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

stability, chemical activity, or resistance to poisoning, once
Transition metal oxides find application in heterogeneous combined [7]. A wide variety of composite materials such as
catalysis and electrocatalysis due to their intrinsic redox dioxides, perovskites, pyrochlores, and spinel-type transi-
properties and tunable chemical, morphological, and tex- tion metal oxides have been investigated. Economical, low
tural properties [1–6]. Transition metal based composite toxicity and high natural abundance attracted significant
materials exhibit synergistic enhancement in activities that attention of the researcher to develop nickel and cobalt-
are much better than a simple combination of individual based materials, which have shown tunable textural proper-
components, for example: bimetallic and multi-metallic ties and exhibited superior electrochemical capacitive
properties [8]. The advantages of using these oxides as
electrode materials are associated with their activity, avail-
n ability, thermodynamic stability, and low electrical resis-
Corresponding author. Tel.: +91 1881 242175;
fax: +91 1881 223395. tance [9]. High electrical conductivity of these materials
E-mail address: rajendra@iitrpr.ac.in (R. Srivastava). 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 1047

relatively low activation energy between cations of differ- Synthesis of Co3O4

ent valencies by hopping processes. Since the electrocata-
lysis depends on the electronic and geometrical factors CoCl2
6H2O (1.79 g) was dissolved in ethylene glycol
[10], therefore, these compounds have demonstrated (60 mL) to form a transparent solution. Sodium acetate
promising activity and stability in the alkaline medium as (5.4 g) was added into the above solution. The mixed
oxygen anode and cathode [11]. solution was magnetically stirred until it became transpar-
Methanol is an economical and readily available raw ent. Reaction mixture was transferred in a Teflon-lined
material for fuel cell and transportation applications [12]. stainless-steel autoclave and hydrothermally treated at
Direct methanol fuel cell (DMFC) is considered as a promis- 453 K for 12 h. After the reaction, autoclave was allowed
ing candidate for future energy demand. Nevertheless, its to cool to room temperature. The products were filtered,
practical application is hindered by high over-potential rinsed with ethanol, and dried at 353 K for 24 h. The
associated with the direct electro-oxidation of methanol. obtained material was calcined using programmable Furness
A great deal of interest has recently been shown with (by maintaining the heating rate of 5 K min−1) at 773 K for
respect to the choice of electrode materials, cheaper than 0.5 h to obtain Co3O4. It may be noted that when material
platinum [13]. Cobalt-containing spinel oxides (MCo2O4, was calcined at 573 K a mixed phase consists of Co(OH)2 and
where M = Cu, Mn, Ni, Zn, Mg, etc.) have drawn considerable Co3O4 was obtained, therefore to obtain pure Co3O4,
attention due to their superior physicochemical properties material was calcined at 773 K.
and exhibited many technological applications, ranging
from catalysts and sensors to electrode materials and Synthesis of NiCo2O4
electrochemical devices [14]. NiCo2O4 materials have shown
excellent electrocatalytic activities for many electrode NiCo2O4 was prepared by following the reported procedure
reactions, for example: O2 [15] and Cl2 evolution [16] and [19]. In a particular synthesis, 2.37 g CoCl2
6H2O, 1.19 g
O2 reduction [17], as well its application as a negative NiCl2
6H2O, and 2.7 g urea were dissolved in 75 mL distilled
electrode for lithium-ion batteries [18,19]. Spinel-oxides water and stirred for about 10 min to obtain a transparent
are low cost, easily available and have outstanding corro- pink colored solution. The reaction mixture was then
sion stability in alkaline solutions [20]. Therefore, in this transferred into a Teflon-lined stainless steel autoclave,
study, we attempted to demonstrate the applicability of and hydrothermally treated at 393 K for 6 h. Autoclave was
NiCo2O4 as an electrode material towards methanol oxida- cooled to room temperature and the reaction mixture was
tion in the alkaline medium. The electrocatalytic activity of filtered, washed with distilled water and ethanol, followed
NiCo2O4 modified electrode was compared with the single by drying at 353 K for 24 h. Finally, the material was
component oxides such as NiO and Co3O4. Furthermore, calcined at 573 K for 4 h using programmable Furness by
cyclic voltammetry and chronoamperometry methods were maintaining the heating rate of 5 K min−1.
used to ascertain the mechanism of methanol oxidation.
Preparation of the working electrodes

Experimental Cyclic voltammetry (CV) and chronoamperometric studies

were performed using Potentiostat-Galvanostat BASi EPSI-
Materials 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
All chemicals were analytical grade and used without
diameter) as the working electrode, and Pt foil as the
further purification. NiNO3
6H2O, NiCl2
6H2O, CoCl2
6H2O,
counter electrode. Before modification of GCE, the polished
sodium acetate, and urea were obtained from Spectrochem
electrode was ultrasonicated in ethanol and deionized
Pvt. Ltd., India. Deionized water from Millipore Milli-Q
water for 5 min, respectively. 10 mL aliquot of NiCo2O4
system (resistivity 18.2 MΩ cm) was used in the electroche-
suspension (a homogenous sonicated solution of 10 mg of
mical studies.
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
Synthesis of NiO surface.

1.45 g NiNO3
6H2O was dissolved in distilled water (250 mL) Materials characterizations
and the solution was stirred for 15 min at room tempera-
ture. 0.6 g of urea was added to the above solution and X-ray diffraction (XRD) patterns were recorded in the
magnetically stirred at room temperature for 3 h. Then the 2θ range of 5–901 with a scan speed of 2°/min on a
reaction mixture was transferred to Teflon lined steel PANalytical X'PERT PRO diffractometer using Cu Kα radiation
autoclave and hydrothermally treated at 373 K for 10 h. (λ = 0.1542 nm, 40 kV, 20 mA). Scanning electron microscopy
The green precipitate of Ni(OH)2 was collected, washed (SEM) measurements were carried out on a JEOL JSM-
with distilled water and dried in an oven at 353 K for 24 h. 6610LV, to investigate the morphology. During the SEM
The obtained Ni(OH)2 was calcined using programmable investigation, energy-dispersive X-ray spectroscopy (EDS)
Furness (by maintaining the heating rate of 5 K min−1) at was utilized in the sample characterization, and the EDS
573 K for 4 h to form black powder NiO. 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 1049

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 when it was compared with the CV of NiCo2O4 modified
investigated using CV in 0.1 M NaOH solution. NiCo2O4 electrode in the absence of methanol (Fig. S4). Similar
modified electrode exhibits a pair of well-defined redox behavior was obtained for NiO modified electrode, but with
peaks (Fig. S3(a)) corresponding to the oxidation of Co(II) a low current response compared to NiCo2O4 modified
and the reduction of Ni(III) [25,26]. These anodic peaks can electrode, indicating that the presence of Nickel is required
be correlated with the oxidation of Co(II) to Co(III) to Co for methanol oxidation (Fig. S5). However, when the similar
(IV). The cathodic peaks correspond to the reduction of Co study was performed at Co3O4 modified electrode in the
(IV) to Co(III) to Co(II) and Ni(III) to Ni(II). It may be noted presence of 1 M methanol, it did not show an increment in
that the redox potential of Ni(II)/Ni(III) is very close to Co the oxidation current (Fig. S6), suggesting no electrocatalytic
(III)/Co(IV) [25,26]. NiO modified electrode exhibits a pair of activity for methanol oxidation. Based on these observations,
well-defined redox peaks corresponding to Ni(II)/Ni(III) one can easily conclude that among the three materials
redox couple (Fig. S3(a)) [27]. These peaks represent the investigated in this study, NiCo2O4 modified electrode exhib-
oxidation of the Ni(OH)2 to the nickel oxy-hydroxide ited the highest activity towards methanol oxidation. Fig. 3a
(NiOOH) in the anodic run and the reduction of the shows a comparison of the CVs obtained at NiCo2O4 and NiO
produced oxy-hydroxide to Ni(OH)2 in the cathodic half modified electrodes in the presence of 1 M methanol. Based
cycle, respectively [27]. The presence of cobalt in the on the CV, one can conclude that the current response at
NiCo2O4 structure increased the charge-acceptance of Ni NiCo2O4 modified is much higher than that of NiO modified
in the form of the Ni(II)/Ni(III), therefore, the redox peaks electrodes. Furthermore, NiCo2O4 modified electrode exhib-
shift to more negative potential values than NiO [28,29]. It ited a decrease in the over-potential compared to NiO
may be noted that the enclosed area of CV loop of the electrode. NiCo2O4 showed higher electrochemical activity,
NiCo2O4 is larger than the NiO; therefore, the current which are originated from the synergistic contributions from
densities of the NiCo2O4 are higher than those of the NiO, both nickel and cobalt ions, than those of the monometallic
implying its better electrochemical reactivity. CV of Co3O4 NiO and Co3O4. The addition of cobalt promotes a redox
in 0.1 M NaOH consists of two pairs of redox peaks (I/IV and processes to less positive potentials, which mean that cobalt
II/III), resulting from the reversible transition between acted as a chemical modifier and caused a structural change
Co3O4 and CoOOH (I/IV) and the transition between CoOOH or electronic effect [31,32]. Secondly, cobalt allows the
and CoO2 (II/III) (Fig. S3(b)) [30]. nickel to reach a higher oxidation state during the oxidation
This section describes the preliminary investigation of process and promotes the electron transfer for methanol
methanol oxidation at NiCo2O4, NiO, and Co3O4 modified oxidation [33,34].
electrodes in the presence of 1 M methanol. CV shows a This section describes the mechanistic investigation for
strong oxidation current in the presence of 1 M methanol 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 responsible for significantly high-current density of a2.
Based on the results obtained (Fig. 3b), one can conclude
500 a2 that the rate limiting step for the methanol oxidation
a1
a1 (methanol concentration40.4 M) at the NiCo2O4 modified
0
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
-500 negative sweep decreases (c). This observation demon-
0.0 0.5 1.0 0.0 0.5 1.0 0.0 0.5 1.0
Potential (V) strates that the methanol reacts with NiOOH formed
on the electrode surface. The amount of NiOOH formed on
Fig. 3 (a) CV of NiCo2O4 and NiO modified electrodes in the the electrode surface decreases due to its involvement in
presence of 1 M methanol in 0.1 M NaOH solution at a scan rate the chemical reaction with methanol, which causes the
of 50 mV s−1. (b) CV of NiCo2O4 modified electrode in 0.1 M decrease in the charge of Ni3+ (NiOOH) in the reverse sweep
NaOH solution at a scan rate of 50 mV s−1 in the presence of direction.
(i) 0.1 M, (ii) 0.4 M, and (iii) 1 M methanol. The effect of scan rate on the methanol oxidation
over NiCo2O4 modified electrode was investigated in the
modified electrode. The electrochemical behavior of presence of 0.03 M methanol using CV (Fig. 4). It was observed
NiCo2O4 modified electrode in the presence of 0.1 M metha- that the current ratio of peak Pa1 and Pa2 (Pa1:Pa2) increases
nol shows an increment in the anodic peak current for peak with the increase in the scan rate. At a scan rate of 200 mV
(a1) followed by the appearance of a new oxidation peak s−1, only peak (a1) was observed, while the peak (a2) had
(a2) at more positive potential and a peak current (c) during almost disappeared. On the other hand, only peak (a2) was
the reverse scan rate of potential (Fig. S7(a)), which is found in the voltammogram recorded at a slow scan rate
indicative of the methanol oxidation at NiCo2O4 modified (10 mV s−1). Therefore, it can be said that the reaction shown
electrode. The anodic peaks (a1) and (a2) demonstrate the in Eq. (3) is not so fast that it does not match with reaction
existence of two different crystallographic structures of Ni shown in Eq. (2). Therefore, the anodic current is mainly
(OH)2, (α-Ni(OH)2 and β-Ni(OH)2), which are responsible for contributed by reaction shown by Eq. (2). As a result, the peak
methanol oxidation (Eqs. (2) and (3)) [35,36]. NiOOH species a2 reduces with the increase of the scan rates and finally
are formed from α-Ni(OH)2 (anodic peak a1), which can be disappeared at a scan rate of 200 mV s−1.
formed even in the absence of methanol (Eq. (2)), further Double potential step chronoamperometry, as well as
chemical reduction of NiOOH with methanol takes place to other electrochemical methods, was employed for the
form β-Ni(OH)2 (Eq. (3)). Subsequently, β-Ni(OH)2) is con- investigation of the electrode processes at NiCo2O4 modified
verted to NiOOH at higher potentials, leading to the electrode. The double-step chronoamperograms for the
appearance of a new anodic peak (a2) (Eq. (4)). A cathodic NiCo2O4 modified electrode by setting the working elec-
peak (c), as a result of the oxy-hydroxide reduction, with trode potential at 700 mV (first step) and 350 mV (second
very low current value compared to anodic peak is also step) vs. Ag|AgCl|KCl (3 M) for different concentrations of
observed. The relative decrease of the cathodic peak height methanol has been shown (Fig. 5). It was found that the
in the presence of methanol is attributed to the partial 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)

300
0.35
-400 200 methanol and redox sites of NiCo2O4 can be evaluated by
0.30
100 chronoamperometry according to the method described in
0.6 0.7 0.8 0.9 1.0 0
2 4 6 8 10 12 the literature [37].
time (s ) time (s )
-800 IC =IL ¼ γ 1=2 ½π 1=2 erfðγ 1=2 Þ þ expð−γÞγ −1=2  ð5Þ
0 5 10 15 20
Time (s) where IC is the catalytic current of the NiCo2O4 in the
presence of methanol, IL is the limiting current in the
Fig. 5 Chronoamperograms obtained at the NiCo2O4 modified
absence of methanol and γ = kC0t (C0 is the bulk concentra-
electrode in the absence (a) and in the presence of (b) 0.03 M,
tion of methanol) is the argument of the error function.
and (c) 0.05 M of MeOH in 0.1 M NaOH solution. First and second
In cases, where γ exceed 2, the error function is almost
potential steps were 700 and 350 mV vs. Ag|AgCl|KCl (3 M),
equal to 1, and the above equation can be reduced to
respectively. Inset (A): dependence of charge (mC) vs. time, (a′)
and (c′) are derived from the data of chronoamperograms of IC =IL ¼ π 1=2 γ 1=2 ¼ π 1=2 ðkC0 tÞ1=2 ð6Þ
(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- where k, C0 and t are the catalytic rate constant (cm3
oamperograms of (a) and (c) in the main panel. Inset (C): mol−1 s−1), methanol concentration (mol cm−3), and time
dependence of current (mA) on time−1/2 is derived from the elapsed (s), respectively. From the slope of the IC/IL vs.
data of chronoamperogram of (a) in the main panel. 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
agreement with the current observed from CV. Further- in the absence and in the presence of 0.05 M methanol. The
more, the current increases as the methanol concentration mean value for k was found to be 5.5  103 cm3 mol−1 s−1.
increases. This result supports our conclusion about the Plotting of net current of NiCo2O4 in the absence of methanol
catalytic role of NiOOH in the methanol oxidation. The with respect to time−1/2, presented a linear dependence (see
forward and backward potential step chronoamperometry the inset C of Fig. 5), which shows that the process is domi-
1052 M.U. Anu Prathap, R. Srivastava

2500
1600 Acknowledgments

Current (μA)
1200
2000 Authors thank Department of Science and Technology, New
800 Delhi for financial assistance (DST Grant SB/S1/PC-91/
400 2012). AP is grateful to CSIR, New Delhi for SRF fellowship.
1500
We acknowledge Director, IIT Ropar for constant
Current (μA)

0
0.0 0.4 0.8 1.2 1.6 2.0 encouragements.
1000 Concentration (M)
0M
500
0.02 M Appendix A. Supporting information
0.05 M
0.1 M
0.4 M Supplementary data associated with this article can be
0 1M
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
-500
0.0 0.2 0.4 0.6 0.8 1.0
Potential (V)

Fig. 6 CV of NiCo2O4 modified electrode in the presence of References

different concentrations of methanol in 0.1 M NaOH solutions at
a scan rate of 50 mV s−1. Inset shows the calibration plot. [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
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[23] M.U. Anu Prathap, Balwinder Kaur, Rajendra Srivastava, Jour- [39] A. Nozad Golikand, S. Shahrokhian, M. Asgari, M. Ghannadi
nal of Colloid and Interface Science 370 (2012) 144–154. Maragheh, L. Irannejad, A. Khanchi, Journal of Power Sources
[24] D. Wang, Z. Zou, J. Ye, Chemical Physics Letters 373 (2003) 144 (2005) 21–27.
191–196.
[25] T.Y. Wei, C.H. Chen, H.C. Chien, S.Y. Lu, C.C. Hu, Advanced M.U. Anu Prathap received his Master in
Materials 22 (2010) 347–351. Technology in Polymer Science and Rubber
[26] Z. Fan, J. Chen, K. Cui, F. Sun, Y. Xu, Y. Kuang, Electrochimica Technology from Cochin University of
Acta 52 (2007) 2959–2965. Science and Technology, India. He is cur-
[27] S.B. Aoun, G.S. Bang, T. Koga, Y. Nonaka, T. Sotomura, rently a graduate student working towards
I. Taniguchi, Electrochemica Commun. 4 (2003) 317–320. PhD degree in Department of Chemistry
[28] M. Oshitani, Y. Sasaki, K. Takashima, Journal of Power Sources from Indian Institute of Technology Ropar,
12 (1984) 219–231. Punjab, India. His research interest includes
[29] M. Oshitani, T. Takayama, K. Takashima, S. Tsuji, Journal of the development of nanomaterials for elec-
Applied Electrochemistry 16 (1986) 403–412. trochemical biosensors and energy conver-
[30] Y. Ding, Y. Wang, L. Su, M. Bellagambaa, H. Zhang, Y. Lei, sion device applications.
Biosensors and Bioelectronics 26 (2010) 542–548.
[31] M. Vidotti, M.R. Silva, R.P. Salvador, S.I. Cordoba de Torresi,
Rajendra Srivastava is an Assistant Profes-
L.H. Dall' Antonia, Electrochimica Acta 53 (2008) 4030–4034.
sor of Chemistry at IIT Ropar. He obtained
[32] J.-W. Kim, S.-M. Park, Journal of Electrochemical Society 150
his doctoral degree from NCL Pune, India.
(2003) E560–E566.
He worked as a post-doctoral research
[33] R.D. Armstrong, E.A. Charles, Journal of Power Sources 25
fellow at KAIST, South Korea and as a JSPS
(1989) 89–97.
fellowship recipient at Hokkaido University,
[34] R.D. Armstrong, G.W.D. Briggs, E.A. Charles, Journal of
Japan. He has published more than 50
Applied Electrochemistry 18 (1988) 215–219.
research papers and has, to his credit,
[35] T. Subbaiah, S.C. Mallick, K.G. Mishra, K. Sanjay, R.P. Das,
seven international patents. His doctoral
Journal of Power Sources 112 (2002) 562–569.
work was adjudged the best thesis for the
[36] Q. Yi, J. Zhang, W. Huang, X. Liu, Catalysis Communications 8
year 2006 by Catalysis Society of India. His research interests are in
(2007) 1017–1022.
the areas of development of nanostructure materials and find their
[37] M.A. Abdel Rahim, H.B. Hassan, R.M. Abdel Hamid, Journal of
applications in catalysis (homogeneous and heterogeneous cataly-
Power Sources 154 (2006) 59–65.
sis/electrocatalysis) and bio-sensing.
[38] R. Ojani, J.B. Raoof, S. Fathi, Electrochimica Acta 54 (2009)
2190–2196.