Mohamed Abdelfattah Ibrahim1

Department of Chemistry,
Faculty of Science,
University of Tabuk,
Tabuk, Saudi Arabia;
Department of Chemistry,
Faculty of Education in El-Arish,
Suez Canal University,
North Sinai, Egypt
e-mail: science1712@gmail.com

Taha Hanfy
Department of Physics,
Faculty of Science,
Fayoum University,
63514 Fayoum, Egypt;
Department of Physics,
Faculty of Science,
University of Tabuk,
Tabuk, Saudi Arabia

A. A. Al-Ghamdi
Department of Physics,
Faculty of Science,
King Abdel Aziz University,
Jeddah, Saudi Arabia

Electrocatalytic Oxidation
of Methanol on an
Pd/Pyy/Niad-atoms Electrode
In this paper we study the effect of Niad-atoms on the activity of a Pd/Pyy nanocomposite
anode, we find that the catalytic activity of an anode towards methanol oxidation
increased by threefold in the presence of Niad-atoms. [DOI: 10.1115/1.4024834]
Keywords: electrochemical oxidation of methanol, palladium nanoparticles, electrolyte
membrane fuel cells

Farid El-Tantawy
Department of Physics,
Faculty of Science,
Suez Canal University,
Ismailia, Egypt

Hossam S. Rageb
Department of Physics,
Faculty of Education in El-Arish,
Suez Canal University,
North Sinai, Egypt

Introduction

In recent years, rapid developments of portable electronic devices

demand new power sources with higher energy density than currently
used Li-ion secondary battery to achieve longer operation hours and
shorter recharging time. Proton exchange membrane electrolyte fuel
cells (PEMFCs) based on hydrogen as a fuel have advanced substantially but their successful commercialization is restricted by safety
and storage efficiency of this flammable gas [14]. Therefore, certain
liquid fuels, such as methanol, ethanol, propanol, ethylene glycol,
and diethyl ether, have been considered for fueling PEMFCs directly
[5]. Among these, methanol, with a theoretical capacity of
5.06 A h g1 and a hydrogen content of 12.8 wt. %, is unambiguously the most attractive organic liquid fuel at present for directly
fueled PEMFCs. Such fuel cells are referred to as direct methanol
fuel cells (DMFCs) [68]. The electro-oxidation of methanol in acid
media has been studied extensively [912] and may be represented
by the general dual-path mechanism described below [13]:
The poising intermediates highlighted above bind strongly to
metal in acid media and lead to serve limitations in the oxidation
kinetics [14], resulting in significant polarization losses. In
addition, the rate of methanol permeation in proton conducting is
1
Corresponding author.
Contributed by the Advanced Energy Systems Division of ASME for publication
in the JOURNAL OF FUEL CELL SCIENCE AND TECHNOLOGY. Manuscript received May 7,
2012; final manuscript received January 14, 2013; published online August 20, 2013.
Editor: Nigel M. Sammes.

particularly high due to the electro-osmotic drag associated with

the proton conduction mechanism (i.e., from anode to cathode).
An alternative approach proposed for the development of the
DMFC is to operate with alkaline electrolytes [15] and is based on
the assumption that electrocatalysis is generally more facile in this
media [16]. Methanol oxidation on some metals single crystal and
polycrystalline electrodes has also been investigated by several
research groups [1723]. On some metals, the bonding of chemisorbed intermediates in alkaline appears weaker than in acidic
media leading to more efficient electro-oxidation [24].
Kho et al. said that the direct methanol fuel cell can be effective
for portable devices that will allow these devices to operate for longer time without being plugged into an electrical outlet [24].
Besides that, fuel cells have potentially 510 times greater energy
densities than rechargeable batteries (Kundu et al.) [25].
The main objective of this work is to study the effect of Ni
ad-atoms on the activity of the Pd/Pyy nanocomposite electrode
for the oxidation of methanol in KOH in order to
(a) find cheap, economic, and reasonable electrodes which
show higher current density at a low overpotential and have
a high tolerance against poisoning
(b) discuss the origin of the catalytic activity of methanol
oxidation at Au and Pd/Pyy nanocomposite electrodes
modified by metal ad-atoms
(c) discuss the different theories which explain the activity of
different electrodes modified by under potential deposition
(upd) metal ad-atoms

Journal of Fuel Cell Science and Technology

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Experiment

2.1 Solutions. Electrolytic solutions were prepared with MX

cm pure water and analytical grade chemicals: H2SO4 (BDH),
CH3OH (Merck), NiSO4 (Winlab), KOH (Koch-light), Pyrrole
(SigmaAldrich), and PdCl2 (Merck). All solutions were purged
with ultrapure nitrogen.
2.2 Instrumentation and Cell. All experiments were performed using a conventional three compartment cell equipped
with a saturated Calomel electrode (SCE) as a reference electrode
and a platinum sheet as a counterelectrode. The working electrode
was a Pd/Pyy sheet with a geometric surface 1 cm2.
Potentiostatic measurements were performed using a combined
wave generator and potentiostat (Oxoford electrode), Goldstar
DM-6135 digital multimeter, and a Gorez xyt recorder model
Serrogor 796.
2.3 Preparation of Working Electrode. PPy (polypyrrole)
films were deposited directly onto a Pt electrode. The Pt was used
as the working electrode in a standard three-electrode electrochemical cell containing a 0.1 M KCl and 0.4 M pyrrole aqueous solution.
The reference electrode was Ag:AgCl and the counterelectrode
was a Au foil sheet. The deposition was carried out potentiostatically at 0.8 V for the PPy deposition [26], until a conducting film
of several thousand nanometers was grown. This value has been
estimated considering that a charge density of about 3 C cm2 was
passed during the deposition and the device active area is about
6 mm2. The Pd nanoparticles inclusions were obtained by applying
a sequence of cathodic pulses to the Pt:PPy electrode that started at
0 V and reached 0.35 V; 0 V is the measured open circuit potential for the elicited electrochemical cell, while 0.35 V is the deposition potential for metallic Pd from a 0.1 M PdCl2 solution.
Cathodic potential pulses were applied until a charge of 1015 mC
was passed through the cell. The choice of a pulse-type potential
function was necessary to obtain the metal deposition; in fact, a
potentiostatic procedure would have reduced the conducting polymeric film leading to its passivation and stopping the metal deposition itself. The oxidation states of the catalytic metal included was
investigated by X-ray photoelectron spectroscopy (XPS) analysis.
The analysis was performed with a Leybold LHS 10 Spectrometer
equipped with a Mg Ka anode source. Scanning electron microscopy (SEM) micrographs were obtained with a JEOL JSM 6400.
The electron energy used was 15 keV. The specimens were coated
with carbon using a vacuum evaporator (JEOL, GEE 500).

Fig. 2

X-ray photoelectron spectra of Pd 3d regions in PdPPy

agglomeration of Pd particles the size of which is around 100 nm, as

evidenced by Fig. 1. Wide voids between clusters of Pd particulates
are clearly seen which provide channels for ionic transport.
In Fig. 2 the Cu Pd 3d signals recorded on a Pd:PPy sample is
shown. The fitting peaks are the result of a theoretical simulation
and correspond to XP signals coming from Pd in its different oxidation states. Our best fit allows us to conclude that in Pd: PPy, Pd
is present as Pd [0] and Pd(II), the latter as PdO and PdCl2,
respectively. A cross-check of the attributions given above comes
from the analysis of the Cl 2p spectra recorded on Pd doped films
and the O 1s region in the Pd. As a matter of fact the peak area of
the Cl 2p signal is in the ratio 1:2; moreover, the energy position
of the O 1s signal is typical of that of an inorganic oxide such as
PdO. The third fitting doublet of the Pd region can be assigned to
PdCl2 on the basis of both binding energy values and the amount
of chloride in the sample (Cl 2p signal area). It is to be underlined
that in Pd-doped samples, the Cl signal cannot be attributable to
the PPy counterion due to the very low (if any) N signal (charged,
oxidized pyrrole).
3.2 Electrocatalytic Oxidation of Methanol at Platinum/
ad-Atoms Modified Electrode in 0.1 M. The electrochemical
oxidation of methanol at the Pd/Pyy electrode modified by under
potential deposition (upd) of nickel in KOH solution is shown in
Fig. 3. The electro-oxidation current was found to be increased by a
factor of about 3 times for concentrations <104 M. The peak current also shifted to a more negative value (about 50100 mV).

Results and Discussion

3.1 Characterization of Nanocomposite Materials. Figure 1

shows, respectively, the SEM pictures of nanocomposite which shows

Fig. 1

SEM of anode material

Fig. 3 Cyclic voltammogram of Pd/Pyy electrode in 0.5 M

CH3OH 1 0.1 M KOH in absence (a) and in presence (b) 1027 M
(c) 1026 M (d) 1025 M (e) 1024 M Ni21. Scan rate 50 mV s21.

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Transactions of the ASME

Increasing the Ni2 concentration leads to a decrease of the current

peak, while the shift of the onset methanol oxidation is still valid.
A qualitative interpretation of the different behavior of these
metal ad-atoms may be given using the reaction mechanism of Pt
in alkaline medium. The reaction rate, i.e., the current density,
which is controlled by the rate-determining step
Pd  COads Pd  OHads ! Pd  COOHads Pd

[9]

[10]

[11]

[12]

may be written as follows:

l kFhO hOH
where k is a rate constant (in s1 cm2), F is the Faraday constant,
hO and hOH are the degree of coverage of the electrode surface,
respectively, by the organic adsorption residue and by hydroxyl
ions. This last equation implies that at least one adsorbed species
moves freely on the electrode surface, which is certainly true
for reversible adsorbed hydroxyl ions. The presence of a metal adatom M modifies both hO and hOH as follows:
(1) If the metal ad-atoms are easily oxidized than Pd, hOH
reaches significant values at potentials more negative than
Pd electrode. Hence, the rate of methanol oxidation
increases according to the bifunctional theory [27,28]. In
addition to that, the change of the electronic properties
(what is so called ligand effect) [27,28] of the electronic
properties of Pd substrate in presence of metal ad-atoms
cannot be excluded.
(2) If the metal ad-atoms are not easily oxidized than Pd, both
hOH and hO decrease due to the blocking of the Pd surface
sites towards methanol oxidation.

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

References
[1] Gottesfeld, S., and Pafford, J., 1988, A New Approach to the Problem of Carbon Monoxide Poisoning in Fuel Cells Operating at Low Temperatures, J.
Electrochem. Soc., 135(10), pp. 26512652.
[2] Igarashi, H., Fujino, T., and Watanabe, M., 1995, Hydrogen Electro-Oxidation
on Platinum Catalysts in the Presence of Trace Carbon Monoxide, J. Electroanal. Chem., 391(12), pp. 119123.
[3] Shukla, A. K., Jackson, C. L., and Scott, K., 2003, The Promise of Fuel CellBased Automobiles, Bull. Mater. Sci. 26(2), pp. 207214.
[4] Pone de Leon, C., Walsh, F. C., Pletcher, D., Browning, D. J., and Akeman,
J. B., 2006, Direct Borohydride Fuel Cells, J. Power Sources, 155(2), pp.
172181.
[5] Lamy, C., Lima, A., LeRuhn, V., Delime, F., Coutanceau, C., and Leger, J. M.,
2002, Recent Advances in the Development of Direct Alcohol Fuel Cells
(DAFC), J. Power Sources, 105(2), pp. 283296.
[6] Han, J., and Park, E.-S., 2002, Direct Methanol Fuel-Cell Combined With a
Small Back-Up Battery, J. Power Sources, 112(2), pp. 477483.
[7] Arico, A. S., Srinivasan, S., and Antonucci, V., 2001, DMFCs: From Fundamental Aspects to Technology Development, Fuel Cells, 1(2), pp. 133162.
[8] Shukla, A. K., Jackson, C. L., Scott, K., and Raman, R. K., 2002, An
Improved-Performance Liquid-Feed Solid-Polymer-Electrolyte Direct Metha-

Journal of Fuel Cell Science and Technology

[23]

[24]

[25]

[26]

[27]

[28]

nol Fuel Cell Operating at Near-Ambient Conditions, Electrochim. Acta

47(21), pp. 34013407.
Clavilier, J., Lamy, C., and Leger, J. M., 1981, Electrocatalytic Oxidation of
Methanol on Single Crystal Platinum Electrodes. Comparison With Polycrystalline Platinum, J. Electroanal. Chem., 125(1), pp. 249254.
Bewick, A., Kunimastsu, K., Pons, B. S., and Russel, J. W., 1984,
Electrochemically Modulated Infrared Spectroscopy (EMIRS): Experimental
Details, J. Electroanal. Chem., 160(12), pp. 4761.
Iwasita, T., and Vielstich, W., 1991, Identification of Methanol Adsorbates on
Platinum: An In Situ FT-IR Investigation, J. Electroanal. Chem., 317(12), pp.
291298.
Meli, G., Leger, J. M., Lamy, C., and Durand, R. C., 1993, Direct Electrooxidation of Methanol on Highly Dispersed Platinum-Based Catalyst Electrodes:
Temperature Effect, J. Appl. Electrochem., 23(3), pp. 197202.
Beden, B., Leger, J. M., and Lamy, C., 1992, Modern Aspects of Electrochemistry, Vol. 22, J. O.M. Bockris, B. E. Conway, and R. E. White, eds., Plenum,
New York, p. 97.
Kadigram, F., Beden, B., Leger, J. M., and Lamy, C., 1981, Synergistic Effect
in the Electrocatalytic Oxidation of Methanol on Platinum+Palladium Alloy
Electrodes, J. Electroanal. Chem., 125(1), pp. 89103.
Parsons, R., and Van der Noot, T., 1988, The Oxidation of Small Organic Molecules: A Survey of Recent Fuel Cell Related Research, J. Electroanal. Chem.,
257(12), pp. 945.
Azdic, R., Armor, M., and Tripkovic, A., 1984, Structural Effects in Electrocatalysis: Oxidation of Formaldehyde on Gold and Platinum Single Crystal Electrodes in Alkaline Solution, J. Electrochem. Acta, 29(10), pp. 13531357.
Bagtotzky, V. S., and Vassilyev, Y. B., 1967, Mechanism of Electro-Oxidation of Methanol on the Platinum Electrode, J. Electrochim. Acta, 12(9), pp.
13231343.
Lamy, C. Leger, J. M., and Clavilier, J., 1982, Structural Effects in the Electrooxidation of Methanol in Alkaline Medium: Comparison of Platinum Single Crystal
and Polycrystalline Electrodes, J. Electroanal. Chem., 135(2), pp. 321328.
Beden, B., Kadrigan, F., Lamy, C., and Leger, J. M., 1982, Oxidation of Methanol on a Platinum Electrode in Alkaline Medium: Effect of Metal ad-Atoms
on the Electrocatalytic Activity, J. Electroanal. Chem., 142(12), pp. 171190.
Morallon, E., Vazquez, J. L., and Aldaz, A., 1990, Electrochemical Behaviour
of Basal Single Crystal Pt Electrodes in Alkaline Medium, J. Electroanal.
Chem., 288(12), pp. 217228.
Tripkovic, A., Popovic, K. D., Molcilvoic, J. D., and Drazic, D. M., 1996,
Kinetic and Mechanistic Study of Methanol Oxidation on a Pt(111) Surface in
Alkaline Media, J. Electroanal. Chem., 418(12), pp. 920.
Tripkovic, A., Popovic, K. D., Molcilvoic, J. D., and Drazic, D. M., 1998,
Kinetic and Mechanistic Study of Methanol Oxidation on a Pt(100) Surface in
Alkaline Media, J. Electroanal. Chem., 448(2), pp. 173181.
Tripkovic, A., Popovic, K. D., Molcilvoic, J. D., and Drazic, D. M., 1998,
Kinetic and Mechanistic Study of Methanol Oxidation on a Pt(110) Surface in
Alkaline Media, J. Electrochim. Acta., 44(67), pp. 11351145.
Kho, B. K., Bae, B., Scibioh, M. A., Lee, J., and Ha, H. Y., 2005, On the Consequences of Methanol Crossover in Passive Air-Breathing Direct Methanol
Fuel Cells, J. Power Sources, 142(12), pp. 5055.
Kundu, A., Jang, J. H., Gil, J. H., Lee, H. R., Kim, S. H., Ku, B, and Oh, Y. S.,
2007, Micro-Fuel CellsCurrent Development and Applications, J. Power
Sor., 170(1), pp. 6778.
Guascito, M. R., Boffi, P., Malitesta, C., Sabbatini, L., and Zambonin, P. G.,
1996, Conductive Polymer Electrodes Modified by Metallic Species for
Electrocatalytic PurposesSpectroscopic and Microscopic Investigation,
Mater. Chem. Phys., 44(1), pp. 1724.
Beden, B., Kadigran, F., Lamy, C., and Leger, J. M., 1982, Oxidation of Methanol on a Platinum Electrode in Alkaline Medium: Effect of Metal ad-Atoms
on the Electrocatalytic Activity, J. Electroanal. Chem. Interfac. Electrochem.,
142(12), pp. 171190.
Samant, P. V., Fernandes, J. B., Rangel, C. M., and Figueiredo, J. L., 2005,
Carbon Xerogel Supported Pt and PtNi Catalysts for Electro-Oxidation of
Methanol in Basic Medium, Catal. Today, 103, pp. 173176.

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