Nano Energy (2013) 2, 1046–1053

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journal homepage: www.elsevier.com/locate/nanoenergy

RAPID COMMUNICATION

Synthesis of NiCo2O4 and its application in

the electrocatalytic oxidation of methanol
M.U. Anu Prathap, Rajendra Srivastavan

Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar 140001, India

Received 28 January 2013; received in revised form 10 April 2013; accepted 10 April 2013
Available online 18 April 2013

KEYWORDS Abstract
Spinel; NiCo2O4 is synthesized by the hydrothermal route in the presence of urea. Material is
Cyclic voltammetry; characterized by a complementary combination of X-ray diffraction, nitrogen sorption, and
Electrocatalytic Scanning electron microscopy. The electrochemical oxidation of methanol is investigated at
oxidation; NiCo2O4 modified electrode in the alkaline medium using cyclic voltammetry and chronoam-
Methanol oxidation
perometry methods. Electrocatalytic activity of NiCo2O4 is compared with the NiO and Co3O4
modified electrodes. A detailed investigation is made for the electrocatalytic oxidation of
methanol by varying several reaction parameters such as potential scan rate, methanol
concentration, etc. Mechanism of methanol oxidation is proposed based on the cyclic
voltammetry study. Double steps chronoamperometry study shows that the methanol electro-
oxidation is an irreversible reaction. Electrocatalytic activity of the methanol oxidation at
NiCo2O4 modified electrode is found to be significantly higher than that of NiO and Co3O4
modified electrodes.
& 2013 Elsevier Ltd. All rights reserved.

Introduction catalysts have shown promising properties with respect to

Transition metal oxides find application in heterogeneous
catalysis and electrocatalysis due to their intrinsic redox
properties and tunable chemical, morphological, and tex-
tural properties [1–6]. Transition metal based composite
materials exhibit synergistic enhancement in activities that
are much better than a simple combination of individual
components, for example: bimetallic and multi-metallic
n ability, thermodynamic stability, and low electrical resis-
Corresponding author. Tel.: +91 1881 242175;
fax: +91 1881 223395.
E-mail address: rajendra@iitrpr.ac.in (R. Srivastava).
stability, chemical activity, or resistance to poisoning, once
combined [7]. A wide variety of composite materials such as
dioxides, perovskites, pyrochlores, and spinel-type transi-
tion metal oxides have been investigated. Economical, low
toxicity and high natural abundance attracted significant
attention of the researcher to develop nickel and cobalt-
based materials, which have shown tunable textural proper-
ties and exhibited superior electrochemical capacitive
properties [8]. The advantages of using these oxides as
electrode materials are associated with their activity, avail-
tance [9]. High electrical conductivity of these materials
is due to the ease of electron transfer taking place with

2211-2855/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.nanoen.2013.04.003
Synthesis of NiCo2O4 and its application in the electrocatalytic oxidation of methanol
relatively low activation energy between cations of differ-
ent valencies by hopping processes. Since the electrocata-
lysis depends on the electronic and geometrical factors
[10], therefore, these compounds have demonstrated
promising activity and stability in the alkaline medium as
oxygen anode and cathode [11].
Methanol is an economical and readily available raw
material for fuel cell and transportation applications [12].
Direct methanol fuel cell (DMFC) is considered as a promis-
ing candidate for future energy demand. Nevertheless, its
practical application is hindered by high over-potential
associated with the direct electro-oxidation of methanol.
A great deal of interest has recently been shown with
respect to the choice of electrode materials, cheaper than
platinum [13]. Cobalt-containing spinel oxides (MCo2O4,
where M = Cu, Mn, Ni, Zn, Mg, etc.) have drawn considerable
attention due to their superior physicochemical properties
and exhibited many technological applications, ranging
from catalysts and sensors to electrode materials and
electrochemical devices [14]. NiCo2O4 materials have shown
excellent electrocatalytic activities for many electrode
reactions, for example: O2 [15] and Cl2 evolution [16] and
O2 reduction [17], as well its application as a negative
electrode for lithium-ion batteries [18,19]. Spinel-oxides
are low cost, easily available and have outstanding corro-
sion stability in alkaline solutions [20]. Therefore, in this
study, we attempted to demonstrate the applicability of
NiCo2O4 as an electrode material towards methanol oxida-
tion in the alkaline medium. The electrocatalytic activity of
NiCo2O4 modified electrode was compared with the single
component oxides such as NiO and Co3O4. Furthermore,
cyclic voltammetry and chronoamperometry methods were
used to ascertain the mechanism of methanol oxidation.
Experimental
Materials
All chemicals were analytical grade and used without
further purification. NiNO3
6H2O, NiCl2
6H2O, CoCl2
6H2O,
sodium acetate, and urea were obtained from Spectrochem
Pvt. Ltd., India. Deionized water from Millipore Milli-Q
system (resistivity 18.2 MΩ cm) was used in the electroche-
mical studies.
Synthesis of NiO
1.45 g NiNO3
6H2O was dissolved in distilled water (250 mL)
and the solution was stirred for 15 min at room tempera-
ture. 0.6 g of urea was added to the above solution and
magnetically stirred at room temperature for 3 h. Then the
reaction mixture was transferred to Teflon lined steel
autoclave and hydrothermally treated at 373 K for 10 h.
The green precipitate of Ni(OH)2 was collected, washed
with distilled water and dried in an oven at 353 K for 24 h.
The obtained Ni(OH)2 was calcined using programmable
Furness (by maintaining the heating rate of 5 K min−1) at
573 K for 4 h to form black powder NiO.
1047
Synthesis of Co3O4
CoCl2
6H2O (1.79 g) was dissolved in ethylene glycol
(60 mL) to form a transparent solution. Sodium acetate
(5.4 g) was added into the above solution. The mixed
solution was magnetically stirred until it became transpar-
ent. Reaction mixture was transferred in a Teflon-lined
stainless-steel autoclave and hydrothermally treated at
453 K for 12 h. After the reaction, autoclave was allowed
to cool to room temperature. The products were filtered,
rinsed with ethanol, and dried at 353 K for 24 h. The
obtained material was calcined using programmable Furness
(by maintaining the heating rate of 5 K min−1) at 773 K for
0.5 h to obtain Co3O4. It may be noted that when material
was calcined at 573 K a mixed phase consists of Co(OH)2 and
Co3O4 was obtained, therefore to obtain pure Co3O4,
material was calcined at 773 K.
Synthesis of NiCo2O4
NiCo2O4 was prepared by following the reported procedure
[19]. In a particular synthesis, 2.37 g CoCl2
6H2O, 1.19 g
NiCl2
6H2O, and 2.7 g urea were dissolved in 75 mL distilled
water and stirred for about 10 min to obtain a transparent
pink colored solution. The reaction mixture was then
transferred into a Teflon-lined stainless steel autoclave,
and hydrothermally treated at 393 K for 6 h. Autoclave was
cooled to room temperature and the reaction mixture was
filtered, washed with distilled water and ethanol, followed
by drying at 353 K for 24 h. Finally, the material was
calcined at 573 K for 4 h using programmable Furness by
maintaining the heating rate of 5 K min−1.
Preparation of the working electrodes
Cyclic voltammetry (CV) and chronoamperometric studies
were performed using Potentiostat-Galvanostat BASi EPSI-
LON, USA. A three electrode electrochemical cell was
employed with Ag/AgCl as the reference electrode (3 M
KCl), NiCo2O4 mounted glassy carbon electrode (GCE) (3 mm
diameter) as the working electrode, and Pt foil as the
counter electrode. Before modification of GCE, the polished
electrode was ultrasonicated in ethanol and deionized
water for 5 min, respectively. 10 mL aliquot of NiCo2O4
suspension (a homogenous sonicated solution of 10 mg of
NiCo2O4 and a mixture of 0.1 mL of Nafion and 0.9 mL of
water) was placed onto the electrode surface, the electrode
was dried in air leaving the material mounted onto the GCE
surface.
Materials characterizations
X-ray diffraction (XRD) patterns were recorded in the
2θ range of 5–901 with a scan speed of 2°/min on a
PANalytical X'PERT PRO diffractometer using Cu Kα radiation
(λ = 0.1542 nm, 40 kV, 20 mA). Scanning electron microscopy
(SEM) measurements were carried out on a JEOL JSM-
6610LV, to investigate the morphology. During the SEM
investigation, energy-dispersive X-ray spectroscopy (EDS)
was utilized in the sample characterization, and the EDS
elemental maps were obtained. Nitrogen adsorption
1048 M.U. Anu Prathap, R. Srivastava

measurement at 77 K was performed by Autosorb-IQ (Fig. 1a). Diffraction peaks observed for NiCo2O4 can be
Quantachrome Instruments volumetric adsorption analyzer. easily indexed as a face-centered cubic NiCo2O4 (JCPDS
Samples were out-gassed at 423 K for 4 h in the degas port Card no. 73-1702). No peaks from other crystallized phases
of the adsorption apparatus. The specific surface area was were observed, indicating the formation of pure NiCo2O4
determined by Brunauer–Emmett–Teller (BET) method using product. It may be noted that the XRD pattern of Co3O4 and
the data points of P/P0 in the range of about 0.05–0.3. NiCo2O4 shown here seems to be similar, but they belong to
different materials, which is well reported in the literature
[21]. The cationic distribution in the Co3O4 lattices can be
Results and discussion
classified as normal spinels, whereas as inverse spinels in
the NiCo2O4 [21].
Materials prepared in this study were subjected to XRD
The textural properties of NiCo2O4 were investigated by
investigation (Fig. 1a). The XRD patterns of NiO exhibited
nitrogen adsorption–desorption measurements (Fig. 1b).
peaks at 2θ =37.381, 43.381, 62.681, 75.481, and 79.481,
Material exhibits type IV isotherm with H3 hysteresis loop,
which can be indexed as cubic NiO phase (JCPDS 02-1216).
which is the characteristics of a mesoporous material. BJH
No reflection peaks corresponding to precursor Ni(OH)2 was
pore size distribution (inset of Fig. 1b) shows a somewhat
detected in the XRD pattern of NiO (Fig. 1a), indicating that
narrow pore size distribution centered at ∼3.8 nm along
the sample is having high phase purity. XRD pattern of
with a wide pore size distribution centered at ∼20.4 nm,
Co3O4, matches well with XRD pattern of the standard cubic
respectively. Surface area of NiO, Co3O4, and NiCo2O4 were
spinel Co3O4 (JCPDS Card no. 43-1003), and the observed
found to be 141, 25, and 68 m2 g−1.
reflections are assigned to (111), (220), (311), (222), (400),
The SEM photomicrographs provide the surface morphol-
(422), (511), and (440) (Fig. 1a). XRD pattern of NiCo2O4
ogy of the NiO, Co3O4, and NiCo2O4 (Fig. 2). SEM results show
shows the formation of a homogeneous spinel phase
nanoflake aggregated micron size ball like morphology for
NiO (Fig. 2a and b). Co3O4 exhibited irregular spheroidal
(200) NiO morphologies (Fig. 2c), which are built with nanometer sized
small crystallites (Fig. 2d). NiCo2O4 exhibited urchin-like
(111)

Co3O4
(220)

NiCo2O4 morphology (Fig. 2e and f), which are composed of nanowires

radially grown from the center, and forming a hierarchical
(311)
(222)

micro/nanostructure. EDS mapping confirms the finely

dispersed metal ions in the NiCo2O4 matrices (Fig. S1).
Intensity (a.u.)

(311) Diffused reflectance UV–visible (DRUV–visible) investiga-

(440)
(220)

(511)

tion was used to determine the electronic structure and

(400)
(111)

(222)

(422)

optical properties of NiCo2O4. It is generally known that in

(311)
the spinel structure of NiCo2O4, the divalent cations Co2+
(one-half of the Co cations) occupy the tetrahedral sites,
whereas the trivalent Ni3+ and Co3+ cations (the other half
(220)

(440)
(400)

(511)
(222)

of Co cations) reside in the octahedral sites [22]. The

(111)

(422)

NiCo2O4 exhibits two broad absorptions in the range of

350–500 and 600–800 nm (Fig. S2), which are due to the
transition from O 2p to Co 3d-eg (or Ni 3d-eg) or from O 2p to
20 30 40 50 60 70 80 90
2θ Co 3d-t2g (or Ni 3d-t2g), and the internal electron transition
from Co 3d-t2g to Co 3d-eg (or from Ni 3d-t2g to Ni 3d-eg).
160 The absorption band gap energy (Eg) can be calculated by
0.3 the following equation:
3.8 nm

20.4 nm
ðαE photon Þ2 ¼ KðE photon −E g Þ ð1Þ
Dv (log d) (cm3/g)

120 0.2
where α is the absorption coefficient, Ephoton is the discrete
Adsorbed amount (mL/g)

photon energy, K is a constant relative to the material [23].

0.1 The plot of (αEphoton)2 vs. Ephoton based on the direct
80 transition is shown in Fig. S2 (inset). The extrapolated value
(the straight lines to the x axis) of Ephoton at α =0 gives an
0.0 absorption edge energy corresponding to Eg. Using DRUV–
0 20 40 60 80 100
Pore diameter (nm) visible, Eg of the NiCo2O4 was found to be 2.06 and 2.63 eV.
40
The internal electron transitions are found to play an
important role in the photo excitation, as in the case of
BaCr2O4 [24].
0
0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0)
Electrocatalytic oxidation of methanol at
NiCo2O4 modified electrode
Fig. 1 (a) XRD patterns of NiO, Co3O4, and NiCo2O4. (b) N2
adsorption–desorption isotherm of NiCo2O4. Inset shows pore Prior to the implementation of NiCo2O4 modified electrode
size distribution. for the oxidation of methanol, the electrochemical behavior
Synthesis of NiCo2O4 and its application in the electrocatalytic oxidation of methanol
0.5 µm
Fig. 2 SEM images of (a, b) NiO, (c, d) Co3O4, and (e, f) NiCo2O4.
of NiCo2O4, NiO, and Co3O4 modified electrodes were
investigated using CV in 0.1 M NaOH solution. NiCo2O4
modified electrode exhibits a pair of well-defined redox
peaks (Fig. S3(a)) corresponding to the oxidation of Co(II)
and the reduction of Ni(III) [25,26]. These anodic peaks can
be correlated with the oxidation of Co(II) to Co(III) to Co
(IV). The cathodic peaks correspond to the reduction of Co
(IV) to Co(III) to Co(II) and Ni(III) to Ni(II). It may be noted
that the redox potential of Ni(II)/Ni(III) is very close to Co
(III)/Co(IV) [25,26]. NiO modified electrode exhibits a pair of
well-defined redox peaks corresponding to Ni(II)/Ni(III)
redox couple (Fig. S3(a)) [27]. These peaks represent the
oxidation of the Ni(OH)2 to the nickel oxy-hydroxide
(NiOOH) in the anodic run and the reduction of the
produced oxy-hydroxide to Ni(OH)2 in the cathodic half
cycle, respectively [27]. The presence of cobalt in the
NiCo2O4 structure increased the charge-acceptance of Ni
in the form of the Ni(II)/Ni(III), therefore, the redox peaks
shift to more negative potential values than NiO [28,29]. It
may be noted that the enclosed area of CV loop of the
NiCo2O4 is larger than the NiO; therefore, the current
densities of the NiCo2O4 are higher than those of the NiO,
implying its better electrochemical reactivity. CV of Co3O4
in 0.1 M NaOH consists of two pairs of redox peaks (I/IV and
II/III), resulting from the reversible transition between
Co3O4 and CoOOH (I/IV) and the transition between CoOOH
and CoO2 (II/III) (Fig. S3(b)) [30].
This section describes the preliminary investigation of
methanol oxidation at NiCo2O4, NiO, and Co3O4 modified
electrodes in the presence of 1 M methanol. CV shows a
strong oxidation current in the presence of 1 M methanol
1049
when it was compared with the CV of NiCo2O4 modified
electrode in the absence of methanol (Fig. S4). Similar
behavior was obtained for NiO modified electrode, but with
a low current response compared to NiCo2O4 modified
electrode, indicating that the presence of Nickel is required
for methanol oxidation (Fig. S5). However, when the similar
study was performed at Co3O4 modified electrode in the
presence of 1 M methanol, it did not show an increment in
the oxidation current (Fig. S6), suggesting no electrocatalytic
activity for methanol oxidation. Based on these observations,
one can easily conclude that among the three materials
investigated in this study, NiCo2O4 modified electrode exhib-
ited the highest activity towards methanol oxidation. Fig. 3a
shows a comparison of the CVs obtained at NiCo2O4 and NiO
modified electrodes in the presence of 1 M methanol. Based
on the CV, one can conclude that the current response at
NiCo2O4 modified is much higher than that of NiO modified
electrodes. Furthermore, NiCo2O4 modified electrode exhib-
ited a decrease in the over-potential compared to NiO
electrode. NiCo2O4 showed higher electrochemical activity,
which are originated from the synergistic contributions from
both nickel and cobalt ions, than those of the monometallic
NiO and Co3O4. The addition of cobalt promotes a redox
processes to less positive potentials, which mean that cobalt
acted as a chemical modifier and caused a structural change
or electronic effect [31,32]. Secondly, cobalt allows the
nickel to reach a higher oxidation state during the oxidation
process and promotes the electron transfer for methanol
oxidation [33,34].
This section describes the mechanistic investigation for
the electrochemical oxidation of methanol at NiCo2O4
1050 M.U. Anu Prathap, R. Srivastava

consumption of NiOOH species for oxidation of methanol

2000 with the formation of nickel hydroxide (Eq. (3)) (Fig. S7(a))
NiCo2O4
[37,38]. NiO modified electrode exhibited similar CV, but
NiO
with a low current response compared to NiCo2O4 modified
1500 electrode (Fig. S7(b)).
α-Ni(OH)2+OH−↔NiOOH+H2O+e−
Current (μA)

(2)
1000
NiOOH+methanol↔β-Ni(OH)2+product (3)

β-Ni(OH)2+OH−↔NiOOH+H2O+e− (4)
500

In order to understand the mechanism of the electro-

0 chemical oxidation of methanol, first the effect of methanol
concentrations on the CV responses of NiCo2O4 modified
0.0 0.2 0.4 0.6 0.8 1.0 electrode was investigated (Fig. 3b). At low concentration
Potential (V) of methanol, two distinguished anodic peaks (a1 and a2)
were observed (Fig. 3b (i, ii)). With the increase in the
methanol concentration, first anodic peak, a1 current
2500 density decreases and further disappeared (methanol con-
(i) (ii) (iii)
centration40.4 M), whereas the current density of anodic
2000 peak, a2 became significant. With the increase in the
methanol concentration, more β-Ni(OH)2 was formed due
a2 to the consumption of more NiOOH (Eq. (3)). Further,
1500
produced β-Ni(OH)2 could be oxidized to form more NiOOH
Current (μA)

a2 with higher current densities (Eq. (4)), [35,36], which is

1000
500 a2
a1
a1
0
-500
0.0 0.5 1.0 0.0 0.5
Potential (V)
Fig. 3 (a) CV of NiCo2O4 and NiO modified electrodes in the
presence of 1 M methanol in 0.1 M NaOH solution at a scan rate
of 50 mV s−1. (b) CV of NiCo2O4 modified electrode in 0.1 M
NaOH solution at a scan rate of 50 mV s−1 in the presence of
(i) 0.1 M, (ii) 0.4 M, and (iii) 1 M methanol.
modified electrode. The electrochemical behavior of
NiCo2O4 modified electrode in the presence of 0.1 M metha-
nol shows an increment in the anodic peak current for peak
(a1) followed by the appearance of a new oxidation peak
(a2) at more positive potential and a peak current (c) during
the reverse scan rate of potential (Fig. S7(a)), which is
indicative of the methanol oxidation at NiCo2O4 modified
electrode. The anodic peaks (a1) and (a2) demonstrate the
existence of two different crystallographic structures of Ni
(OH)2, (α-Ni(OH)2 and β-Ni(OH)2), which are responsible for
methanol oxidation (Eqs. (2) and (3)) [35,36]. NiOOH species
are formed from α-Ni(OH)2 (anodic peak a1), which can be
formed even in the absence of methanol (Eq. (2)), further
chemical reduction of NiOOH with methanol takes place to
form β-Ni(OH)2 (Eq. (3)). Subsequently, β-Ni(OH)2) is con-
verted to NiOOH at higher potentials, leading to the
appearance of a new anodic peak (a2) (Eq. (4)). A cathodic
peak (c), as a result of the oxy-hydroxide reduction, with
very low current value compared to anodic peak is also
observed. The relative decrease of the cathodic peak height
in the presence of methanol is attributed to the partial
responsible for significantly high-current density of a2.
Based on the results obtained (Fig. 3b), one can conclude
that the rate limiting step for the methanol oxidation
(methanol concentration40.4 M) at the NiCo2O4 modified
electrode is the reaction between methanol and NiOOH [39].
Furthermore, it was also observed that with the increase in
the methanol concentration, the reduction current in the
negative sweep decreases (c). This observation demon-
1.0 0.0 0.5 1.0
strates that the methanol reacts with NiOOH formed
on the electrode surface. The amount of NiOOH formed on
the electrode surface decreases due to its involvement in
the chemical reaction with methanol, which causes the
decrease in the charge of Ni3+ (NiOOH) in the reverse sweep
direction.
The effect of scan rate on the methanol oxidation
over NiCo2O4 modified electrode was investigated in the
presence of 0.03 M methanol using CV (Fig. 4). It was observed
that the current ratio of peak Pa1 and Pa2 (Pa1:Pa2) increases
with the increase in the scan rate. At a scan rate of 200 mV
s−1, only peak (a1) was observed, while the peak (a2) had
almost disappeared. On the other hand, only peak (a2) was
found in the voltammogram recorded at a slow scan rate
(10 mV s−1). Therefore, it can be said that the reaction shown
in Eq. (3) is not so fast that it does not match with reaction
shown in Eq. (2). Therefore, the anodic current is mainly
contributed by reaction shown by Eq. (2). As a result, the peak
a2 reduces with the increase of the scan rates and finally
disappeared at a scan rate of 200 mV s−1.
Double potential step chronoamperometry, as well as
other electrochemical methods, was employed for the
investigation of the electrode processes at NiCo2O4 modified
electrode. The double-step chronoamperograms for the
NiCo2O4 modified electrode by setting the working elec-
trode potential at 700 mV (first step) and 350 mV (second
step) vs. Ag|AgCl|KCl (3 M) for different concentrations of
methanol has been shown (Fig. 5). It was found that the
current observed from chronoamperograms was in good
Synthesis of NiCo2O4 and its application in the electrocatalytic oxidation of methanol 1051

1200 1200 1000

(i) (ii) 800 (iii)
800
800
Current (μA)
a1
600
400 a1
400 400 a2
0 a1
200
0
-400 0
-400 -200
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

800 800
(iv) (v)
600 600
Current (μA)

400
a2 400
a1 a2
200
200
0
0
-200
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Potential (V) Potential (V)

Fig. 4 CV of NiCo2O4 modified electrode recorded in 0.1 M NaOH+0.03 M methanol at a scan rate of (i) 600, (ii) 200, (iii) 100,
(iv) 50, and (v) 10 mV s−1.

of the modified electrode in the blank solution showed an

2000 almost symmetrical chronoamperogram with almost equal
800 (A) c'
1500 charges consumed for the oxidation and reduction of
Q (μC)

1000
a' surface-confined Ni(II)/Ni(III) sites (Fig. 5A (a′)). However,
in the presence of methanol, the charge value associated
400 a b c 500 with the forward chronoamperometry is greater than that
0 observed for the backward chronoamperometry (Fig. 5A (c′)).
0 5 10 15 20
The current is negligible when potential is stepped down to
I (μA)

0.45 time (s)

0 (B) 350 mV, indicating that the electrocatalytic oxidation of
500
0.40
400
(C) methanol is irreversible.
I /I

The rate constant for the chemical reaction between the

I (μA)

0.35
-400
0.30
0.6 0.7 0.8 0.9 1.0
time (s )
-800
0 5 10
Time (s)
Fig. 5 Chronoamperograms obtained at the NiCo2O4 modified
electrode in the absence (a) and in the presence of (b) 0.03 M,
and (c) 0.05 M of MeOH in 0.1 M NaOH solution. First and second
potential steps were 700 and 350 mV vs. Ag|AgCl|KCl (3 M),
respectively. Inset (A): dependence of charge (mC) vs. time, (a′)
and (c′) are derived from the data of chronoamperograms of
(a) and (c), respectively in the main panel. Inset (B): depen-
dence of IC/IL on time1/2 is derived from the data of chron-
oamperograms of (a) and (c) in the main panel. Inset (C):
dependence of current (mA) on time−1/2 is derived from the
data of chronoamperogram of (a) in the main panel.
agreement with the current observed from CV. Further-
more, the current increases as the methanol concentration
increases. This result supports our conclusion about the
catalytic role of NiOOH in the methanol oxidation. The
forward and backward potential step chronoamperometry
300
200 methanol and redox sites of NiCo2O4 can be evaluated by
100 chronoamperometry according to the method described in
0
2 4 6 8 10 12 the literature [37].
time (s )
IC =IL ¼ γ 1=2 ½π 1=2 erfðγ 1=2 Þ þ expð−γÞγ −1=2  ð5Þ
15 20
where IC is the catalytic current of the NiCo2O4 in the
presence of methanol, IL is the limiting current in the
absence of methanol and γ = kC0t (C0 is the bulk concentra-
tion of methanol) is the argument of the error function.
In cases, where γ exceed 2, the error function is almost
equal to 1, and the above equation can be reduced to
IC =IL ¼ π 1=2 γ 1=2 ¼ π 1=2 ðkC0 tÞ1=2 ð6Þ
where k, C0 and t are the catalytic rate constant (cm3
mol−1 s−1), methanol concentration (mol cm−3), and time
elapsed (s), respectively. From the slope of the IC/IL vs.
time1/2 plot, the value of k for a given concentration of
methanol can be calculated. Inset B of Fig. 5 shows one such
plot, constructed from the chronoamperogram of the NiCo2O4
in the absence and in the presence of 0.05 M methanol. The
mean value for k was found to be 5.5  103 cm3 mol−1 s−1.
Plotting of net current of NiCo2O4 in the absence of methanol
with respect to time−1/2, presented a linear dependence (see
the inset C of Fig. 5), which shows that the process is domi-
1052
2500
1600
Current (μA)
1200
2000
800
400
1500
Current (μA)
0
0.0 0.4 0.8 1.2
1000 Concentration (M)
500
0 1M
-500
0.0 0.2 0.4
Fig. 6 CV of NiCo2O4 modified electrode in the presence of
different concentrations of methanol in 0.1 M NaOH solutions at
a scan rate of 50 mV s−1. Inset shows the calibration plot.
nated by diffusion. The mean values of the sensitivity were
found to be 80 and 700 μA M−1 for NiO and NiCo2O4 modified
electrodes, respectively.
An excellent linear relationship (based on CV responses)
between oxidation peak currents and methanol concentra-
tions was observed in the range of 0.01–1.8 M for NiCo2O4
with high-current (see the inset of Fig. 6). Linear relation-
ship between oxidation peak currents and methanol con-
centrations was observed in the range of 0.01–1.6 M (see the
inset of Fig. S8) for NiO but with low current compared to
NiCo2O4. High electrocatalytic activity of NiCo2O4 compared
with the NiO may be correlated with the facile internal
electron transitions between Co 3d-t2g to Co 3d-eg (or from
Ni 3d-t2g to Ni 3d-eg). Based on the experimental evidence,
one can conclude that NiCo2O4 exhibited superior current
sensitivity compared to NiO modified electrodes investi-
gated in this study.
Conclusions
The electrocatalytic oxidation of methanol on NiCo2O4, NiO,
and Co3O4 modified electrodes was studied in the alkaline
solution. The electrocatalytic activity of NiCo2O4 modified
electrode in the methanol oxidation is significantly higher
than that of NiO modified electrode. Co3O4 modified
electrode was found to be inactive for the methanol
oxidation. Double steps choronoamperograms confirm that
the oxidation of methanol at NiCo2O4 modified electrode is
an irreversible and diffusion controlled process. A significant
reduction in the over-potential was observed for the
NiCo2O4 modified electrode when compared to the NiO
modified electrode. The linear proportionality of catalytic
peak current for methanol oxidation and also relatively low
over-potential toward methanol oxidation lead us to con-
clude that NiCo2O4 modified electrode provides a promising
new catalyst for the methanol oxidation.
M.U. Anu Prathap, R. Srivastava
Acknowledgments
Authors thank Department of Science and Technology, New
Delhi for financial assistance (DST Grant SB/S1/PC-91/
2012). AP is grateful to CSIR, New Delhi for SRF fellowship.
We acknowledge Director, IIT Ropar for constant
1.6 2.0 encouragements.
0M
0.02 M Appendix A. Supporting information
0.05 M
0.1 M
0.4 M Supplementary data associated with this article can be
1.4 M found in the online version at http://dx.doi.org/10.1016/
1.6 M j.nanoen.2013.04.003.
1.8 M
0.6 0.8 1.0
Potential (V)
References
[1] M.U. Anu Prathap, R. Srivastava, Journal of Colloid and Inter-
face Science 358 (2011) 399–408.
[2] R. Srivastava, M.U. Anu Prathap, R. Kore, Colloids and Surfaces
A: Physicochemical and Engineering Aspects 392 (2011)
271–282.
[3] M.U. Anu Prathap, B. Kaur, R. Srivastava, Journal of Colloid
and Interface Science 381 (2012) 143–151.
[4] B. Kaur, M.U. Anu Prathap, R. Srivastava, Chem Plus Chem 77
(2012) 1119–1127.
[5] D. Cao, J. Chao, L. Sun, G. Wang, Journal of Power Sources 179
(2008) 87–91.
[6] V.L.N. Dias, E.N. Fernandes, L.M.S. da Silva, E.P. Marques,
J. Zhang, A.L.B. Marques, Journal of Power Sources 142 (2005)
10–17.
[7] B.K. Boggs, G.G. Botte, Electrochimica Acta 55 (2010)
5287–5293.
[8] B. Cui, H. Lin, J.B. Li, X. Li, J. Yang, J. Tao, Advanced
Functional Materials 18 (2008) 1440–1447.
[9] D.D. Zhao, W.J. Zhou, H.L. Li, Chemistry of Materials 19 (2007)
3882–3891.
[10] J.H. Kim, S.H. Kang, K. Zhu, J.Y. Kim, N.R. Neale, A.J. Frank,
Chemistry Communications 47 (2011) 5214–5216.
[11] V. Rashkova, S. Kitova, I. Konstantinov, T. Vitanov, Electro-
chimica Acta 47 (2002) 1555–1560.
[12] Z. Wei, H. Guo, Z. Tang, Journal of Power Sources 58 (1996)
239–242.
[13] M. Jafarian, M.G. Mahjani, H. Heli, F. Gobal, H. Khajehsharifi,
M.H. Hamedi, Electrochimica Acta 48 (2003) 3423–3429.
[14] G. Zhang, B. Guo, J. Chen, Sensors and Actuators B 114 (2006)
402–409.
[15] B. Marsan, N. Fradette, G. Beaudoin, Journal of Electroche-
mical Society 139 (1992) 1889–1896.
[16] R. Bogglo, A. Carugati, G. Lodi, S. Trasatti, Journal of Applied
Electrochemistry 15 (1985) 335–349.
[17] R.N. Singh, J.F. Koenig, G. Poillerat, P. Chartier, Journal of
Electroanalytical Chemistry 314 (1991) 241–257.
[18] R. Alcantara, M. Jaraba, P. Lavela, J.L. Tarado, Chemistry of
Materials 14 (2002) 2847–2848.
[19] Q. Wang, B. Liu, X. Wang, S. Ran, L. Wang, D. Chen, G. Shen,
Journal of Materials Chemistry 22 (2012) 21647–21653.
[20] R.N. Singh, J.P. Pandey, N.K. Singh, B. Lal, P. Chartier,
J.-F. Koenig, Electrochimica Acta 45 (2000) 1911–1919.
[21] M.R. Tarasevich, B.N. Efremov, in: S. Trasatti (Ed.), Electrodes
of Conductive Metallic Oxides Part A, Elsevier, Amsterdam,
1980, p. 221.
[22] P.D. Battle, A.K. Cheetham, J.B. Goodenough, Materials
Research Bulletin 14 (1979) 1013–1024.
Synthesis of NiCo2O4 and its application in the electrocatalytic oxidation of methanol
[23] M.U. Anu Prathap, Balwinder Kaur, Rajendra Srivastava, Jour-
nal of Colloid and Interface Science 370 (2012) 144–154.
[24] D. Wang, Z. Zou, J. Ye, Chemical Physics Letters 373 (2003)
191–196.
[25] T.Y. Wei, C.H. Chen, H.C. Chien, S.Y. Lu, C.C. Hu, Advanced
Materials 22 (2010) 347–351.
[26] Z. Fan, J. Chen, K. Cui, F. Sun, Y. Xu, Y. Kuang, Electrochimica
Acta 52 (2007) 2959–2965.
[27] S.B. Aoun, G.S. Bang, T. Koga, Y. Nonaka, T. Sotomura,
I. Taniguchi, Electrochemica Commun. 4 (2003) 317–320.
[28] M. Oshitani, Y. Sasaki, K. Takashima, Journal of Power Sources
12 (1984) 219–231.
[29] M. Oshitani, T. Takayama, K. Takashima, S. Tsuji, Journal of
Applied Electrochemistry 16 (1986) 403–412.
[30] Y. Ding, Y. Wang, L. Su, M. Bellagambaa, H. Zhang, Y. Lei,
Biosensors and Bioelectronics 26 (2010) 542–548.
[31] M. Vidotti, M.R. Silva, R.P. Salvador, S.I. Cordoba de Torresi,
L.H. Dall' Antonia, Electrochimica Acta 53 (2008) 4030–4034.
[32] J.-W. Kim, S.-M. Park, Journal of Electrochemical Society 150
(2003) E560–E566.
[33] R.D. Armstrong, E.A. Charles, Journal of Power Sources 25
(1989) 89–97.
[34] R.D. Armstrong, G.W.D. Briggs, E.A. Charles, Journal of
Applied Electrochemistry 18 (1988) 215–219.
[35] T. Subbaiah, S.C. Mallick, K.G. Mishra, K. Sanjay, R.P. Das,
Journal of Power Sources 112 (2002) 562–569.
[36] Q. Yi, J. Zhang, W. Huang, X. Liu, Catalysis Communications 8
(2007) 1017–1022.
[37] M.A. Abdel Rahim, H.B. Hassan, R.M. Abdel Hamid, Journal of
Power Sources 154 (2006) 59–65.
[38] R. Ojani, J.B. Raoof, S. Fathi, Electrochimica Acta 54 (2009)
2190–2196.
1053
[39] A. Nozad Golikand, S. Shahrokhian, M. Asgari, M. Ghannadi
Maragheh, L. Irannejad, A. Khanchi, Journal of Power Sources
144 (2005) 21–27.
M.U. Anu Prathap received his Master in
Technology in Polymer Science and Rubber
Technology from Cochin University of
Science and Technology, India. He is cur-
rently a graduate student working towards
PhD degree in Department of Chemistry
from Indian Institute of Technology Ropar,
Punjab, India. His research interest includes
the development of nanomaterials for elec-
trochemical biosensors and energy conver-
sion device applications.
Rajendra Srivastava is an Assistant Profes-
sor of Chemistry at IIT Ropar. He obtained
his doctoral degree from NCL Pune, India.
He worked as a post-doctoral research
fellow at KAIST, South Korea and as a JSPS
fellowship recipient at Hokkaido University,
Japan. He has published more than 50
research papers and has, to his credit,
seven international patents. His doctoral
work was adjudged the best thesis for the
year 2006 by Catalysis Society of India. His research interests are in
the areas of development of nanostructure materials and find their
applications in catalysis (homogeneous and heterogeneous cataly-
sis/electrocatalysis) and bio-sensing.