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Synthesis and characterization of nickel oxide nanoparticle with wide band

gap energy prepared via thermochemical processing

Article  in  Journal of Nanoscience and Nanotechnology · March 2014

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Nanoscience and Nanotechnology: An International Journal

Universal Research Publications. All rights reserved

ISSN: 2278-1374
Original Article
Synthesis and characterization of nickel oxide nanoparticle with wide band gap
energy prepared via thermochemical processing
M. Mohammadijooa,b,*, Z. Naderi Khorshidia,b, S.K. Sadrnezhaadb and V. Mazinanic
a
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, T6G 2V4, Canada
b
Department of Materials Science and Engineering, Sharif University of Technology, P.O. Box 11365-9466, Tehran, Iran
c
Mining and Metallurgical Engineering Department, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran,
Iran
1 Corresponding author: Tel.:+1 780 8079376; fax: +1 780 4922881. E-mail address: mo1@ualberta.ca
(M. Mohammadijoo)
Received 19 February 2014; accepted 06 March2014
Abstract
In this research, nickel oxide (NiO) nanoparticles with the wide range of band gap energy were synthesized via facile and
low cost thermochemical process which is a potential route to make the large scale production feasible. Characterization of
nanoparticles was investigated by scanning electron microscopy, X-ray diffractometer, transmission electron microscopy,
thermogravimetric analysis, Brunauer- Emmett- Teller surface area analysis (BET), and uv-visible spectrophotometer. The
uv-visible spectrophotometry analyzing showed the strong absorption peak and nearly transparent nature of the particle at
visible region. The wide range of band gap energy with value of 3.85 to 3.45 eV for NiO nanoparticle was achieved by
increasing the processing temperature from room temperature (RT) to 75 oC which was surprisingly comparable to the
band gap energies reported by different researchers. The SEM micrographs of nanoparticles revealed that the particles had
wall shape and this shape changed from flake walls to sharp walls while thermochemical processing temperature increased.
© 2014 Universal Research Publications. All rights reserved
Keywords: Nickel oxide; Nanoparticle; Characterization; Thermochemical processing; Optical absorption

1. Introduction investigate on development of newer approach for

Nanostructured metal oxides have been extensively
explored for various fundamental scientific and
technological interests and to access new classes of
functional materials with unprecedented properties and
noteworthy applications. Nickel oxide has a wide range of
applications in the manufacturing of magnetic materials,
alkaline battery cathodes, dye-sensitized solar cells,
semiconductors, solid oxide fuel cells (SOFC), anti
ferromagnetic layers, p-type transparent conducting films,
electrochromic films, heterogeneous catalytic materials and
gas sensors [1-7]. Also, nanocrystalline NiO powder shows
superparamagnetism effect; then which can be used for
drug delivery and MRI agent [8]. Numerous routes like
thermal decomposition [9-11], carbonyl method, sol-gel
technique [12], microwave pyrolysis [13], solvothermal
[14], anodic arc plasma [15], Sonochemical [16],
precipitation-calcination [17] and microemulsion [18] have
previously been investigated for production of nickel oxide
nanoparticles. Many of the reported techniques are limited
to laboratory scale due to specific conditions required,
tedious procedure, complex apparatus, low-yield and high-
cost. From practical point of view, it is essential to further
manufacture of high-quality low-cost nanoparticles of
better optical properties. Traditional methods do not fully
satisfy our needs for mass scale production of NiO
nanoparticles. Thermochemical processing utilized in this
research is a two-stage deposition method consisting of a
nickel containing complex that decomposes to nickel oxide.
The complex can simply be produced by reaction of NiCl 2
anhydrous and NH3-H2O dissolved in water. This study
then focuses on morphology and optical absorption
properties of the nickel oxide nanoparticles and their
dependence on the processing temperature. The results
shows that by increasing the processing temperature, wall-
shape nickel oxide particles with narrow size distribution
and lower band gap energy achieved.
2. Materials and Method
The research has been focused on the preparation and
characterization of nickel oxide nanoparticles synthesized
by thermochemical methods. To synthesize nickel oxide
nanoparticles, 20 ml ammonia was gradually added
(approximately 30 min) to 2 g anhydrous NiCl2 powder
(Merk, 99.7%), under vigorous stirring (550-700 rpm) to
produce the solution containing Ni+2. Because of the

Nanoscience and Nanotechnology: An International Journal 2014; 4(1): 6-9

6
exothermic reaction of NiCl2 with ammonia, ammonia
should be slowly added to the precursor. The solution
temperature was set at RT, 33, 55 and 75 ˚C and the pH
was also set in the range of 7.5 to 9. Distilled water was
subsequently added as a precipitant agent while vigorous
stirring of solution continued until green precipitate
formed. The resulting precipitate was filtered and washed
twice with deionized water and ethanol. To produce black
NiO nanoparticles, green precipitates were dried at 105 ˚C
for 90 min in oven and then heated at 410 ˚C for 1 hr in a
tube furnace.
X-ray diffractometry (Siemens D-500, Germany),
transmission electron microscopy (Philips CM-200,
Netherlands), scanning electron microscopy (Hitachi S-
4160, Japan), BET surface area analysis (Micromeritics
Gemini, U.S.A.), thermogravimetric analysis and UV-
visible spectrophotometry (Perkin Elmer Lambda 25,
U.S.A.) were conducted to characterize the nanoparticles.
3. Results and discussion
Fig. 1 depicts the X-ray diffraction (Cu Kα radiation)
spectrum of the nanoparticle samples produced by
thermochemical method in various solution temperatures.
Fig. 1 (a and b) illustrates the XRD patterns of the dried
precipitates and calcined product at RT. No significant peak
is observed in the dried precipitate. This indicates that the
precipitate is an amorphous phase containing different
nickel salt or precipitation agent. When calcined at 410 ˚C,
cubic crystal of NiO forms. The experimental values
obtained for the lattice parameter, d, of the particles are
comparable with those given by ASTM (card no. 4-0835).
Application of the data obtained from the diffraction peaks
into the Scherrer formula, d=0.9λ/B(cosθ), gives the
average crystal size of the NiO nanoparticles at different
temperatures, ~13-15 nm. According to the picks illustrated
in Fig. 1 (c, d and e), the processing temperature had not
any effect on crystal structure of nanoparticles and it was
the same by increasing the processing temperature.
Figure 1. The diffractogram of nanoparticle produced by
thermochemical processing at (a) RT and dried at 105 ˚C
for 24 hrs, (b) RT and calcined at 410 ˚C for 1 hr, (c) 33 ˚C,
(d) 55 ˚C and (e) 75 ˚C
Nanoscience and Nanotechnology: An International Journal 2014; 4(1): 6-9
7
Figure 2. SEM micrograph of agglomerated
nanocrystalline NiO particles produced at (a) RT, (b) 33 ˚C,
(c) 55 ˚C and (d) 75 ˚C
Clustering of nanoparticles into walls with nano-size
thickness occurs during thermochemical processes. Fig. 2
illustrates the SEM micrograph of the NiO products
processed by thermochemical method at different
temperatures. Nanothickness flake-walls appear at the
lower temperatures (RT). By increasing the temperature,
the shape of flake-walls significantly changes towards
sharp-walls. It seems that the thermochemical processing
nature significantly affects the morphology and thickness of
the products. Fig. 2 (a and b) indicates that the flake-walls
prevail when processing occurs at RT and 33 ˚C. Flake
proportion reduces, however, while processing temperature
increases. At 55 and 75 ˚C, the particles accumulate into
sharp walls, observable in Fig. 2 (c and d). Partial
agglomeration of particles is observed at all temperatures.
Ultrasonic vibrator was used to disperse the wall-shape
agglomerated product of the thermochemical synthesis.
Fig. 3 indicates the TEM image of separate nanoparticles
produced at RT. To have a better estimation of the size
distribution of nanoparticles, agglomerated particles were
gently sonicated for 20 sec. The powder consists of
nanoparticles having average size of ~20 nm diameter. The
BET surface area of the ultrasonicated NiO particles at
different temperature is mentioned in table 1. By increasing
the processing temperature to 75 ˚C, the specific surface
area of nanoproducts is decreased. It could be explained in
term of increasing the growth rate of particles with
processing temperature which leads to the increase of
particle size and subsequently a decrease in specific surface
area of particles.
Figure 3. TEM image of NiO nanoparticle produced by
thermochemical processing at RT (agglomerated nano-
particles was dispersed under ultrasonication)
 A slight shift towards higher wavenumber is seen for the
absorption edges by increasing the processing temperature.
This shift indicates a decrease in the band gap, which can
be attributed to an increase in particle size. The value of the
absorption edge of NiO particles prepared at RT, 33, 55, 75
˚C was 307, 308, 322 and 341 nm respectively. According
to the data of the absorption spectra, the optical band gaps
(Eg) of NiO nanoparticles can be estimated by using the
following equation [19]:
(αhν)n = A(hν - Eg)
Where hν is photo energy, α is absorption coefficient, A is a
constant relative to the material and n is either 2 for direct
band gap material or 1/2 for an indirect band gap material.
Figure 4. TG and DTG curves of precipitates produced at According to the equation, the optical band gap for the
RT absorption peak can be obtained by extrapolating the linear
TG and DTG curves of the nanoparticles produced by the portion of the (αhν)n – hν curve to zero. The corresponding
thermochemical process at RT are shown in Fig. 4. The TG band gap energies of produced nanoparticles at different
curve shows that the weight loss occurs in three stages. At temperature are reported in table 1 which are comparable to
the first stage, a weight loss of ~8% occurs in the the value reported by Boschloo [20], Anandan [14], Davar
temperature range 40 to 230 ˚C. The curves may be [21] and Wang [22]. The increasing trends of the band gap
evidence of physisorbed water, crystalline water and energy upon the decreasing particles size is likely due to the
humidity in pores liberated over this temperature range. At defects or vacancies present in the intergranular regions
the second stage, due to the Ni(OH)2 decomposition from generating new energy level to reduce the band gap energy
230 to 385 ˚C, a weight loss of ~10.6% occurs. Eventually, [23]. No linear relation was found for n = 1/2, suggesting
the third stage is related to the production of NiO that may that the as-synthesized NiO nanostructures are
take place above 385 ˚C. semiconducting with direct transition at this energy [24].
Fig. 5 depicts the UV-visible absorption spectrum of the 4. Conclusion
NiO particles obtained at different temperatures and Nickel oxide nanoparticle was synthesized by chemical
dispersed in ethanol. The optical band gap energy of NiO treatment of an aqueous nickel containing solution.
nanoparticle produced at RT, 33, 55 and 75 ˚C is listed in Depending on the temperature used, the clusters of nickel
table 1. oxide particle consist of a proportionate amount of both
nano sharp-walls and nano flake-walls. The SEM
micrographs showed that by increasing the processing
temperature from room temperature to 75 ˚C, the shape of
clusters was changed from flake wall to sharp wall. The
optical absorption band gap of nickel oxide nanoparticles
was decreased by the processing temperature which is
comparable with the band gap energy of NiO reported
previously by researchers. Also, a wide range of band gap
was achieved by varying the processing temperature up to
75 oC.
Acknowledgements
The authors appreciate financial support of INSF and
technological assistance of the thermal analysis laboratory
of IPPI and materials characterization laboratory of Sharif
University of Technology.
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