/2 of the polarization
curve of ORR on the Pd/C and Pd-HTRuSe(2:1)/C is almost
the same while methanol oxidation current on the latter is
200 mA cm–2 less than that on the former. Hence, Pd-
HTRuSe(2:1)/C is a suitable methanol tolerant cathode mate-
rial for oxygen reduction in ADMFCs as it shows good stabil-
ity, oxygen reduction activity, and methanol tolerance.
Potential / V, vs. MMO

Acknowledgements
Financial support from CSIR, New Delhi through a supra-
Current density / mA cm-2

institutional project under XI Five Year Plan is gratefully ac-

knowledged. S. Maheswari is grateful to CSIR, New Delhi,
for a Senior Research Fellowship. Authors are thankful to Dr.
K. Vijayamohanan Pillai for his constant encouragement and
support.

Potential / V, vs. MMO
Fig. 8 Linear sweep voltammograms of (a) Pd-HTRuSe(2:1)/C and (b)
Pd/C in oxygen saturated 0.1 M KOH in presence and absence of 0.1M
CH3OH solution at 1600 rpm.
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