Materials Chemistry and Physics 128 (2011) 341–347

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Materials Chemistry and Physics

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Synthesis of a carbon-coated NiO/MgO core/shell nanocomposite as a Pd

electro-catalyst support for ethanol oxidation
C. Mahendiran a , T. Maiyalagan b , K. Scott b , A. Gedanken a,∗
a
Department of Chemistry and Kanbar Laboratory for Nanomaterials at the Bar-Ilan University Center for Advanced Materials and Nanotechnology, Bar-Ilan University,
Ramat-Gan 52900, Israel
b
School of Chemical Engineering & Advanced Materials, University of Newcastle Upon Tyne, Newcastle Upon Tyne NE1 7RU, United Kingdom

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

Article history: Carbon coated on NiO/MgO in a core/shell nanostructure was synthesized by the single-step RAPET
Received 2 June 2010 (reaction under autogenic pressure at elevated temperatures) technique, and the obtained formation
Received in revised form 13 February 2011 mechanism of the core/shell nanocomposite was presented. The carbon-coated NiO/MgO and its sup-
Accepted 16 February 2011
ported Pd catalyst, Pd/(NiO/MgO@C), were characterized by SEM, HR-TEM, XRD and cyclic voltammetry.
The X-ray diffraction patterns confirmed the face-centered cubic crystal structure of NiO/MgO. Raman
Keywords:
spectroscopy measurements provided structural evidence for the formation of a NiO/MgO compos-
Core–shell structure
ite and the nature of the coated carbon shell. The high-resolution transmission electron microscopy
Nanoparticles
Ethanol oxidation
images showed the core and shell morphologies individually. The electrocatalytic properties of the
Pd/(NiO/MgO@C) catalyst for ethanol oxidation were investigated in an alkaline solution. The results
indicated that the prepared Pd–NiO/MgO@C catalyst has excellent electrocatalytic activity and stability.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction lutants, such as SO2 and H2 S [16,17]. Magnesium oxide (MgO)

Recently, the focus on the chemical synthesis of nanoparti-
cles has shifted from single component nanoparticles to hybrid
nanoparticles. Hybrid nanoparticles usually contain two or more
different nanoscale domains, which lead to synergistic properties
due to their interfacial interactions. Therefore, hybrid nanoparticles
(non-symmetrical dimmers, symmetric core–shell and any other
hetero-structures) are promising due to their multi-function and
designable properties [1–3]. The design of core/shell structured
composites has received much attention as a means to improve
the stability and surface chemistry of the core materials, and as a
way of obtaining unique structures, properties, and applications via
a combination of the different characteristics of the components
that are not available with their single-component counterparts
[4–7]. The synthesis and characterization of hybrid nanostructure
material is aimed at designing and arranging nanomaterials in com-
plex functional structures, resulting in unique physical properties
[8–11].
Carbon-coated nanomaterials are of great interest due to their
stability towards oxidation and degradation [12–15]. The creation
of core/shell nanostructures containing bi-metal oxides has greatly
enhanced the efficiency of these structures over pure single metal
oxide particles as destructive adsorbents for environmental pol-
∗ Corresponding author.
E-mail address: gedanken@mail.biu.ac.il (A. Gedanken).
is a typical wideband-gap insulator. It has found many impor-
tant applications for use in catalysis, refractory materials, toxic
waste remediation, paint, superconductors, and substrates for thin
film growth [18–20]. NiO is a very successful material used in
various fields, such as catalysis [21], battery cathodes [22] and
fuel cell electrodes [23], and it is also widely studied as an ant
ferromagnetic as it is a chemically-stable ionic insulator with
high thermal stability and good resistance to corrosion. Many
researchers have prepared NiO and MgO nanomaterials by various
methods, e.g., the solvo-thermal technique [24], the laser technique
[25], the sol–gel method [26] and thermal decomposition [27]. The
preparation of core–shell nano-wire structures of ZnO/MgO [28]
obtained by hydrothermal, atomic layer deposition [29] and chemi-
cal vapor deposition (CVD) [30] methods has already been reported.
NiO/MgO thin films were prepared by an ion beam-assisted depo-
sition technique and were used for chemical transformations and
catalysis applications [31].
Direct ethanol fuel cells (DEFs) have attracted much attention
because ethanol has a low toxicity, as compared to the methanol
used in direct methanol fuel cells (DMFs). Ethanol can be easily pro-
duced in great quantities by the fermentation of sugar-containing
raw materials [32]. Pt-based catalysts are extensively studied for
electrocatalytic fuel cell applications. Indeed, platinum is very effi-
cient for the different reactions involved in fuel cells, such as
methanol oxidation and oxygen reduction [33]. However, it is well
known that the anode activity of Pt is adversely affected by poison-
ing from CO species. Several studies have investigated the addition

0254-0584/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2011.02.067
342 C. Mahendiran et al. / Materials Chemistry and Physics 128 (2011) 341–347

of Ru or other metals to Pt, in order to improve the activity of the

catalysts [34–36]. Nevertheless, it has been shown recently that
palladium is more active than platinum for ethanol oxidation in
basic media [37–39]. As Pd is 50 times more abundant in the earth
and cheaper than Pt, Pd-based nanomaterials are potential elec-
trocatalysts for replacing Pt in DAFCs. Palladium also plays a vital
role in catalysis and is involved in various reactions, such as Heck,
Suzuki, and Stille coupling [40–43]. In order to reduce the amount
of noble-metal loading on the electrodes, improvements to the dis-
persion of the noble metal on the support have been investigated.
Metal nanoparticles have been dispersed on a wide variety of sub-
strates, such as carbon nanomaterials [44,45], polymer matrices
[46], and oxide matrices [47,48]. Recently, metal oxides such as
CeO2 [49], NiO [50], MgO [51], TiO2 [52] and In2 O3 [53] have been
used as electrocatalysts for the direct oxidation of alcohol, and
which resulted in a significantly improved electrode performance
in terms of the enhanced reaction activity. The noble-metal shell
in the core/shell nanoparticles has two roles. First, it protects the
non-noble core from contact with the alkaline electrolyte. Second,
the coated Pd on the shell should improve the catalytic properties Fig. 1. XRD of NiO/MgO@C core/shell structure (a) and Pd–NiO/MgO@C (b).
of the substrate. We therefore report herein on a one-stage, repro-
ducible, solvent free, competent, and straightforward approach for
the synthesis of NiO/MgO@C core shell nanostructures, followed 2.4. Preparation of the working electrode
by its decoration by Pd using simple impregnation. The prepared
Glassy carbon (GC) (Bas Electrode, 0.07 cm2 ) was polished to a mirror finish
material was evaluated for the electrochemical ethanol oxidation with 0.05 ␮m alumina suspensions before each experiment and served as an under-
reaction for fuel cell applications in alkaline media. lying substrate of the working electrode. The working electrodes were fabricated
by coating Nafion-impregnated catalyst ink on a glassy carbon electrode. Thin-film
electrodes were prepared by dispersing 35 mg of the catalyst in 800 ␮L of deion-
2. Experimental ized water. 200 ␮L of a 5 wt% Nafion solution was then added and ultrasonicated
for 20 min. A known amount of the suspension was added to the glassy carbon
2.1. Synthesis of a NiO/MgO@C core/shell nanocomposite (GC) electrode and slowly dried in air. The loading of the noble metal catalyst was
0.3 mg cm−2 . A solution of 1 M of KOH containing 1 M of ethanol was used to study
The synthesis of a NiO–MgO@C core/shell nanocomposite was carried out by the activity of ethanol oxidation.
the thermal dissociation of a mixture of nickel acetate (Ni(C4 H6 O2 )2 ) and magne-
sium acetylacetonate (Mg(C5 H7 O2 )2 ), purchased from Sigma Aldrich and used as 2.5. Electrochemical measurements
received. The 3 mL closed vessel cell was assembled from stainless steel Swagelok
parts. A 1/2 union part was plugged from both sides by standard caps. In a typical Electrochemical measurements were collected using a computer-controlled Gill
synthesis of NiO/MgO@C core/shell material, 0.248 g of nickel acetate (0.072 mols) AC potentiostat (ACM Instruments Ltd., Cumbria, UK). All experiments were car-
and 0.516 g of magnesium acetylacetonate (0.072 mol) were introduced into the cell ried out in a glass cell using a traditional three-electrode assembly incorporating
at room temperature. The filled cell was closed tightly by the other plug and then a glassy carbon working electrode (0.07 cm2 ), a mercury–mercury oxide reference
placed inside an iron pipe at the center of the tubular furnace. The temperature electrode, and a platinum mesh (25 mm × 25 mm) counter electrode. All electro-
was raised at a rate of 10 ◦ C min−1 . The closed vessel cell was heated at 600 ◦ C for chemical experiments were carried out at room temperature in 1 M of aqueous KOH.
3 h. The reaction took place at the autogenic pressure of the precursor. The closed The electrolyte solution was purged with high pure nitrogen for 30 min prior to a
cell (Swagelok) was gradually cooled (∼5 h) to room temperature and opened. In series of voltammetric experiments. The current densities reported are based on the
fact, we expected to obtain 0.764 g of NiO/MgO@C for a 100% product yield, but geometric area. Triply-distilled water was used throughout for the preparation of
during the chemical reaction inside the Swagelok some of the acetate molecules solutions.
might have evaporated at the higher temperature. Thus, we achieved only 0.519 g
(∼68%) of black-colored NiO/MgO@C. The synthesis was repeated five times in order
to confirm the reproducibility of the process, and identical products were obtained. 3. Results and discussion

3.1. XRD
2.2. Preparation of Pd/(NiO/MgO@C) catalysts

3.13 mL of 0.045 mol L−1 PdCl2 were dissolved in 10 mL of ultrapure water and
60 mg of NiO/MgO@C was added. The solution was mixed by magnetic stirring for 3 h
and ultrasonicated to achieve 20% Pd loading. A freshly prepared aqueous solution
of NaBH4 was added drop wise under N2 atmosphere to the solution to reduce the Pd
species to form the electrocatalyst, which was then repeatedly washed with distilled
water to remove residual salts, centrifuged, and dried at 70 ◦ C.
2.3. Structural characterizations
XRD patterns were collected using a Bruker AXS D* Advance Powder X-ray
diffractometer (Cu KR radiation, wavelength 1.5406 Å). High-resolution scanning
electron microscopy (HRSEM) measurements of the products were carried out on
a JEOL-JSM 840 scanning electron microscope operating at 20 and 30 kV. The mor-
phologies and nanostructure were further characterized with a JEM-1200EX TEM
model and a JEOL-2010 HR-TEM model using an accelerating voltage of 80 and
200 kV, respectively. SAEDS (selected area energy dispersive X-ray analysis) of one
individual particle was conducted using a JEOL-2010 HR-TEM model. The Olympus
BX41 (Jobin Yvon Horiba) Raman spectrometer was employed, using the 514.5 nm
line of an Ar laser as the excitation source to analyze the nature of the carbon present
around the core particle.
The X-ray diffraction (XRD) pattern of the as-prepared
NiO/MgO@C core/shell nanocomposites is shown in Fig. 1(a). Sharp
and well-defined peaks are observed at 2 values of 36.95, 42.91,
62.64, 75.00, and 79.00◦ corresponding to planes of (1 1 1), (2 0 0),
(2 2 0), (3 1 1) and (2 2 2), respectively, according to JCPDS No.
024-0712 of NiO/MgO. All these peaks could be indexed to a face-
centered cubic structure with a lattice constant of a = 4.192A◦ of
NiO/MgO. The obtained lattice constants matched well with the
JCPDS values of the bulk materials of the NiO/MgO. Due to their very
similar structure, not much difference is observed in the XRD pat-
terns of NiO and NiO/MgO. Therefore, the formation of NiO/MgO can
be identified using the above diffraction peaks. Fig. 1(b) shows the
XRD patterns of the Pd doped on the NiO/MgO@C core/shell struc-
ture. The strong diffraction peaks observed at 2 values of 40.10◦ ,
46.49◦ and 68.08◦ , correspond to the (1 1 1), (2 0 0) and (2 2 0) facets
of Pd nanocrystals. The application of the Debye–Scherrer formula
to the strongest diffraction peaks for Pd at 39.9◦ gives a crystallite
size of 12.0 nm.
 C. Mahendiran et al. / Materials Chemistry and Physics 128 (2011) 341–347
Fig. 2. SEM images of NiO/MgO@C core/shell structure (a–c), EDAX spectrum of NiO/MgO@C core/shell structure (d).
3.2. SEM and TEM
SEM and TEM images for the prepared materials are shown in
Figs. 2 and 3. Fig. 2(a)–(c) shows the SEM images of NiO/MgO at dif-
ferent magnifications. The core–shell morphology is clearly distinct
in the product. The obtained EDAX (Fig. 2(d)) analysis confirmed the
presence of C, Ni, Mg and O elements in the synthesized compos-
ites. The calculated atomic ratio of MgO (0.071):NiO (0.069) from
EDAX is more or less 1:1, which is comparable to the precursors
ratio. The SEM and TEM images of the Pd/(NiO/MgO@C) catalysts
are shown in Fig. 3(a)–(c). The SEM image (Fig. 3(a)) shows that the
Pd nanoparticles are dispersed above the NiO/MgO@C core/shell
structures.
Because of the lower magnification, the shape and size of the
Pd particles cannot be not clearly seen. The TEM images (Fig. 3(b)
and (c)) of Pd/(NiO/MgO@C) catalysts show that the materials con-
tain rod- and film-shaped Pd particles deposited on the core–shell
structure of NiO/MgO@C. The measurements of the energy disper-
sive spectra of Pd (NiO/MgO@C) catalysts indicated that both the
343
Pd/C catalysts contain about 20.0 wt% of Pd, illustrating that almost
all the PdCl2 has been reduced.
The HRTEM images of NiO/MgO@C are shown in Fig. 4 and cor-
roborate the morphologies observed in the SEM/HRSEM images in
Fig. 2. The core/shell structure is clearly visible in the TEM pictures
(Fig. 4(a)–(c)). The nearly spherical nanocrystals are agglomerated
within the carbon shell (Fig. 4(a)). The dimensions of the nanocrys-
tal core are estimated to be 20 ± 5 nm. The size of the C shell
observed in Fig. 4(c) is 5.0 nm. Fig. 4(a)–(c) presents the HRTEM
images of a nanocrystalline NiO/MgO@C composite. It illustrates
the well-defined lattice fringes, indicating the high crystalline
nature of the materials. The measured inter-planar spacing “d”
value is 2.09 Å, which corresponds to the lattice plane of (2 0 0)
with the face-cantered cubic phase of the NiO–MgO material.
These values are in agreement with the reported JCPDS value of
d200 = 2.12 Å (JCPDS No. 024-0712 of NiO/MgO). The selected area
electron diffraction (SAED) pattern (Fig. 4(d)) shows the formation
of ring patterns, which infer the polycrystalline characteristic of the
materials.
344 C. Mahendiran et al. / Materials Chemistry and Physics 128 (2011) 341–347
Fig. 3. SEM images of Pd/(NiO/MgO@C) core/shell structure (a), TEM images of Pd/(NiO/MgO@C) (b and c) and EDAX spectrum of Pd/(NiO/MgO@C) core/shell structure (d).
3.3. Raman spectra
Fig. 5(a) and (b) shows the room-temperature Raman spec-
tra of the products, where the bands in 100–1300 cm−1 and
1200–1700 cm−1 corresponding to the spectral regions of the
NiO/MgO core and carbon shell, respectively. The Raman spec-
tra of the synthesized NiO/MgO@C (Fig. 5(a)) show peaks at 530,
720, 880 and 1080 cm−1 , while the literature values of the Raman
bands of NiO/MgO are 490, 720, 860, 980 and 1050 cm−1 [54,55].
The observed peaks of the NiO–MgO@C core/shell are shifted to
the red, or unchanged, when compared to commercial NiO/MgO
(Fig. 5(a)). This may be due the interaction between NiO and MgO
when they are mixed together. The Raman spectrum in the region
1100–1700 cm−1 is characteristic of graphitic and disordered car-
bon [56]. The Raman peaks at 1330 and 1600 cm−1 are the D- and
G-bands (Fig. 5(b)). The D-band is attributed to the Raman-inactive
A1g vibration mode assigned to the vibrations of carbon atoms
with dangling bonds in planar terminations of disordered graphite
[57]. The G-band is the Raman active optical mode, E2g , of two-
dimensional graphite, and which is closely related to the vibrations
in sp2 -bonded carbon atoms [58].
3.4. Electrochemical ethanol oxidation
The Pd/(NiO/MgO@C) catalyst performance for the electrocat-
alytic oxidation of 1 M of ethanol in 1 M of KOH was evaluated
by cyclic voltammetry (Fig. 6) at a scan rate of 10 mV s−1 . The
following parameters, including the onset potential (Eonset ), the
forward peak potential (Ef ), the backward peak potential (Eb ), and
the forward peak current intensity (If ) expressed in mA cm−2 , are
shown in Table 1. The Pd/(NiO–MgO@C) catalyst showed a bet-
ter activity for ethanol oxidation than Pd/C. The onset potential
for the ethanol oxidation reaction on a Pd/(NiO/MgO@C) electro-
catalyst was 200 mV more negative in comparison to that of a
Pd/C electro-catalyst. Values for Pd–NiO/C, similar to those of
Pd–NiO/MgO@C, were previously reported [50]. It is clear that
the involvement of metal oxides significantly increased the cat-
alytic activity at the same Pd loadings. The peak current density
for ethanol oxidation, 69.3 mA cm−2 for the Pd/(NiO–MgO@C) cat-
alyst, was higher than on the Pd/C electrode (47.8 mA cm−2 ). The
forward peak potential for the electro-oxidation of ethanol on the
Pd/(NiO/MgO@C) electrode was −0.17 V (vs. Hg/HgO), lower than
−0.03 V (vs. Hg/HgO) for the Pd/C catalyst. The high peak oxidation
current and low anodic peak potential show that Pd/(NiO/MgO@C)
electrocatalysts were more active than the Pd/C electrode. More-
over, the higher catalytic currents at more negative potentials on
Pd/(NiO/MgO@C) electrocatalysts could potentially improve DEFC
efficiency.
Fig. 7 shows the current density–time curves measured at a con-
stant potential of −0.2 V. The current density of ethanol oxidation
for the Pd–NiO/MgO@C composite catalyst was higher than that for
the Pd/C catalyst, as found above in the cyclic voltammetry tests.
After polarization for 60 min, Pd/(NiO/MgO@C) and Pd/C catalysts
reached their steady-state current densities of 33 and 25 mA cm−2
at a potential of −0.2 V, respectively. The data indicate that the
Pd/(NiO/MgO@C) composite catalyst has a higher catalytic activity
 C. Mahendiran et al. / Materials Chemistry and Physics 128 (2011) 341–347 345

Fig. 4. HRTEM images of NiO/MgO@C core/shell structure (a–c), SAED patterns of NiO/MgO@C core/shell structure (d).

for ethanol oxidation than the Pd/C catalyst, owing to the addition
of a core shell structure and oxide.
3.5. Formation mechanism of NiO/MgO@C core–shell
nanocomposites
The decomposition of metal acetates and metal acetylacetonates
under their autogenic pressure at elevated temperatures yielded
two different products, depending on the nature of the metal. The
decomposition of the acetates of noble metals, or metals having a
positive reduction potential, yields the metal as a core and carbon
as the shell. These results were obtained for silver acetate, copper
acetate, and even for nickel and cobalt acetates. On the other hand,
when the decomposition of the acetates of strong metals (stan-
dard reduction potential <−0.3 V) such as zinc and iron is conducted
under the autogenic pressure, the core that is obtained is composed
of their oxides. To obtain the metallic core for these strong met-
als, the decomposition of the alkyl-metal compound is conducted
under their autogenic pressure, and metallic cores (zinc, cadmium,
and aluminum) surrounded by a carbon shell are obtained. In the
current case, magnesium as a strong metal would yield MgO as the
core, but it is surprising to find nickel oxide as its partner, and not
metallic nickel. It is suggested that the MgO aids (catalyzes) the
oxidation of the nickel. It is also possible that since the reaction is

Table 1
Comparison of activity of ethanol oxidation between Pd/C and Pd/(NiO/MgO@C) electrodes.

S. no. Electrode Onset potential (V) Activitya

Forward sweep Reverse sweep

If (mA cm−2 ) Ef (V) Ib (mA cm−2 ) Eb (V)

1 Pd/C −0.5 47.8 −0.03 72.5 −0.14

2 Pd/(NiO–MgO@C) −0.7 69.3 −0.13 52.9 −0.2
3 Pd–NiO(6:1)/Cb −0.62 95 −0.08 – –
4 Pt–MgO(4:1)/Cc −0.58 51 – – –
a
Activity evaluated from cyclic voltammogram in 1 M KOH/1 M ETOH.
b
From Ref. [50].
c
From Ref. [51].
346 C. Mahendiran et al. / Materials Chemistry and Physics 128 (2011) 341–347

carried out at a lower temperature (600 ◦ C instead of 700 ◦ C), the

carbon cannot reduce the nickel oxide to metallic nickel.

4. Conclusion

Carbon-coated NiO/MgO core/shell nanostructures were syn-

thesized by the single-step RAPET technique. For electrochemical
ethanol oxidation, a Pd electrocatalyst was doped on NiO/MgO@C
by a simple reduction method. XRD and Raman spectral studies of
the as-prepared samples confirmed the formation of NiO/MgO@C,
whereas TEM studies revealed a spherical shape NiO/MgO@C
core/shell structure. The high order crystallinity of these materials
has been confirmed by HRTEM images. The electrocatalytic prop-
erties of Pd/(NiO/MgO@C) composites for ethanol oxidation were
investigated in an alkaline solution. Electrocatalytic studies show
that the prepared Pd/(NiO/MgO@C) composites have an excellent
electrocatalytic activity and stability in alkaline media.

Fig. 5. Raman spectra of NiO/MgO@C core (a) and C-shell (b).

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