J Mater Sci: Mater Electron
DOI 10.1007/s10854-015-3419-z
NiAl2O4 nanoparticles: synthesis and characterization through
modify sol–gel method and its photocatalyst application
Mahnaz Maddahfar1 • Majid Ramezani2 • Masoud Sadeghi1 • Ali Sobhani-Nasab1
Received: 10 April 2015 / Accepted: 26 June 2015
Ó Springer Science+Business Media New York 2015
Abstract In this work, modify sol–gel method was used
to synthesize nickel aluminate (NiAl2O4) nanoparticles
with aid of nickel nitrate hexahydrate and aluminium
nitrate nonahydrate as the starting reagents in the presence
of ethanol as the solvent. Besides, to examine the effect of
different chelate agent such as citric acid monohydrate,
oxalic acid, salicylic acid, and malic acid on the mor-
phology and particle size of final products several tests
were performed. The structural, morphological, and optical
properties of as-obtained products were characterized by
techniques such as Fourier transform infrared spec-
troscopy, X-ray diffraction, energy dispersive X-ray
microanalysis, scanning electron microscopy and ultravi-
olet–visible. The photocatalytic degradation was investi-
gated using methyl orange under visible light irradiation
(k [ 400 nm). The resulting degradation rates of the
methyl orange were measured to be as high as 90 % in
270 min.
1 Introduction
Nanomaterials have attracted extensive interest because of
their unique properties in various fields in comparison with
their bulk counterparts [1–5]. Transition metal-oxide spi-
nels are important in many application fields because of
their high thermal resistance and catalytic, electronic and
& Ali Sobhani-Nasab
Ali.sobhaninasab@gmail.com
1
Young Researchers and Elites Club, Arak Branch, Islamic
Azad University, Arak, Iran
2
Department of Chemistry, Arak Beranch, Islamic Azad
University, Arak, Iran
optical properties. They are commonly used in semicon-
ductor and sensor technology as well as in heterogeneous
catalysis [6–14]. Transition metal aluminates are com-
monly prepared by a solid state reaction [15], co-precipi-
tation method [16], hydrothermal [17], combustion [18],
and sol–gel [19, 20]. The disadvantages of solid-state
routes, such as inhomogeneity, lack of stoichiometry con-
trol, high temperature and low surface area, are improved
when the material is synthesized using a solution-based
method. Compared with other techniques, the sol–gel
method is a useful and attractive technique for the prepa-
ration of aluminate spinels because of its advantage of
producing pure and ultrafine powders at low temperatures.
In this study, we have synthesized nickel aluminate
nanocrystals using modify sol–gel method. Furthermore, to
investigation the effect of difference chelate agent such as
citric acid monohydrate, oxalic acid, salicylic acid, and
malic acid on the morphology, particle size, and crystal
structure of the products several experiments were per-
formed. To evaluate the catalytic properties of nanocrys-
talline nickel aluminate, the photocatalytic degradation of
methyl orange under visible light irradiation was carried
out.
2 Experimental
2.1 Characterization
Nickel nitrate hexahydrate Ni(NO3)26H2O, aluminium
nitrate nonahydrate Al(NO3)39H2O, citric acid monohy-
drate, oxalic acid, salicylic acid, and malic acid were
purchased from Merck Company and used without further
purification. X-ray diffraction (XRD) patterns were recor-
ded by a Philips-X’PertPro, X-ray diffractometer using Ni-
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filtered Cu Ka radiation at scan range of 10 \ 2h \ 80.
The energy dispersive spectrometry (EDS) analysis was
studied by XL30, Philips microscope. Scanning electron
microscopy (SEM) images were obtained on LEO-1455VP
equipped with an energy dispersive X-ray spectroscopy.
Fourier transform infrared (FT-IR) spectrum was recorded
on a magna Nicolet 550 spectrophotometer in KBr pellets.
The electronic spectra of the nickel aluminate were
obtained on a Scinco UV–vis scanning spectrometer
(Model S-10 4100).
temperature. Aliquots of the mixture were taken at definite
interval of times during the irradiation, and after centrifu-
gation they were analyzed by a UV–vis spectrometer. The
methyl orange degradation percentage was calculated as:
A0  A
Degradation rate ð%Þ ¼  100
A0
where A0 and A are the absorbance value of solution at A0
and A min, respectively.

2.2 Synthesis of NiAl2O4 nanoparticles

At first, 1 mmol of Ni(NO3)26H2O was dissolved in

50 mL of distilled water. Then, 3 mmol of different acid
was subsequently added to the above solution under mag-
netic stirring at 70 °C for 30 min (Table 1). Afterwards,
2 mmol of Al(NO3)39H2O was dissolved in 50 mL of
distilled water and was added to the above solution under
magnetic stirring. A green solution was obtained and fur-
ther heated at 100 °C for 1 h to remove excess water.
During continued heating at 100 °C for 1 h, the solution
became more and more viscous to become a xerogel.
Finally, the obtained product was calcinated at 800 °C for
3 h in a conventional furnace in air atmosphere and then
cooled it to room temperature.

2.3 Photocatalytic experimental

The methyl orange (MO) photodegradation was examined

as a model reaction to evaluate the photocatalytic activities
of the NiAl2O4 nanoparticles. The photocatalytic experi-
ments were performed under an irradiation wavelength of
k [ 400 nm. The photocatalytic activity of nanocrystalline
nickel aluminate obtained from sample no.3 was studied by
the degradation of methyl orange solution as a target pol-
lutant. The photocatalytic degradation was performed with
0.0005 g of methyl orange solution containing 0.05 g of
NiAl2O4. This mixture was aerated for 270 min to reach
adsorption equilibrium and several UV–vis analyses were
performed. According to the Fig. 6a, MO concentration
does not change after 270 min. Later, the mixture was
placed inside the photoreactor in which the vessel was
15 cm away from the visible source of 400 W tungstate Fig. 1 XRD patterns of NiAl2O4 nanoparticles a sample no 1
lamps. The photocatalytic test was performed at room b sample no 2 c sample no 3 d sample no 4

Table 1 Reaction conditions

Sample no Solvent Chalet agent Temperature (°C) Decolorization MO
for NiAl2O4 nanoparticles
1 Water Oxalic acid 800 –
2 Water Citric acid 800 –
3 Water Salicylic acid 800 90 %
4 Water Malic acid 800 –

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J Mater Sci: Mater Electron

Fig. 2 SEM images of NiAl2O4

nanoparticles a sample no 1
b sample no 2 c sample no 3
d sample no 4

3 Results and discussion Dc ¼ Kk=b cos h ð1Þ

where b is the breadth of the observed diffraction line at
To investigate the effect of different acid as chelating agent
its half intensity maximum, K is the so-called shape
on the chemical structure of NiAl2O4 nanoparticles several
factor, which usually takes a value of about 0.9, and k is
experiments were performed. XRD patterns of NiAl2O4-
the wavelength of X-ray source used in XRD. Chelating
in presence of citric acid monohydrate (sample no 1),
agents are used in inorganic chemistry to prevent particle
oxalic acid (sample no 2), salicylic acid (sample no 3), and
agglomeration by reducing condensation reactions in
Malic acid (sample no 4) are shown in Fig. 1a–d, respec-
liquid phase synthesis; therefore, to investigate the effect
tively. The XRD patterns of the as-synthesized NiAl2O4
of different acid as chelating agent such as citric acid
(Fig. 1a–d) indicate the formation of monophasic spinel
monohydrate (sample no 1), oxalic acid (sample no 2),
cubic of NiAl2O4 (JCPDS No. 44-0160), with the calcu-
salicylic acid (sample no 3), and malic acid (sample no 4)
lated cell parameter of a = b = c 8.1040 Å. No other
on the surface morphology of NiAl2O4 nanoparticles
crystalline phases are detected in the product. According to
several experiments were performed at constant calcina-
XRD data, the crystallite diameter (Dc) of NiAl2O4
tions temperature 800 °C and molar ratio of Ni(NO3)2
nanoparticles obtained from sample 1–4 are calculated to
6H2O to different acid to 1:3. Figure 2a–d illustrate the
be 70, 44, 35, and 58 nm using the Scherer Eq. (1):

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SEM images of the products synthesized in the presence
of different acid. According to the Fig. 2a–d, the mor-
phology of all samples is particle-like. Moreover, by
comparing these results, it is clear that the optimum
chelating agent is oxalic acid (sample no 2). FT-IR
analysis was performed to identify the presence of certain
functional groups in NiAl2O4 nanoparticles and confirm
the purity of NiAl2O4. Therefore, the FT-IR spectra of
NiAl2O4 nanoparticles in the molar ratio of nickel nitrate
to salicylic acid 1:3 at 800 °C (sample 3) was recorded in
the range of 400–4000 cm-1 (Fig. 3). The weak absorp-
tion bond observed at 1627 cm-1 is due to the bending
vibration of absorbed water [21] and the absorption bond
at 3427 cm-1 is because of the O–H stretching mode
[22]. Nickel-oxygen stretching frequencies appeared in
the range 579–727 cm-1, associated with the vibrations
of Ni–O, Al–O, and Ni–O–Al bonds [23]. Energy dis-
persive X-ray microanalysis (EDS) is an analytical tech-
nique which used for the chemical characterization of
NiAl2O4- nanoparticles (sample 3, Fig. 4). Figure 4
demonstrates the presence of Ni, Al, and O elements in
these nanoparticles. Moreover, neither N nor C signals
were detected in the EDS spectrum, which means the
Fig. 3 FT-IR spectrum of NiAl2O4 nanoparticles (sample no 3)
Fig. 4 EDS pattern of NiAl2O4 nanoparticles (sample no 3)
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J Mater Sci: Mater Electron
product is pure and free of any impurity. To investigate
the optical properties of the nanocrystalline NiAl2O4-,
UV–vis spectra was recorded. Figure 5 shows the UV–vis
diffuse reflectance spectrum of sample no.3. Using Tauc’s
formula, the band gap can be obtained from the absorp-
tion data. The energy gap (Eg) of the nanocrystalline
NiAl2O4 has been estimated by extrapolating the linear
portion of the plot of (ahm)2 against hm to the energy axis.
The Eg value of the nanocrystalline nickel aluminate
calculated to be 2.85 eV. Photodegradation of methyl
orange under visible light irradiation was employed to
evaluate the photocatalytic activity of the as-synthesized
nanocrystalline NiAl2O4- (sample no 3). The obtained
result is depicted in Fig. 6a–c. No methyl orange was
practically broken down after 270 min without using
Visible light irradiation or nanocrystalline NiAl2O4. This
observation indicated that the contribution of self-degra-
dation was insignificant. The probable mechanism of the
photocatalytic degradation of methyl orange can be
summarized as follows:
NiAl2 O4 þ hm ! NiAl2 O4 þ e þ hþ ð2Þ
þ 
h þ H2 O ! OH ð3Þ
e þ O2 ! O
2 ð4Þ

OH þ O
2 þ methyl orange ! Degradation products
Using photocatalytic calculations by Eq. (2), the methyl
orange degradation was about 90 % after 270 min irradi-
ation of visible light, and nanocrystalline NiAl2O4 pre-
sented high photocatalytic activity) Fig. 6a). The
spectrofluorimetric time-scans of methyl orange solution
illuminated at 365 nm with nanocrystalline NiAl2O4 are
depicted in Fig. 6b. Figure 6b shows continuous removal
of methyl orange on the NiAl2O4 under UV light irradia-
tion. It is generally accepted that the heterogeneous pho-
tocatalytic processes comprise various steps (diffusion,
Fig. 5 Diffuse reflectance spectrum of NiAl2O4 nanoparticles (sam-
ple 3)
J Mater Sci: Mater Electron
Fig. 6 a Photocatalytic methyl orange degradation of NiAl2O4
nanoparticles obtained from sample no 3 under visible light b fluo-
rescence spectral time scan of methyl orange illuminated at 365 nm
with NiAl2O4 nanoparticles and c reaction mechanism of methyl
orange photodegradation over NiAl2O4 under visible light irradiation
adsorption, reaction, and etc.), and suitable distribution of
the pore in the catalyst surface is effective and useful to
diffusion of reactants and products, which prefer the pho-
tocatalytic reaction. In this investigation, the enhanced
photocatalytic activity can be related to appropriate dis-
tribution of the pore in the sponge-like nanocrystalline
NiAl2O4 surface, high hydroxyl amount and high separa-
tion rate of charge carriers (Fig. 6c) [24].
4 Conclusions
We employed a facile modify sol–gel method to synthesize
NiAl2O4 nanoparticles. Oxalic acid monohydrate, citric
acid, salicylic acid, and malic acid were used as the chalet
agents to investigate their effect on the morphology, par-
ticle size, and chemical structure of final product. NiAl2O4
nanoparticles were characterized by EDS, SEM, XRD,
UV–vis, and IR spectroscopy. When as-prepared
nanocrystalline nickel aluminate was utilized as photocat-
alyst, the percentage of methyl orange degradation was
about 90 % after 270 min irradiation of visible light.
Acknowledgments Authors are grateful to council of University of
Arak for providing financial support to undertake this work.
Compliance with Ethical Standards
Conflict of interest The author declares that the research was
conducted in the absence of any commercial or financial relationships
that could be construed as a potential conflict of interest.
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