Solid State Sciences 8 (2006) 425–430

www.elsevier.com/locate/ssscie

Magnetic and electrochemical properties of nickel oxide nanoparticles

obtained by the reverse-micellar route
Tokeer Ahmad a , Kandalam V. Ramanujachary b , Samuel E. Lofland b , Ashok K. Ganguli a,∗
a Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India
b Department of Chemistry and Physics, Center for Materials Research and Education, Rowan University, 201 Mullica Hill Road, Glassboro, NJ 08028, USA

Received 5 July 2005; received in revised form 27 December 2005; accepted 30 December 2005
Available online 15 February 2006

Abstract
Homogeneous nanoparticles of nickel oxide (NiO) of 25 nm size with narrow size distribution have been synthesized by the reverse-micellar
route using CTAB (cetyltrimethyl ammonium bromide) as the surfactant. FTIR studies show a broad absorption around 405–415 cm−1 and a weak
absorption around 82 cm−1 corresponding to a surface-active mode, which is indicative of the nanocrystalline nature of the oxide. Magnetization
studies show nearly temperature independent paramagnetism with high magnetic moment compared to bulk NiO. Cyclic voltammetric (CV)
studies show well-resolved anodic peak (Ni+2 → Ni+3 + e− ) at 0.45 V at a scan rate of 1 mV/s, which shifts to 0.47 V at the scan rate of
100 mV/s. The cathodic peak (Ni+3 + e− → Ni+2 ) is also observed at 0.34 V, which remains at the same position irrespective of the sweep rate.
The quasireversible nature of the voltammograms suggests the usefulness of these materials for ultracapacitor applications.
 2006 Elsevier SAS. All rights reserved.

Keywords: Nickel oxide; Reverse micelle; Nanomaterials; Transmission electron microscopy

1. Introduction
NiO is an important transition metal oxide which has been
of interest due to its interesting magnetic properties [1–5]. Bulk
crystals of NiO possess a rhombohedral structure and exhibit
antiferromagnetic behaviour below 523 K (TN ) whereas it has
a cubic (NaCl-type) structure and is paramagnetic above that
temperature [1]. It has been earlier suggested [2–5] that fine
particles of NiO should exhibit weak ferromagnetism or super-
paramagnetism.
Apart from the studies of magnetic properties of oxide
nanoparticles, there has been considerable interest in the elec-
trochemistry of nanostructured metal oxide films prepared from
the colloidal solutions as the nanostructured electrodes have
several advantages over the conventional electrodes in many
applications such as photochemical solar cells [6] and elec-
trochromic windows [7–9]. Electrochemical capacitors (EC)
are used along with batteries or fuel cells in electric vehicles
* Corresponding author. Tel.: +91 11 26591511; fax: +91 11 26854715.
E-mail address: ashok@chemistry.iitd.ernet.in (A.K. Ganguli).
1293-2558/$ – see front matter  2006 Elsevier SAS. All rights reserved.
doi:10.1016/j.solidstatesciences.2005.12.005
and other electronic devices for energy storage and conversion,
especially if high power density is desirable. These capacitors
also have flexible charging rates and longer cycling life as com-
pared to normal batteries. Nanostructured nickel oxide has been
of interest over the last few years due to its interesting elec-
trochemical properties [10–13]. Apart from the electrochemical
applications as above, NiO has applications in several other ar-
eas [14–20].
The large number of applications as mentioned above for
nanostructured NiO has led to several attempts to prepare nano-
sized NiO in controlled sizes and shapes and to have a firm han-
dle on the size-property relations. Most of the synthetic studies
of nanosized NiO, however, have been carried by the Sol–Gel
method [5,10] or by the coprecipitation route [7]. In such meth-
ods it is very difficult to have uniformity and monodispersity.
An important route to synthesize nanoparticles is the mi-
croemulsion method [21,22] in which size-controlled reverse-
micelles may be used as nanoreactors. The reverse micellar
route is of special importance since it provides homogeneous
and mono-disperse nanoparticles. The reverse-micelles ob-
tained at a particular ratio of the aqueous phase to the surfactant
leads to uniform-sized nanoreactors and have an aqueous core
426 T. Ahmad et al. / Solid State Sciences 8 (2006) 425–430
(in the nanometer range) in which precipitation of the inorganic
compound or the initial precursor is carried out. The material
obtained is homogeneous since the desired stoichiometry is al-
ways maintained. It is possible to control not only the size but
also the morphology of the nanoparticles by proper choice of
the composition of the micro-emulsion system. Previously there
have been reports on the synthesis of metal oxides through the
reverse-micellar route of oxides [23–28]. There has been only
one report [29] on the reverse-micellar (water-in-oil microemul-
sion) synthesis of NiO nanoparticles using Triton X-100 as the
surfactant. However, no discussion of size distribution or prop-
erties have been reported.
In this paper we report the synthesis of NiO nanoparti-
cles using a reverse micellar route using a cationic surfactant.
We have extensively characterized the nickel oxide nanopar-
ticles by X-ray diffraction, transmission electron microscopy,
electron diffraction, dynamic light scattering studies, Fourier
transform infrared spectroscopy, X-ray photoelectron spec-
troscopy, field-dependent magnetization and electrochemical
studies. Our studies lay down a convenient procedure using
reverse-micelles for the synthesis of homogenous nanoparticles
of NiO (∼25 nm) with a narrow size distribution which show
interesting magnetic and electrochemical characteristics.
2. Experimental
The synthesis of nickel oxide is carried out in two steps.
First, we synthesized the nanoparticles of nickel oxalate di-
hydrate from two micro-emulsions (I and II) as described be-
low. In the second step, the nickel oxalate dihydrate particles
were subjected to a careful thermal decomposition to yield
nanoparticulate nickel oxide. Micro-emulsion I is composed of
cetyltrimethylammonium bromide (CTAB) as the surfactant, n-
butanol as the co-surfactant, isooctane as the hydrocarbon phase
and 0.1 M nickel nitrate solution as the aqueous phase. Mi-
croemulsion II composed of the same constituents as above
except for having 0.1 M ammonium oxalate instead of nickel
nitrate as the aqueous phase. The weight fractions of various
constituents in these micro-emulsions are as follows: 16.76% of
CTAB, 13.90% of n-butanol, 59.29% of isooctane and 10.05%
of the aqueous phase. These two micro-emulsions were mixed
slowly and stirred overnight on a magnetic stirrer, and the re-
sulting precipitate was separated from the apolar solvent and
surfactant by centrifuging and washing it with 1 : 1 mixture of
methanol and chloroform. The precipitate was dried in an oven
at 120 ◦ C for 1 h. The precursor on heating in air at 450 ◦ C for
6 h leads to the formation of monophasic NiO.
X-ray diffraction (XRD) studies were carried out on a
Bruker D8 advance X-ray diffractometer using Ni-filtered Cu-
Kα radiation. Normal scans were recorded with a step of
0.02 deg and a residence time of 1 sec. The Kα2 -reflections
were removed by a stripping procedure to obtain accurate lat-
tice constants and grain sizes. For a more detailed X-ray study
(for grain size) slow scans with step size of 0.002◦ in 2θ and
a step time of 2 sec were employed. To obtain the grain size
from X-ray line broadening, we applied Scherrer’s formula
(t = 0.9λ/B cos θ ), where t is the diameter of the grain, λ is the


wavelength (for Cu-Kα, λ = 1.5418 Å) and B = BM 2 − B2
S
(BM is the full width at half maximum of the sample and BS is
that of a standard sample of quartz (grain size of around 2 µm).
The grain size analyses based on two different reflections were
identical. The cell parameters were determined using a least-
squares fitting procedure on all the observed reflections using
quartz as an external standard.
Thermogravimetric (TGA) and Differential thermal analy-
sis (DTA) were carried out using Perkin–Elmer TGA and DTA
system on well ground samples in flowing nitrogen atmosphere
with a heating rate of 5 ◦ C/min. On the basis of the TGA/DTA
studies, we calcined the precursor (nickel oxalate dihydrate) ob-
tained by the reverse micellar route at 450 ◦ C for 6 h to effect
the complete conversion to nickel oxide nanoparticles.
Dynamic light-scattering experiments were performed on a
particle-size analyzer, model nano ZS90 (Malvern instruments,
UK). A He–Ne laser with a power of 4 mW was used as a light
source. All the measurements were carried at a scattering an-
gle of 90◦ and a temperature of 25 ◦ C, which was controlled by
means of a thermostat. A dilute sample was prepared by dis-
persing the powder in water followed by ultrasonic treatment
for 10 minutes.
Transmission electron microscopic (TEM) studies were car-
ried out using a JEOL JEM 200CX electron microscope oper-
ated at 200 kV. TEM specimens were prepared by dispersing the
powder in acetone by ultrasonic treatment. A few drops were
poured onto a porous carbon film supported on a copper grid,
and was then dried in air. An IR spectrum of the nanostructured
NiO powders (using KBr disks) was recorded in the transmitted
geometry in the far IR region (50–500 cm−1 ) using a Nicolet
Protege 460 FTIR spectrometer.
X-ray photoelectron spectroscopic (XPS) measurements
were performed on a Perkin–Elmer (model 1257) X-ray Pho-
toelectron spectrometer operating at a base pressure of 6 ×
10−10 torr. From the dual anode X-ray source Mg-Kα
(1253.6 eV) line was used. The spectra of the samples were
recorded before and after sputtering at the top surface. Argon
ion bombardment was done by a differentially pumped ion gun.
The sputtering of the sample was carried out by a 3 keV ar-
gon beam, at a pressure of 10−8 torr for 2 minutes. The binding
energy (BE) was calibrated with respect to the peak position
of the C (1s) core level. The XPS wide scan was acquired us-
ing a 100 eV pass energy at a step of 1.0 eV and XPS C (1s)
core level spectra was acquired at 0.05 eV step with a pass en-
ergy of 40 eV. X-ray photoelectron spectroscopic (XPS) spectra
of the Ni region show the peaks corresponding to the Ni 2p3/2
and Ni 2p1/2 (as in pure NiO) suggesting the Ni2+ state in the
nanoparticles studies.
Temperature and field dependent magnetization measure-
ments were carried out at temperatures ranging from 5 to 300 K,
and in applied fields of up to 10 kOe with a Quantum Design
Physical Properties Measurement System.
Electrochemical cyclic voltammetric study was performed
with a computer controlled Potentiostat/Galvanostat (Autostat
PGSTAT 100 with GPES software) using a three-electrode as-
sembly in 6 M KOH. The working electrode was fabricated by
mixing 75% NiO with 20% graphite and 5% ethyl cellulose
 T. Ahmad et al. / Solid State Sciences 8 (2006) 425–430
binder, this mixture was then pasted onto a titanium mesh with
the help of tetrahydrofuran as the solvent. The electrode was
pressed at room temperature at a pressure of 200 psi and dried at
70 ◦ C to remove the adsorbed solvent. Blank experiments were
carried out with graphite binder pasted on similar Ti mesh to
eliminate the possibility of voltammetric signals arising from
impurities or Ti mesh. Platinum foil was used as the counter
electrode and Hg/HgO was used as the reference electrode.
3. Results and discussion
We could obtain pure NiO after decomposing the nickel
oxalate dihydrate precursor at low temperature (450 ◦ C). The
powder obtained was green in colour (as it should be if Ni is
in the divalent state). The sample was kept in an evacuated and
sealed container as expose to air over a long period slowly and
turns the colour dark indicating the oxidation of Ni2+ to Ni3+ .
The presence of Ni2+ was also confirmed by XPS studies (see
Section 2). The powder X-ray diffraction pattern of the nickel
oxide nanoparticles (Fig. 1) could be satisfactorily indexed on
the basis of a cubic cell with the refined lattice parameter of
a = 4.1743(2) Å. The grain size was evaluated from X-ray line
broadening (using Scherrer’s equation) and was found to be
30 nm. The grain size obtained from line broadening studies is
in close agreement with the transmission electron microscopic
(TEM) studies which show grains of 25 nm (Fig. 2(a)) and are
nearly spherical. Electron diffraction studies (Fig. 2(b)) confirm
the nanocrystalline nature of the nickel oxide particles. The ED
pattern exactly matches with the reflections corresponding to
Fig. 1. Powder X-ray diffraction pattern of NiO nanoparticles in the 2-theta range of 30–80 degrees. Inset shows XRD with larger 2-theta range (10–70 degrees).
427
cubic NiO. The particle size distribution of NiO particles ob-
tained from dynamic light scattering studies is shown in Fig. 3.
The average size obtained by the size distribution plot was
∼30 nm which supports the TEM result. The size distribution
plot also suggests a uniform size distribution.
Fig. 4(a) shows the FTIR study of nanosized nickel oxide
in the far IR range between 50–500 cm−1 . The spectrum ex-
hibits a broad absorption maximum located in the range of 405–
415 cm−1 . The shape of the peak is suggestive of nanocrys-
talline NiO. Note that bulk NiO shows an absorption in the
range of 390 to 405 cm−1 [30]. The spectrum of nanostruc-
tured NiO has also been recorded in the low frequency region
of 50–100 cm−1 . A magnified view of the spectra in this region
is shown in Fig. 4(b), which clearly reveals the presence of a
weak absorption centered at 82 cm−1 . The occurrence of this
low frequency absorption has been identified as due to a sur-
face induced acoustic mode which should not be IR active for
bulk NiO [31,32]. In the nanosized NiO there will be disruption
of long range periodicity (translational symmetry is affected),
which may result in the low frequency acoustic modes in the
far IR region.
We have studied the magnetization behavior of nanocrys-
talline NiO as function of temperature. These studies (Fig. 5(a))
show that the magnetization remains nearly temperature-inde-
pendent in the range 30–300 K. We also note a broad minimum
in the magnetization centered around 100 K. The high field
magnetic moment (Fig. 5(b)) values of the nanoparticles are
much larger (nearly twice as much) than that of bulk nickel
oxide. Nevertheless, the observed magnetization values are con-
428 T. Ahmad et al. / Solid State Sciences 8 (2006) 425–430

(a)

(a)

(b)

Fig. 2. (a) TEM and (b) Electron diffraction micrograph of NiO nanoparticles. (b)

Fig. 4. FTIR spectrum of nanostructured NiO (a) in the frequency range

50–500 cm−1 , (b) magnified view in the frequency range 50–100 cm−1 .

Fig. 3. Size distribution plot obtained by the dynamic light scattering studies
for the nanoparticles of nickel oxide.

sistent with similar measurements on nanoparticulate NiO [5].

The unusually large moment is attributed to both the uncompen-
sated surface spins and re-orientation of magnetic sublattices
due to finite-size effects. We also studied the variation of the
magnetization with magnetic field at 10 and 300 K (Fig. 6).
The variation in magnetization at 300 K is slightly non-linear
as compared to that at 10 K. The higher values of magnetiza-
tion at 300 K (Fig. 6(a)) compared to those at 10 K (Fig. 6(b))
suggest the presence of weak antiferromagnetic interactions.
(a)
Fig. 5. (a) Temperature dependence of the magnetization of NiO nanoparticles
at 5 kOe and (b) the plot of magnetic moment as a function of magnetic field.
Cyclic voltammograms at different sweep rates (1, 5, 10, 20,
50, 100) in 6 M KOH reveal interesting electrochemical be-
haviour in the voltage range 0.2–0.5 V. For example, Fig. 7(a)
 T. Ahmad et al. / Solid State Sciences 8 (2006) 425–430 429

(a)
(b)

Fig. 5. Continued.

(a) (b)

(b)

Fig. 6. Magnetization (M) versus magnetic field (H) plot at (a) 300 K and (b)
10 K.

shows cyclic voltammogram (CV) of nickel oxide (NiO), where

a well-resolved anodic peak (Ni+2 → Ni+3 + e− ) at 0.45 V is
(c)

distinct at the scan rate of 1 mV/s, although there is a minor
shift to 0.47 V when the scan rate is 100 mV/s. Cathodic peak
(Ni+3 +e− → Ni+2 ) is observed at 0.34 V, which remains at the
same position irrespective of the sweep rate. This along with
the peak width suggests that the nature of voltammograms is
quasireversible. The interesting dependence of the anodic peak
Fig. 7. Cyclic voltammograms of nanostructured NiO (a) at different scan rates,
(b) at 1 mV/s and 100 mV/s and (c) overlaid cyclic voltammograms of first five
cycles at the scan rate of 100 mV/s.
current on scan rate could be attributed to facile oxidation in
alkaline medium causing significant change of resistance since
Ni(III) is more conducting.
430 T. Ahmad et al. / Solid State Sciences 8 (2006) 425–430
In order to understand the scan rate dependence of these
voltammograms, a superimposed voltammogram at 1 and
10 mV/s scan rates is shown in Fig. 7(b). It is interesting to
see that the oxidation and reduction processes are symmetric
at a low scan rate of 1 mV/s while the oxidation processes be-
come very predominant over reduction when the scan rate is
100 mV/s. Faster scan rate corresponds to lower time scales
and this indirectly reflects the enhanced stability of Ni(III) at
this pH. The shift in peak potential is in good agreement with
the quasireversible nature of the voltammograms. The shape at
higher scan rates also indicates the presence of adsorption in-
duced capacitance, a feature which is critical for supercapacitor
applications. The specific capacitance calculated on the basis of
this plot is about 210 F/g and interestingly this charge storage
ability is invariant with respect to cycling as demonstrated in
Fig. 7(c), where voltammograms corresponding to the first five
cycles are presented at a fixed scan rate of 100 mV/s. These
results suggest the reversible nature of the surface redox reac-
tions.
4. Conclusion
Nearly spherical nanoparticles (25 nm) of nickel oxide crys-
tallizing in the cubic structure were synthesized using the
reverse micellar route. The methodology results in uniform
nanoparticles with a narrow size distribution as observed by
TEM and dynamic light scattering studies. FTIR studies give
the broad absorption maxima in the frequency range 405–
415 cm−1 and also a weak absorption at 82 cm−1 suggestive of
nanocrystalline particles. Nearly temperature independent mag-
netism was observed in the range of 25 to 300 K with twice as
large moments compared to bulk NiO, implying considerable
amount of uncompensated spins and/or reordering of magnetic
sublattices through finite size effects. Electrochemical studies
suggest the redox nature of this material with a strong pseudo-
capacitance contribution which enables its application potential
for ultracapacitors.
Acknowledgements
AKG thanks the Department of Science & Technology,
Govt. of India for financial support and also Dr. K. Vijayamo-
hanan and M. Dandekkar of NCL, Pune, India for help in carry-
ing out the voltammetric experiments. The authors thank NPL
Delhi for the TEM micrographs. TA thanks CSIR, Govt. of In-
dia for a fellowship.
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