J Mater Sci: Mater Electron (2012) 23:728–732

DOI 10.1007/s10854-011-0479-6

Synthesis and characterization of NiO nanoparticles by sol–gel

method
M. Alagiri • S. Ponnusamy • C. Muthamizhchelvan

Received: 3 May 2011 / Accepted: 26 July 2011 / Published online: 11 August 2011
Ó Springer Science+Business Media, LLC 2011

Abstract Nickel oxide nanoparticles have been synthe- that differ considerably from those of the corresponding
sized in the presence of agarose polysaccharide by sol–gel bulk magnets, including modifications of the intrinsic
method. The structure, morphology, optical and magnetic properties, superparamagnetism, enhanced coercivity and
properties of the product was examined by X-ray diffrac- shifts of the hysteresis loops or the absence of magnetic
tion, transmission electron microscopy, UV–visible spec- saturation at high fields [2]. Recently, nickel oxide (NiO)
trophotometer and superconducting quantum interference nanoparticles have been extensively studied due to its
device magnetometer. The result of thermogravimetric mechanical, electronic, magnetic and optical properties
analysis of the precursor product showed that the proper [3–6]. NiO nanoparticles were widely used in different
calcination temperature was 400 °C. X-ray diffraction fields, such as catalysis [7], electrochromic films [8–10]
result revealed that the obtained product was nickel oxide and fuel cell electrodes [11, 12]. Bulk NiO showed anti-
with face-centered cubic structure. TEM image demon- ferromagnetic character below the Neel temperature of
strated that the nickel oxide nanoparticles have spherical 523 K. The magnetic properties of NiO are modified by
shape with size around 3 nm. Analysis of FTIR spectra reduction of particle size. It was found that the antiferro-
confirmed the composition of product. The optical absorp- magnetic character of NiO becomes superparamagnetic
tion band gap of the NiO nanoparticles was estimated to be (300 K) as the particle size reaches about 100 nm [13].
3.51 eV. Magnetic measurement showed that the nickel Various approaches have been developed to prepare NiO
oxide nanoparticles exhibit superparamagnetic behavior at nanoparticles, including electrospinning technique [14],
300 K. Moreover, the nanoparticles show ferromagnetic microemulsion technique [15], organic solvent method
interactions at 4.2 K owing to the existence of uncompen- [16], solvothermal process [17] and sol–gel method [18].
sated moments on the surface of the nanoparticles. Yang et al. [18] and Li et al. [19] prepared NiO nano-
particles by sol–gel method in the presence of citric acid
and malic acid, respectively without any surfactant and
1 Introduction reducing agent. In the present work, NiO nanoparticles
were synthesized through a simple sol–gel route in the
Nano materials have received much attention over the past presence of agarose without any surfactant and reducing
decades because of their excellent electronic, optical, agent. Agarose is an excellent gel-forming polysaccharide
magnetic, chemical and thermal properties [1]. In particu- produced by red seaweeds with an average molecular
lar, magnetic nanoparticles often exhibit novel properties weight of 120,000 Da, which consisting of 1,3-L-D-galac-
topyranose and 1,4-linked 3,6-anhydro-K-L-galactose units
[20, 21]. The molecular structure of agarose polysaccharide
[21] is illustrated in Fig. 1. The synthesis method presented
M. Alagiri  S. Ponnusamy  C. Muthamizhchelvan (&) in this study is versatile, low cost, environment safe and
Department of Physics, Center for Material Science and Nano
could be extended to synthesize other magnetic metal
Devices, SRM University, Kattankulathur, Kancheepuram,
Chennai, Tamil Nadu 603203, India oxides. The synthesized NiO nanoparticles have been
e-mail: [email protected] investigated by various characterization techniques.

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Fig. 1 Structure of agarose

2 Experimental

The materials used in this study were Nickel (II) nitrate Fig. 2 TG curve of the precursor
hexahydrate (AR grade) and agarose polysaccharide (MB
grade). These materials were used as such without any weight loss occurs between 85 and 215 °C region, which is
further purification. Agarose powder (2 g) was added ascribed to the evaporation of the absorbed water and the
gradually to a beaker containing distilled water of 100 mL decomposition of agarose polysaccharide. The second
with vigorous stirring at 50 °C; after 20–30 min the solu- weight loss occurs between 216 and 396 °C region, which
tion became clear. Then 1 wt% of Ni(NO3)26H2O aqueous can be attributed to the conversion of Ni(OH)2 into NiO
solution was added with agarose gel with vigorous stirring (Ni(OH)2 ? NiO ? H2O). Above 400 °C, the TG curve
at 80 °C until a homogeneous gel was obtained. The gel become flat; obviously there is no change in the weight of
was heated at 100 °C for 4 h; a dried precursor was the precursor on the TG curve. It leads to choose the cal-
obtained. The precursor was calcined at 400 °C for 3 h to cine temperature.
obtain NiO nanopowder. The phase composition, purity and structure of the
The X-ray powder diffraction patterns of the samples products were examined by XRD. Figure 3a depicts the
were carried out with a PANalytical (X’pert PRO) X-ray XRD pattern of precursor sample. No diffraction peaks
diffractrometer using CuKa1 radiation (k = 1.5406 Å), the were detected, which indicates that the structure of the
samples were scanned from 20° to 85° (2h) with a scanning precursor sample is amorphous. This is in good agreement
rate of 1° min-1. TG curve was obtained under flowing air with the literature [19]. Figure 3b displays the XRD pattern
on a SDT Q600 V8.3 Build 101 thermal analysis device of NiO nanoparticles calcined at 400 °C. All of the peaks
with a temperature-increasing rate 10 °C/min in air. Raman match well with Bragg reflections of the standard face-
spectrum was recorded using a Renishaw InVia Laser centered cubic structure [International Centre for Diffrac-
Raman microscope with a He–Ne laser. The excitation tion Data: 04-0835, Space group: Fm3m (225)], the
wavelength is 633 nm and output power is 18 mW. TEM
and HRTEM images were recorded on a JEOl-2010 at an
accelerating voltage of 200 kV. FTIR spectra were recor-
ded from 450 to 4,000 cm-1 with a Perkin Elmer spec-
trometer using KBr pellet technique. Optical properties
were measured using Perkin Elmer lambda 5 UV–visible
spectrophotometer. Magnetization measurements were
carried out using a SQUID Magnetometer, Quantum
Design, MPMS XL (evercool).

3 Results and discussion

The thermogravimetric analysis is used to study the ther-

mal characteristics of the product. The typical TG curve of
the precursor product is shown in Fig. 2. It can be seen
clearly that the weight loss occurs in two temperature Fig. 3 XRD pattern of a precursor, b NiO nanoparticles calcined at
regions: (1) 85–215 °C and (2) 216–396 °C. The first 400 °C and c NiO nanoparticles calcined at 500 °C

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Fig. 4 Raman spectrum of NiO nanoparticles calcined at 400 °C

Fig. 6 FTIR spectrum of a precursor and b NiO nanoparticles

calcined at 400 °C
diffraction peaks at 37.28°, 43.29°, 62.91°, 75.44° and
79.39° can be indexed as (111), (200), (220), (311), and
(222) crystal planes, respectively. Figure 3c depicts the In order to reveal the morphology and size of the syn-
XRD pattern of NiO nanoparticles calcined at 500 °C. The thesized products, a typical TEM and HRTEM images have
breadth of the NiO peaks decreases with an increase in the been recorded, as shown in Fig. 5a–c. Figure 5a shows the
temperature from 400 to 500 °C, because of crystallite TEM image of NiO nanoparticles calcined at 400 °C. It can
growth. The average crystallite size is measured by X-ray be clearly observed that the synthesized product consisted
diffraction line broadening using the Debye–Scherrer of spherical shape with size around 3 nm. The lattice
formula. fringes can be clearly seen from the HRTEM image
(Fig. 5b), in which the interplanar distance is determined to
Kk
D¼ ð1Þ be about 0.24 nm, which is consistent with the d spacing of
b cos h
(111) of fcc NiO. On increasing the calcination temperature
In Eq. 1 D represents the average crystallite size, to 500 °C, the growth and agglomeration of nanoparticles
K = 0.89 is the Scherrer constant, k = 1.5406 Å is the occur (Fig. 5c). The size of the NiO nanoparticles calcined
wavelength of the X-ray (Cu Ka1 radiation), h is the at 500 °C is around 25 nm. Finally, the particle sizes
diffraction angle of the peak and b represents the full width obtained from TEM is well matched with those measured
at half maximum of the peaks. The average crystallite size from the XRD peak broadenings.
of NiO products calcined at 400 and 500 °C are found to be Figure 6a, b displays the FTIR spectra of precursor and
3 and 25 nm, respectively. Figure 4 depicts the Raman NiO nanoparticles calcined at 400 °C, respectively. Fig-
spectrum of NiO nanoparticles. It can be clearly observed ure 6a shows that the broad absorptions bands at 3,430 and
that the Raman peak at 518 cm-1 is assigned to Ni–O 1,630 cm-1 are assigned to O–H stretching and bending
stretching mode, which is in good agreement with the modes of water, respectively [23]. The wide absorption
literature value [22]. band around 1,384 cm-1 can be ascribed to CO2 3 ions

Fig. 5 a TEM image and b HRTEM image of NiO nanoparticles calcined at 400 °C and c TEM image of NiO nanoparticles calcined at 500 °C

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Fig. 7 a UV–visible spectrum

and b band gap plot [hm vs.
(ahm)2] of NiO nanoparticles
calcined at 400 °C

Fig. 8 a Zero-field cooled and

field-cooled curves and
b hysteresis loops of NiO
nanoparticles calcined at 400 °C

[24], the peak at 1,114 cm-1 corresponds to stretching and product has an Eg lower than the bulk one. This effect is
bending vibrations of the intercalated C–O species [24] and likely due to the chemical defects or vacancies present in
the bands at 2,946 and 2,869 cm-1 can be assigned to CH2 the intergranular regions generating new energy level to
vibration [25]. The precursor peaks were disappeared after reduce the band gap energy [25].
400 °C, as shown in Fig. 6b. But a new peak is observed at The magnetic properties of the NiO nanoparticles cal-
475 cm-1, which correspond to Ni–O nanoparticles cined at 400 °C was accessed by recording both the tem-
stretching mode [25]. perature-dependence magnetization (M-T) and hysteresis
UV–visible absorption spectrum of the NiO nanoparti- (M-H) loops. The Zero-field cooling (ZFC) and Field
cles calcined at 400 °C is shown in Fig. 7a. A strong cooling (FC) curves are shown in Fig. 8a. For the ZFC
absorption in the UV region is observed at wavelength measurement, the sample was cooled to 4.2 K in the
about 353 nm. The band gap (Eg) plot of NiO nanoparticle absence of an external magnetic field. A field of 50 Oe was
is shown in Fig. 7b. The Eg of NiO nanoparticles is found then applied and the magnetization was measured with
to be 3.51 eV, which is close to the value (3.55 eV) increasing temperature. For the FC measurement, the
reported by Boschloo and Hagfeldt [26]. First principle sample was cooled to 4.2 K in the presence of a field of 50
electronic structure calculations including on site Coulomb Oe and then the magnetization was measured with
interaction predicts that the top of the valence band consists increasing temperature in the same field. The ZFC curve
of the oxygen 2p band and the bottom of the conduction exhibits a maximum magnetization at a temperature
band is mainly derived from Ni 3d states. The energy band defined as the blocking temperature (TB). The TB is about
structure suggests that the absorption peak arises from 2p 20 K for NiO nanoparticles, which is the transformation
states of oxygen to 3d states of Ni [13]. Compared with temperature from ferromagnetic to superparamagnetic
bulk NiO (4.0 eV), the NiO nanoparticles exhibit decrease state. Figure 8b displays the hysteresis loops of NiO
in Eg. It is well known that semiconductors with nanoscale nanoparticles. It shows a superparamagnetic behavior at
size show a blue shift in their spectra due to the quantum room temperature and ferromagnetic behavior at 4.2 K.
confinement effects [25]. However, the as-synthesized The ferromagnetic behavior arises from the interaction

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