J Clust Sci (2013) 24:289–297
DOI 10.1007/s10876-012-0521-8
ORIGINAL PAPER
Synthesis and Characterization of Nickel Oxide
Nanoparticles from Ni(salen) as Precursor
Afsaneh Khansari • Morteza Enhessari
Masoud Salavati-Niasari
•
Received: 23 June 2012 / Published online: 20 January 2013
Ó Springer Science+Business Media New York 2013
Abstract Nickel oxide nanoparticles have been synthesized by thermal treatment
of N,N0 -(bis(salicylidene)-ethylene-1,2-diamine)Nickel(II); [Ni(salen)]; as precursor
which has been synthesized via two methods: [Ni(salen)] were obtained by solid
state reaction in absence solvent and co-precipitation reaction in presence of propanol as solvent, respectively. Nickel oxide nanoparticles were characterized by
X-ray diffraction, scanning electron microscopy, transmission electron microscopy
and Fourier transform infrared spectroscopy.
Keywords
Nickel oxide Thermal treatment Nanoparticles Solid state reaction
Introduction
As one kind of transition metal oxide, NiO has recently received a great deal
of attention due to its applications in various fields such as fabrication of
p–n heterojunctions [1], energetic material [2], magnetic properties[3–5], catalysis
[6, 7], solar cells [8], gas sensors [9, 10], lithium ion battery [11, 12]. In the past
decade, various different physical or chemical synthetic approaches have been
developed to produce NiO nanoparticles, including solvo thermal [13, 14], hydrothermal [15, 16], sol–gel [17, 18], sonochemical method [19, 20], microemulsion
A. Khansari
Department of Inorganic Chemistry, Faculty of Chemistry, University of Guilan,
P. O. Box 413354-1914, Rasht, Islamic Republic of Iran
M. Enhessari
Islamic Azad University, Naragh Branch, Naragh, Islamic Republic of Iran
M. Salavati-Niasari (&)
Institute of Nano Science and Nano Technology, University of Kashan,
P. O. Box 87317–51167, Kashan, Islamic Republic of Iran
e-mail: salavati@kashanu.ac.ir
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[21] thermal treatment and thermal decomposition [22–27] and chemical precipitation [28] methods.
Solid state synthesis is a novel method involving the mechanical activation of
solid-state displacement chemical reactions, either during milling or during
following heat treatment [29]. A wide variety of nanoparticles have been
synthesized by solid state processing, including ZnO [30], MnS, NiS [31], CdS
[32], SnO2 [33], BiNbO4 [34], Co3O4 [35] and NiO [36]. Recently our group has
been synthesized ZnO nanoparticles [37] by this method. Solid state synthesis is
particularly suitable for large-scale production because of its simple process and low
cost [38]. However, there are few reports on the solid state preparation of nanosized
NiO.
Herein we report synthesis of NiO nanoparticles by thermolysis of N,N0 (bis(salicylidene)-ethylene-1,2-diamine)nickel(II); [Ni(salen)]; as precursor at low
temperature (500 °C) in the absence of any other template or surfactant. Precursors
were obtained by solid state reaction in absence solvent and co-precipitation
reaction in presence of propanol as solvent, respectively. The obtained NiO were
characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy
(FT-IR), transmission electron microscopy (TEM) and scanning electronic microscopy (SEM).
Experimental
Materials
All the chemical reagents used in our experiments were of analytical grade and were
used as received without further purification. Nickel(II) acetate tetrahydrate,
salicylaldehyde, 1,2-ethylenediamine and propanol were obtained from Merck Co.
Characterization
XRD patterns were recorded by a Rigaku D-max C III, X-ray diffractometer using
Ni-filtered Cu Ka radiation. Scanning electron microscopy (SEM) images were
obtained on Philips XL-30ESEM equipped with an energy dispersive X-ray
spectroscopy. Transmission electron microscopy (TEM) images were obtained on a
Philips EM208 transmission electron microscope with an accelerating voltage of
100 kV. Fourier transform infrared (FT-IR) spectra were recorded on Varian 4300
spectrometer in KBr pellets.
Preparation of N,N-Bis(salicylidene)-ethylene-1,2-diamine; H2salen [39]
The stoichiometric amount of salicylaldehyde (0.02 mol, 2.44 g) in dissolved
methanol (25 ml) is added drop by drop to 1,2-ethylenediamine solution (0.01 mol,
0.61 g) in 25 ml methanol. The contents were refluxed for 3 h and a bright yellow
precipitate of symmetrical Schiff-base ligand (H2salen) was obtained. The yellow
precipitate was separated by filtration, being washed and dried in the vacuum. It was
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then recrystalized from methanol to yield H2salen (92 %). Elemental and spectroscopic analysis of neat complex confirmed the molecular composition of ligand.
Preparation of [Ni(salen)] by Solid State Route
The Ni(CH3COO)24H2O salt and bis(salicylaldehyde) ethylenediimine; (H2salen)
were mixed and grinding for 15 min in an agate mortar at room temperature in a
molar ratio of 1:1, 1:2, 1:3 and 1:4. After grinding, above mixtures were heated at
65 °C for 4 h. The resultant mixtures were washed several times using distilled
water and dried in the air. The identification of the resulting products were based on
powder X-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR)
and elemental analysis in addition to visual observation of the color of the reaction
mixture, respectively. Anal. Calc. for [Ni(salen)]; NiC16H14N2O2: C, 59.13; H, 4.29;
N, 8.61; Ni, 18.06 %. Found C, 59.18; H, 4.38; N, 8.59; Ni, 18.10 %.
Preparation of [Ni(salen)] by Co-Precipitation Method [40]
The flask containing a stirred suspension of Nickel(II) acetate tetrahydrate
0.012 mol in propanol (50 cm3), and then warmed to 50 °C. N,N0 -bis(salicylidene)-ethylene-1,2-diamine 0.012 mol was added in one portion, and the resulting
yellow suspension was then stirred and heated under reflux for 2 h. Then the
mixture was cooled and filtered under reduced pressure. The collected solid was
washed with diethyl ether and dried in air, to give yellow crystalline [Ni(salen)]
which was purified by recrystallization from chloroform. The identification of the
resulting products was based on powder X-ray diffraction (XRD), Fourier transform
infrared spectrometer (FT-IR) and elemental analysis in addition to visual
observation of the color of the reaction mixture, respectively. Anal. Calc. for
[Ni(salen)]; NiC16H14N2O2: C, 59.13; H, 4.29; N, 8.61; Ni, 18.06 %. Found C,
59.18; H, 4.38; N, 8.67; Ni, 18.12 %.
Synthesis of NiO Nanoparticles
Black nanoparticles were produced by subjecting 0.01 mol of the as-prepared
[Ni(salen)] powders obtained by solid state methods and co-precipitation to thermal
treatment at a relatively low temperature (500 °C) in the air. An average temperature
increase of 30 °C is recorded every minute, before the temperature reached 500 °C,
and after keeping the thermal treatment at 500 °C for 5 h, it was allowed to cool
unaffectedly in the room temperature. The NiO nanoparticles were washed with
ethanol and distilled water for several times and dried in air at 50 °C.
Result and Discussion
Figure 1a shows the XRD patterns (10° \ 2\80°) of the obtained [Ni(salen)]
precursor prepared via solid state route in a molar ratio of 1:1 at 65 °C for 4 h. All
the reflection peaks in this pattern could be readily indexed to crystalline
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Fig. 1 XRD patterns of a the precursor Ni(salen) in a molar ratio 1:1, b NiO nanoparticles obtained by
the thermal treatment of Ni(salen) via solid state method in a molar ratio 1:1, c 1:2, d 1:3 and e NiO
nanoparticles obtained via co-precipitation method at 500 °C for 5 h
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Fig. 2 IR spectra of a Ni(salen) in a molar ratio of 1:1, b NiO nanparticles obtained from Ni(salen) in a
molar ratio of 1:1 and c NiO nanoparticles obtained via co-precipitation method on thermal treatment at
500 °C for 5 h
[Ni(salen)]. No obvious peaks of impurities were seen in this pattern. The XRD
pattern shown in Fig. 1b–d are corresponding to the samples obtained by thermal
treatment and oxidization of [Ni(salen)] complexes in a molar ratio of 1:1, 1:2 and
1:3 compounds at 500 °C for 5 h. All of the reflection peaks could be readily
indexed to crystalline cubic phase NiO with a lattice constant of a = 4.1700 Å,
which is consistent with the standard value of a = 2.9552 Å (JCPDS Card file No.
75-0197). The XRD pattern shown in Fig. 1e is also corresponding to the sample
obtained by thermal treatment and oxidization of [Ni(salen)] complex compound
precursor prepared via co-precipitation method at 500 °C for 5 h. All of the
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Fig. 3 SEM images of NiO nanoparticles prepared from Ni(salen) in a molar ratio a 1:1, b 1:2, c 1:3, and
d 1:4 by the thermal treatment of precursors at 500 °C for 5 h. Figure 3e, f show SEM images of NiO
nanoparticles obtained by co-precipitation method on thermal treatment at 500 °C for 5 h
reflection peaks could be readily indexed to crystalline rhombohedra phase NiO
with a lattice constant of a = 2.9552 Å, which is consistent with the standard value
of a = 2.9552 Å (JCPDS Card file No. 44-1159). The crystallite sizes of the
as-synthesized nickel, Dc, were calculated from the major diffraction peaks using
the Scherrer formula;
Dc ¼
Kk
:
b cos h
ð1Þ
where K is a constant (ca. 0.9); k is the X-ray wavelength used in XRD (1.5418 Å);
h the Bragg angle; b is the pure diffraction broadening of a peak at half-height, that
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Synthesis and Characterization of Nickel Oxide
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Fig. 4 TEM images of NiO nanoparticles prepared by thermal treatment of precursors which were
obtained from Ni(salen) a in a molar ratio 1:2 via solid state route and b co-precipitation method in
solvent
is, broadening due to the crystallite dimensions. The diameter of the crystalline
calculated by the Scherrer formula are 20, 18 and 15 nm, respectively. No other
peaks for impurities were detected.
Figure 2 shows a comparison of FT-IR spectrum of (a) [Ni(salen)] obtained via
co-precipitation, (b) and (c) NiO nanoparticles of [Ni(salen)] complex compound
precursor prepare via solid state reaction and co-precipitation methods, respectively.
The broad absorption bands at *3,400 cm-1 encompass the O–H stretching
vibrations of adsorbed water on the NiO surface. The spectrum also contains one
strong absorption bands at 453.53 and 429.52 cm-1 which confirm the stretching
vibration NiO bands [41]. The observed blue shift is related to differences in
properties of nanometer-scale surfaces.
Figure 3 shows scanning electron microscopy images of the NiO nanoparticles
obtained from Ni(salen) complex. Typical SEM images of as-obtained NiO
nanoparticles are shown in Fig. 3a–f. SEM images (Fig. 3a–d) indicated that molar
ratio changes of metal salt to ligand, resulted in morphological changes in
nanoparticles. Although our aim was change of nanoparticles size, with increase
distribution around [Ni(salen)] complex by ligand excess.
SEM images NiO nanopaticles could not exhibit clear and antiseptic
morphology.
Figure 4 shows the TEM images of the NiO nanoparticles via solid state route
and co-precipitation method in solvent, respectively. The TEM image (Fig. 4a)
shows the presence of dense agglomerates. The particles have a spherical shape, and
their distribution, likewise, is not uniformed. TEM image NiO nanoparticles with
average size between 15 and 30 nm. TEM image (Fig. 4b) shows the NiO
nanoparticles have spherical shapes with an average size of 20 nm.
Summary
In our synthesis NiO powders, the source materials were only [Ni(salen)].
[Ni(salen)] has been synthesized by solid state reaction. As a fast, simple and
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interesting method, precursors have been simply synthesized. In solid state
synthesis, the metal contact surfaces and ligand have been increased, with the
using of grind. Temperature and time were two additive reaction parameters. By
increasing molar ratio of ligand, we could increase distribution around metal
complexes. As a result, nanoparticles were obtained in smaller size.
Acknowledgments The authors are grateful to the council of Iran National Science Foundation and
University of Kashan for supporting this work by Grant No. (159271/16).
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