Electrochemistry Communications 26 (2013) 97–100

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Pd–TiO2/C as a methanol tolerant catalyst for oxygen reduction reaction in

alkaline medium
S. Maheswari, P. Sridhar ⁎, S. Pitchumani
CSIR — Central Electrochemical Research Institute-Madras Unit, CSIR Complex, Chennai — 600 113, India

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

Article history: TiO2 on carbon was prepared by sol–gel method. Pd supported on TiO2–C comprising Pd and Ti in varying atomic
Received 7 September 2012 ratios namely, 1:1, 2:1 and 3:1 was prepared and characterized by X-ray diffraction and Transmission electron
Received in revised form 12 October 2012 microscopy techniques. The electrocatalytic activity for oxygen reduction reaction in aqueous 0.1 M KOH solu-
Accepted 13 October 2012
tion containing methanol was characterized by rotating disk electrode. Catalytic activity of Pd–TiO2(3:1)/C for
Available online 22 October 2012
ORR and methanol tolerance was found to be superior in relation to Pd/C.
Keywords:
© 2012 Elsevier B.V. All rights reserved.
Electro-catalyst
Methanol-tolerant catalyst
Alkaline medium
Pd–TiO2/C

1. Introduction
An alkaline fuel cell using an anion exchange membrane as an electro-
lyte is called alkaline polymer electrolyte membrane fuel cell (APEMFC)
[1] and APEMFCs using methanol as fuel is referred as alkaline direct
methanol fuel cells (ADMFCs) [2,3]. Methanol crossover in ADMFCs may
not be completely eliminated though it is lesser than that in DMFCs [4].
Hence, the development of suitable methanol-tolerant non-Pt based
electrocatalysts is desired.
Pd/C is a promising substitute for Pt/C because of its outstanding
electro-catalytic activity for alcohol oxidation [5] and oxygen reduction
reaction (ORR) [6–9] in alkaline medium, besides cost and availability.
The modification of Pd with transition metals (M) (M = Ni, Co, Fe, V,
and Ti) has resulted in higher electro-catalytic activity toward ORR
than pure Pd [10]. Catalysts based on metal–transition metal oxide are
known to improve the ORR activity and methanol tolerance. The hypo-
d-electron transition metal oxides have high chemical-stability, good
corrosion-resistance, and strong metal-support interaction, which can
enhance the activity of the catalysts. They, as catalyst supports, are able
to stabilize and disperse adequately a number of active phases, as well
as to retain a high surface area [11]. Among different metal oxides, TiO2
is attractive due to its promising electrochemical properties, chemical
stability, non-toxic nature and when combined with carbon as catalyst
support shows better catalytic activity than metal supported on TiO2
[12] due to poor conductivity of the latter compared with carbon.
Further, Pt–TiO2/C shows improved stability in PEMFCs compared with
Pt/C [13].
⁎ Corresponding author. Tel.: +91 44 22542068; fax: +91 44 22542456.
E-mail address: psridhar@csircmc.res.in (P. Sridhar).
Recently, F. Hu et al. have shown better ethanol oxidation and sta-
bility for Pd supported on carbonized TiO2 nanotube in alkaline medi-
um compared with Pd/C [14]. Nguyen et al. investigated the ethanol
oxidation on Pd/TiO2 and Pd/TinO2n−1 in alkaline medium and found
Pd/TinO2n−1 to be suitable. But TinO2n−1 showed lower electronic con-
ductivity than carbon [15]. Mentus et al. have reported higher ORR activ-
ity for Pd/TiO2 in alkaline medium than in acidic medium [16]. Pioneering
work on ORR activity of Pt-TiO2 in alkaline medium was reported by of
Temmeveski et al. [17]. To the best of our knowledge, only a few studies
have been performed on Pd–TiO2/C in alkaline medium, however, they
do not cover the methanol tolerance behavior and also the optimum re-
quirement of Ti.
In the present study, Pd–TiO2/C comprising Pd and Ti in varying
atomic ratios namely, 1:1, 2:1 and 3:1 were prepared, and evaluated
for ORR in the presence of methanol.
2. Experimental section
2.1. Preparation of Pd–TiO2/C
A sol–gel route was adopted to prepare TiO2/C. The amount of Pd–
TiO2/C was fixed to be 1.0 g. Pd was fixed at 200 mg. Titanium
isopropoxide and carbon were taken proportionately so as to have Pd:Ti
in varying ratios of 1:1, 2:1 and 3:1 in the final catalyst. For example in
the preparation of Pd–TiO2 (3:1)/C, 190.26 mg of titanium isopropoxide
was diluted with isopropanol and made into a homogeneous solution
by ultrasonication. 50 μL of 0.1 M aqueous H2SO4 was added to titanium
isopropoxide solution to make the titania sol and sonicated for half an
hour followed by the addition of 734 mg of Vulcan carbon (XC72R)
under stirring condition. To form a gel, the resultant mixture was left for

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98 S. Maheswari et al. / Electrochemistry Communications 26 (2013) 97–100

12 h under stirring condition and heated up to 80 °C, for 1 h to remove all glassy carbon disk (0.196 cm 2) which was used as a working elec-
volatile substances present in it. The resulting TiO2/C powder was ground. trode. A pre-calibrated silver–silver chloride (Ag/AgCl, 0.210 V vs.
The prepared TiO2/C was suspended in deionized water and SHE) electrode and a platinized Pt foil were used as the reference
subjected to ultrasonication for 30 min and the resulting ink was and counter electrodes, respectively, in the three-electrode configura-
added to the solution containing 333.32 mg of PdCl2 with constant stir- tion. All electrochemical experiments were carried out at room tem-
ring followed by the addition of alkaline 0.5 M NaBH4. The mixture was perature (~ 25 °C).
constantly stirred for 1 h, then filtered, washed with deionized water, In order to clean and activate the working electrode, it was cycled
and dried in an oven overnight at 80 °C. The prepared Pd–TiO2/C between −1 and 0.5 V at a sweep rate of 50 mV/s in high pure nitrogen
containing Pd and Ti in varying atomic ratios namely, 1:1, 2:1 and 3:1 purged aqueous solution containing 0.1 M KOH and 0.1 M CH3OH until
is designated and referred as Pd–TiO2(1:1)/C, Pd–TiO2(2:1)/C and Pd– stable and reproducible voltammograms were obtained. The CVs were
TiO2(3:1)/C, respectively. recorded once the working electrode was well equilibrated. LSV experi-
ments were performed using RDE in oxygen saturated aqueous solution.
2.2. Characterization of catalysts LSV data were recorded in the cathodic-sweep direction from 0.1 V to
−0.5 V over a range of rotations (400 to 2400 rpm) at a scan rate of
X-ray diffraction (XRD) patterns were obtained on a PANalytical 3 mV s −1.
X-ray Diffractometer using CuKα radiation (λ = 1.5406 Ǻ) between
10° and 90° in reflection geometry in steps of 5° min −1. The micro- 3. Results and discussion
scopic features of the samples were examined by using TECNAI 20
G2 TEM (200 kV). The crystalline structures of Pd–TiO2/C comprising Pd and Ti in vary-
All the catalysts were electrochemically characterized using Cyclic ing ratios are characterized by XRD and shown in Fig. 1(A). For compar-
Voltammetry (CV) and ORR was evaluated based on the Liner Sweep ative purpose, the XRD pattern of 20 wt.% of Pd/C is also included in the
Voltammetry (LSV) measurements. The electrochemical setup, the figure. The diffraction peaks at 2θ values of 40.1°, 46.68°, 68.08° and
cell arrangement, preparation of electrodes and catalyst ink are the 82.0° are due to the (111), (200), (220) and (311), respectively for the
same as that is reported elsewhere [18]. 70 μg of Pd was loaded on crystalline planes of Pd/C with a face centered cubic (fcc) structure.

(B)
(A) (111)
Carbon

(200)
(220)
(d) (311)

(c)

50 (C)
(b)
% of intensity

SD=1.18nm
40

30

(a) 20

10
10 20 30 40 50 60 70 80 90
0
2 (degree) 4.5 5.0 5.5 6.0 6.5 7.0 7.5
Particle size (nm)

3 (D) 25 Pd/C
Pd-TiO2(3:1)/C
(E)
Current density (mA/cm2)
Current density (mA/cm2)

2 20 Pd-TiO2(2:1)/C
Pd-TiO2(1:1)/C
1
15
0
10
-1
5
-2
Pd/C 0
-3 Pd-TiO2(3:1)/C
Pd-TiO2(2:1)/C -5
-4
Pd-TiO2(1:1)/C
-5 -10
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4
Potential (V) vs. Ag/AgCl Potential (V) vs Ag/AgCl

Fig. 1. (A) XRD patterns of (a) Pd/C (b) Pd–TiO2(3:1)/C (c ) Pd–TiO2 (2:1)/C and (d) Pd–TiO2 (1:1)/C, (B) TEM image for Pd–TiO2 (3:1)/C and (C) corresponding histogram, (D) CV of Pd/C and
Pd–TiO2/C in 0.1 M KOH and (E) in aqueous 0.1 M KOH solution containing 0.1 M Methanol.
 S. Maheswari et al. / Electrochemistry Communications 26 (2013) 97–100 99

Furthermore, no characteristic peak of TiO2 is found in XRD pattern,
suggesting that titanium oxide is in amorphous form. The mean particle
size is calculated from the (111) diffraction line using Scherrer equa-
tion. The particle sizes of Pd/C, Pd–TiO2(1:1)/C, Pd–TiO2(2:1)/C and
Pd–TiO2(3:1)/C are 8, 6.1, 6.5 and 7.1 nm, respectively revealing that
the mean crystallite size increases with decreasing TiO2 content. Addi-
tion of TiO2 suppressed the growth of Pd particle due to the interaction
between Pd and TiO2.
The TEM images of Pd–TiO2(1:1)/C, Pd–TiO2(2:1)/C and Pd–
TiO2(3:1)/C are obtained and a typical TEM image for Pd–TiO2(3:1)/C is
shown in Fig. 1(B) and its histogram is shown in Fig. 1(C). It can be seen
that all the nanoparticles are crystalline and uniformly dispersed on
carbon. The mean particle size decreases with increasing TiO2 content in
the catalysts. This indicates that TiO2 hinders the aggregation of Pd parti-
cles. The average particle sizes are 6.2, 6.4 and 6.8 nm for Pd–TiO2(1:1)/C,
Pd–TiO2(2:1)/C and Pd–TiO2(3:1)/C, respectively that are in agreement
with XRD data.
Fig. 1(D) shows the CVs for Pd/C and Pd–TiO2/C containing Pd and
Ti in varying atomic ratios in high pure nitrogen saturated 0.1 M KOH
solution at 25 °C. The peak obtained in the forward scan for Pd/C
below −0.55 V due to oxidation of the adsorbed hydrogen is relatively
larger than that obtained with Pd–TiO2/C on account of reduced avail-
ability of Pd active sites. The electrochemical surface area (ESA) is deter-
mined from the charge corresponding to the reduction of oxide, which is
formed due to adsorption of a monolayer of chemisorbed oxygen and is
two times as large as that (QH =210 μC cm−2) of the hydrogen mono-
layer, [18] i.e. (QH =1/2QO). i.e.,
 
  Q O μC=cm2  
2 2
ESA cm =mgPd ¼  electrodeloading mgPd =cm :
420 μC=cm 2
The ESA values of Pd/C, Pd–TiO2(1:1)/C, Pd–TiO2(2:1)/C and Pd–
TiO2(3:1)/C, are 35, 17, 32 and 34 m2 g−1 respectively. The higher
ESA for Pd/C than Pd–TiO2/C is attributed to decreased availability of ac-
tive Pd sites. Pd–TiO2(3:1)/C shows higher ESA compared with Pd–
TiO2(2:1)/C and Pd–TiO2(1:1)/C suggesting that higher amount of
TiO2 may hinder the electrocatalytic activity of Pd possibly encapsulat-
ing the Pd active sites. In the reverse scan, the oxide reduction onset
potential for Pd is observed at −0.031 V in Pd/C, while for Pd–TiO2/C
containing Pd and Ti in varying atomic ratios of 1:1, 2:1 and 3:1 the cor-
responding potential is observed at −0.197, −0.108 and −0.103 V,
respectively. This indicates that the TiO2 effects a fundamental change
in Pd atoms and its interaction with H2O and possibly O2. This change
could manifest in the kinetic measurements. It is interesting to note
that the trend observed in electrochemical surface area with respect
to increase in TiO2 content is similar to that reported for Pt–TiO2/C [19].
Fig. 1(E) shows the CVs for methanol oxidation reaction (MOR) in
deaerated aqueous solution containing 0.1 M KOH and 0.1 M methanol.
Pd/C shows a larger anodic current for MOR above −0.4 V than that
observed for Pd–TiO2(3:1)/C, Pd–TiO2(2:1)/C and Pd–TiO2(1:1)/C. The
reduced MOR on Pd–TiO2/C reveals that TiO2 addition possibly might
not only block the active Pd sites for the oxidation of methanol but also
inhibit methanol adsorption as revealed by Sanchez et al. [20].
Fig. 2(A) shows the LSVs on the Pd and Pd–TiO2/C in aqueous
solution containing 0.1 M KOH and 0.1 M methanol under an oxygen
atmosphere at a rotation rate of 1600 rpm. Pd exhibited a large anodic
(reversal) current above −0.2 V. The current reversal is due to MOR.
Among all the catalysts, Pd–TiO2(2:1)/C shows the least oxidation
current due to methanol. MOR caused the onset of cathodic limiting
current to shift by ~−200 mV. This is due to the formation of a mixed
potential which is caused by MOR and ORR simultaneously on the sur-
face of Pd/C. Such a mixed potential at the cathode would negatively
affect the cathode performance of the ADMFCs. The enhanced catalytic
activity of Pd–TiO2(3:1)/C is due to the hypo-hyper d-electron interac-
tion between TiO2 and Pd [21]. It is well known that RuSe/C is methanol
tolerant due to its activity for ORR with complete inactivity for methanol
oxidation. In our earlier study, RuSe/C, heat treated at 500 °C, was

0
(A) 0
(B)
Pd-TiO 2 (1:1)/C Pd-HTRuSe(2:1)/C with methanol
Current density (mA/cm2)

Current density (mA/cm2)

Pd-TiO (3:1)/C without methanolC

Pd-TiO 2 (2:1)/C Pd-TiO (3:1)/C with methanol
-1 -1
Pd-TiO 2 (3:1)/C Pd/C without methanol
Pd/C Pd/C with methanol
-2 -2

-3 -3

-4 -4

-5 -5

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 -0.5 -0.4 -0.3 -0.2 -0.1 0.0
Potential (V) vs. Ag/AgCl Potential (V) vs. Ag/AgCl

Pd-TiO2(3:1)/C
0.8 (D)
Potential (V) vs. Ag/Agcl

Without methanol
-0.05 With methanol
1/i (mA-1cm2)

0.6
-0.10
0.4

-0.15
0.2 Pd-TiO2 (3:1)/C-with methanol
@-0.1V
(C) @-0.2V

-0.20 0.0
-0.6 -0.3 0.0 0.3 0.6 0.06 0.08 0.10 0.12 0.14 0.16
-1/2 -1/2 1/2
log i (mA/cm2) (rad s )

Fig. 2. (A) LSV of Pd/C and Pd–TiO2/C in aqueous 0.1 M KOH solution containing 0.1 M methanol; (B) comparative LSVs in aqueous 0.1 M KOH solution on Pd–TiO2 (3:1)/C, Pd–
HTRuSe (2:1)/C and Pd/C at 1600 rpm; (C) Tafel slopes for Pd–TiO2(3:1)/C; (D) K–L plots for Pd–TiO2(3:1)/C at −0.1 and −0.2 V.
100 S. Maheswari et al. / Electrochemistry Communications 26 (2013) 97–100
incorporated with Pd (Pd–HTRuSe(2:1)/C) to improve the catalytic ac-
tivity for ORR in presence of methanol and found to give almost the
same onset and half-wave potentials, and less parasitic current com-
pared to Pd/C [22]. It is interesting to note that Pd–TiO2(3:1)/C shows
much improved performance over Pd–HTRuSe(2:1)/C as revealed in
Fig. 2(B). It is clearly established that RuSe/C can be replaced by TiO2 in
carbon-supported Pd for improved ORR with methanol tolerance in
ADMFCs.
ORR activity of Pd–TiO2(3:1)/C in absence of methanol is compared
with that in presence of methanol as shown in Fig. 2(B). Onset and
half-wave potentials for ORR in presence of methanol are more positive
compared with that in the absence of methanol while the trend is
reversed in the case of Pd/C. The above trend is also reflected in the spe-
cific activities of Pd–TiO2/C containing Pd and Ti in varying atomic ratios
of 1:1, 2:1 and 3:1 and Pd/C for ORR, which are found to be 0.28, 0.20,
0.50 and 0.22 mA/cm2, respectively in the presence of methanol, and
0.12, 0.18, 0.41 and 0.34 mA/cm2, respectively in the absence of metha-
nol. Fig. 2(C) shows two Tafel slope regions accounted for an initial fast
charge-transfer step followed by a chemical step, which is the rate-
determining step [8]. The Tafel slope values are almost the same in pres-
ence and absence of methanol, suggesting that methanol does not affect
the kinetics of oxygen reduction on Pd–TiO2(3:1)/C. The number of elec-
trons for the reduction of oxygen on Pd–TiO2/C is found to be four based
on Koutecky–Levich plot shown in Fig. 2(D).
4. Conclusions
Pd/TiO2/C catalysts with varying atomic ratios (1:1, 2:1 and 3:1) of
Pd to Ti were prepared and evaluated for ORR in the presence of metha-
nol. The ORR studies with methanol shows that Pd–TiO2(3:1)/C has
higher methanol tolerance and better selectivity.
Acknowledgments
Financial support from CSIR, New Delhi through a supra-institutional
project under XI Five Year Plan is gratefully acknowledged. S. Maheswari
is grateful to CSIR, New Delhi, for a Senior Research Fellowship. Authors
are thankful to Dr. K. Vijayamohanan Pillai for his constant encourage-
ment and support.
References
[1] M. Cifrain, K.V. Kordesch, Journal of Power Sources 127 (2004) 234.
[2] H.F. Hunger, Proceeding of Annual Power Sources Conference 14 (1960) 55.
[3] C. Bianchini, P.K. Shen, Chemical Review 109 (2009) 4183.
[4] E.H. Yu, K. Scott, Journal of Power Sources 137 (2004) 248.
[5] L. Jiang, A. Hsu, D. Chu, R. Chen, Journal of the Electrochemical Society 156 (3)
(2009) B 370.
[6] F.H.B. Lima, J. Zhang, M.H. Shao, K. Sasaki, M.B. Vukmirovic, E.A. Ticianelli, R.R.
Adzic, Journal of Physical Chemistry C 111 (2007) 404.
[7] H. Erikson, A. Kasikov, C. Johans, K. Kontturi, K. Tammeveski, A. Sarapuu, Journal
of Electroanalytical Chemistry 652 (2011) 1.
[8] N. Alexeyeva, A. Sarapuu, K. Tammeveski, F.J. Vidal-Iglesias, J. Solla-Gullón, J.M.
Feliu, Electrochimica Acta 56 (2011) 6702.
[9] H. Erikson, A. Sarapuu, N. Alexeyeva, K. Tammeveski, J. Solla-Gullón, J.M. Feliu,
Electrochimica Acta 59 (2012) 329.
[10] M. Shao, P. Liu, J. Zhang, R. Adzic, The Journal of Physical Chemistry. B 111 (2007) 6772.
[11] E.N. Muhamad, T. Takeguchi, G. Wang, Y. Anzai, W. Ueda, Journal of the Electro-
chemical Society 156 (1) (2009) B32.
[12] X. Guo, D.J. Guoa, X.P. Qiu, L.Q. Chen, W.T. Zhu, Journal of Power Sources 194 (2009)
281.
[13] S. Vinod Selvaganesh, G. Selvarani, P. Sridhar, S. Pitchumani, A.K. Shukla, Journal
of the Electrochemical Society 157 (7) (2010) B1000.
[14] F. Hu, F. Ding, S. Song, P.K. Shen, Journal of Power Sources 163 (2006) 415.
[15] S.T. Nguyen, J.-M. Lee, Y. Yang, X. Wang, Industrial & Engineering Chemistry Research
51 (30) (2012) 9966.
[16] S. Mentus, A. Abu-Rabi, D. Jašin, Electrochimica Acta 69 (2012) 174.
[17] K. Tammeveski, T. Tenno, A. Rosental, P. Talonen, L.S. Johansson, L. Niinistöd, Journal of
the Electrochemical Society 146 (2) (1999) 669.
[18] S. Maheswari, S. Karthikeyan, P. Murugan, P. Sridhar, S. Pitchumani, Physical
Chemistry Chemical Physics 14 (2012) 9683.
[19] G. Selvarani, S. Maheswari, P. Sridhar, S. Pitchumani, A.K. Shukla, Journal of the
Electrochemical Society 156 (11) (2009) B1354.
[20] V.M. Sanchez, E.D. Llave, D.A. Scherlis, Langmuir 27 (2011) 2411.
[21] J.M. Jakšić, C.M. Lačnjeva, N.V. Krstajič, M.M. Jakšić, Chemical Industry and Chem-
ical Engineering Quarterly 14 (2) (2008) 119.
[22] S. Maheswari, P. Sridhar, S. Pitchumani, Fuel Cells (2012), http://dx.doi.org/10.
1002/fuce.201200069.