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Materials Today: Proceedings 4 (2017) 10664–10671 www.materialstoday.com/proceedings

AMMMT 2016

Synthesis and characterization of spinel metal aluminate by a

a
Department of chemistry, Madanapalle Institute of Technology and Science, Madanapalle-517325, Andhra Pradesh, India.
b
Department of chemistry, Jawaharlal Nehru Technological University Anantapur, Ananthapuram – 515002, Andhra Pradesh, India.

Abstract

In the current research report we present a simple, eco-friendly, cost and time saving biosynthesis of ZnAl2O4 spinel nano and
micro particles using Pomegranate peel extract, that act as the reducing as well as stabilizing agent. Thus synthesized products
are then consistently characterized under powder X-ray diffraction (PXRD), scanning electron microscopy (SEM). The powder
XRD analysis has confirmed their chemical composition. Optical properties including diffuse reflectance spectroscopy (DRS),
photoluminescence (PL) spectroscopy and fourier transform infrared spectroscopy (FTIR) are also investigated. The ZnAl2O4
nanoparticles formation is been confirmed by PXRD, FT-IR and SEM. From XRD the calculated crystalline size of the ZnAl2O4
nanoparticles is in the range of 11.2 nm.

© 2017 Elsevier Ltd. All rights reserved.

Keywords: ZnAl2O4, Pomegranate fruit peel extract, Microwave assistance, powder XRD, Optical properties;

1. Introduction:

Nanocrystalline spinels are a class of binary transition metal oxide, exhibits interesting mechanical,
magnetic, optical and thermal properties compared to that of their bulk materials [1]. Zinc aluminate (ZnAl2O4) is a
well-known spinel oxide, and has attracted considerable attention in various interdisciplinary areas. Zinc aluminate
is have typical applications in ceramic industries, optical and sensing devises, as catalyst and catalyst supports in
manufacture industries, as paints in aerospace industry, dielectrics and electronic applications and these applications

* Corresponding author. Tel.: +00919000451689;

2214-7853 © 2017 Elsevier Ltd. All rights reserved.

of Zinc aluminate is because of its unique properties, mechanical, thermal and chemical stability, low surface
acidity, excellent optical transparency, wide band-gap energy and high quantum yields [2, 3]. ZnAl2O4 is used in
optoelectronic devices operated in the ultraviolet region, photo electronic devices, because of its wide-band gap of
3.8 eV and also used as optical and thermal controlled coating for spacecraft [4]. ZnAl2O4 spinels are good enough
for a range of catalytic applications as heterogeneous catalyst in the reactions like cracking, dehydration,
hydrogenation and dehydrogenation of organic compounds [5] and they are also used as catalyst support because of
less surface acidity, chemical inactiveness and thermal durability [6]. In recent years, ZnAl2O4 is also employed for
dehydrogenation of chemicals in chemical and petrochemical industries (Shu Fen Wang et al 2005), degrading the
gaseous toluene [7], restoring of ethanol steam [8], trans-esterification of oils of vegetable [9] and iso-butane
combustion [10-11].
Several synthesis approaches are reported so far, for the preparation of ZnAl2O4 such as ceramic method,
mechano-chemical synthesis [12], solid-state reaction synthesis [13], citrate-gel method [14], hydrothermal [15–18],
wet chemical method [19], co-precipitation method [20], sol–gel method [21–24], and microwave assisted-hydro-
thermal method [25]. In green synthesis method various plant material extracts are used in the preparation of spinal
nanoparticles, where these extract of plant materials act as both reducing and stabilizing agent. Opuntia dilenii [26],
Sesamum indicum [27] are the two plant extracts explored for the synthesis of ZnAl2O4 nanoparticles. Although
there is a good progress in exploring nano sized aluminate spinels, some issues like the preparation route and optical
properties of ZnAl2O4 nanoparticles still challenging and needed further study.

2. Characterization:

Zinc aluminate nanoparticles synthesized through green synthesis route are annealed in muffle furnace at
700 oC for about 3 hours and then characterized by powder-XRD, SEM, FTIR and UV-Vis spectroscopy for its
physical and optical properties. The powder-X ray diffraction patterns for the sample is recorded under the Bruker
D8 diffractometer instrument with 2θ value ranging from 10o to 80o. The surface morphologies of the metal
aluminate is studied under scanning electron microscope (SEM), using a Ziess-SEM instrument, before that the gold
sputtering device is used to coat the sample with gold for the better visibility. FT-IR spectra of sample is recorded
under Jasco FT/IR-4200 infrared spectrophotometer instrument in transmittance mode and the wavelength ranging
from 400 to 4000 nm, the sample is mixed with heat dehydrated potassium bromide powder and made into pellet for
the analysis. The optical measurements for the sample is recorded under Jasco UV-670 spectrophotometer
instrument for UV-Vis diffuse reflectance spectra with the wavelength range from 200 to 900 nm, at room
temperature. And Jasco FP-6300 spectrofluorometer instrument is used to record the photoluminescence
measurements of sample at room temperature.

3. Results and Discussion:

The reaction mechanism of spinel preparation can be described as follows and the schematic synthesis
procedure is illustrated in Figure-1. below, in mechanism nitrogen dioxide and oxygen is liberated from nitrate salts
and carbon dioxide and water vapour from peel extract solution.

Zn(NO3)2+ 2Al(NO3)3+ P-Extract → ZnAl2O4+ NO2↑+ 2O2↑ + CO2↑ + H2O↑.

3.1. Powder X-ray Diffraction (PXRD):

The powder X-ray diffraction patterns for the ZnAl2O4 sample is recorded under the Bruker D8
diffractometer instrument with 2θ value ranging from 10o to 80o. The PXRD measurements are taken to analyze the
crystal purity and phase recognition. The PXRD measurements obtained for the spinel sample is presented in
Figure-2(a). The diffraction pattern for ZnAl2O4 are observed at 2θ values at 31.4°, 36.9°, 45.5°, 55.8°, 59.5° and
65.4°, that can be correlated to (220), (311), (400), (422), (511), and (440) planes respectively, and these planes are
associated with the cubic phase of ZnAl2O4 with JCPDS card No. 73-1961 (space group Fd3m). The peaks of any
other phase are not detected, that suggests the complete development of ZnAl2O4 spinel under applied experimental
condition in the present work and no other phases or elements are identified in the sample.
10666 R.Yuvasravana, P.P.George, N.Devanna / Materials Today: Proceedings 4 (2017) 10664–10671

The diffraction pattern had sharp peaks, indicating the good crystallinity and purity of the spinel sample. The
average particle size of thus synthesised spinel samples is calculated with the help of Debye Scherrer formula, as
demonstrated below

Where L is the average crystal particle size (Ao), λ is the wavelength of X-ray used (0.154 nm), θ is the diffraction
angle, and β the peak position and the FWHM (full-width at half maximum). The average particle size is found to be
11.2 nm.

Figure-1: Schematic representation of synthesis of ZnAl2O4 spinels.

3.2. Scanning electron microscopy (SEM) studies:

The SEM images provide illustration of surface morphology of the ZnAl2O4 spinels, and are shown in
Figure-2(b). It can be seen from SEM images that the presence of nearly spherical like agglomerated nanoparticles
that have the diameter range from 0.1 to 0.6 µm. The nano and micro particles are evenly scattered in the form of
small particles and large agglomerates having nearly spherical like structure. The agglomerated structures of these
samples are due to the solid state welding of fine particles that may be formed at the time of annealing at 700 oC.
The size of agglomerated ZnAl2O4 nanoparticles prepared in this work are comparatively similar to that of the
ZnAl2O4 nanoparticles synthesized by microwave method using Sesamum (Sesamum indicum L.) extract by C.
Ragupathi and his co-workers [27]. C. Ragupathi’s procedure involves microwave heating for 10 minutes using
Sesamum (Sesamum indicum L.) extract. Whereas the current microwave assistance method involves the use of
pomegranate fruit peel extract and are irradiated under microwaves for five minutes. Precursor solution containing
fruit peel extract and metal nitrates react to form complex matrix on microwave irradiation, followed with the
formation of aluminate samples at the end, this confirms that addition of fruit peel extract may have influenced the
size of nanoparticles, as we know that the structure of the samples changes accordingly with respect to the synthesis
procedure. Metal aluminates are excellent microwave adsorptive materials, hence can be readily heated to the higher
temperatures with in short time. And hence the microwave application in the field of nanoparticles synthesis is more
advantageous and significant in the reduction of time of synthesis, growth and morphology of nanoparticle, at the
specified stable reaction conditions. The estimated particle size from XRD is observed to be slightly different from
that of SEM images, that can be explained by structural disorder resulted due to the lattice strain caused by different
ionic radii or clustering of nanoparticles.
 R.Yuvasravana, P.P.George, N.Devanna / Materials Today: Proceedings 4 (2017) 10664–10671 10667

Figure-2: (a) XRD of ZnAl2O4 spinels. (b) SEM image of ZnAl2O4 spinels.

3.3. Fourier transform infrared (FT-IR):

The FT-IR spectrum of ZnAl2O4 is shown in Figure-3 was recorded in the frequency range from 400 –
4000 cm−1, respectively. In the spectra, the broad bands near 3432 and 1626 cm−1 are referred to the –OH stretching
and deformative vibrations of water molecules, the water molecules may be absorbed by sample from atmosphere at
the time of sample preparation in the presence of atmosphere. The peaks at 1411 cm−1 can be attributed to the Al–O
stretching vibrations. In the spectra, the metal–oxygen stretching frequencies are related to the peaks that appear in
the range 400–1000 cm−1 and are assigned to the vibrations of Zn–O, Al–O and Zn–O–Al bonds. From figure 3 FT-
IR spectra of ZnAl2O4 exhibits two sharp peaks centered at 599 and 443 cm−1 respectively and they are related to
the metal-oxygen stretching and bending frequencies like Al–O–Zn, Al–O and Zn-O stretching and bending
vibration. C. Ragupathi and his co-workers reported the similar IR spectra of ZnAl2O4 with bands observed at 650
and 490 cm−1 for ZnAl2O4 [27]. The characteristic absorption band at 924 cm−1 represented by IR spectra of
ZnAl2O4 of C. Ragupathi’s work can also be seen at 1025 cm−1 in the IR spectra in the current work. The peaks at
2922 and 2855 cm−1 in the IR spectra are may be due to the presence of CO32- ion. The existence of CO2 in the
sample can be explained by two reasons that are, mixing of aerial CO2 that occurred at the time of sample
preparation and the presence of CO2 inside the powders sample that may be formed due to annealing of plant
material.

Figure-3: FTIR of ZnAl2O4 spinels.

3.4. Optical properties:

Zinc aluminate [ZnAl2O4] nanoparticles are widely used for the photo electronic devices because of its
large band gap [27]. The optical study for Zinc aluminates was performed using a Jasco UV-670, a UV-VIS-NIR
diffuse reflectance spectrophotometer and the reflectance spectra are recorded at room temperature. Metal
aluminates exhibit colour due to d-d electron transitions, where as ZnAl2O4 a normal spinal is colourless compound
that is because Zn+2 ion is tetrahedrally coordinated and have completely filled d-orbitals. Figure-4(a) shows the
typical UV–Vis absorbance spectrum of ZnAl2O4 nanoparticles and shows UV-absorption bands peaked at 218, 262,
304 and 370 nm respectively. UV–Vis reflectance spectrum is recorded to estimate the optical band gap of ZnAl2O4
nanoparticles and is shown in Figure-4(b). The optical band gap for a semiconductor is estimate by using the
following equation:

α(ν) = A(ħν/2 – Eg)m/2,

The band gap is determined by relating diffuse-reflectance (R) of the samples with the Kubelka–Munk function F(R)
in the equation F(R) = (1-R)2 /2R and the energy intercept plot of (F(R)*hν)2 versus hν is plotted which yields the
Eg, dir for a direct-allowed transition, when the linear regions are extrapolated to the zero ordinate, one can get the
band gap of the sample. Hence by this method, the band gap is calculated for ZnAl2O4 nanoparticles and the band
gap is found to be 4.1 eV for ZnAl2O4 and it is shown in Figure 5(a). The decrease in nanoparticles size leads to the
increase in optical band gap, because of the quantum confinement the decrease in crystal size, band gap energy
exhibits an increasing trend. Thus the results from UV–Vis reflectance spectra are in good agreement with that of
XRD results.

Figure-4: (a) UV-Vis absorbance spectrum (b) UV-Vis reflectance spectrum.

The oxygen vacancy and defect related transitions are can be determined by using Photoluminescence (PL)
spectrum. The surface states and quantity of defects can be varied with reference to the crystallite size and
morphology and synthesis conditions [27]. The PL spectra of ZnAl2O4 nanoparticles synthesised by microwave
assistance method are shown in Figure-5(b). The emission spectra of ZnAl2O4 nanoparticles are recorded in
wavelength ranges from 220 to 600 nm by exiting them at 210 nm wavelength. The PL emission spectra of neat
ZnAl2O4 nanoparticles, demonstrate the emission bands peaked at three wavelength regions 335 nm, 422 nm and
472 nm respectively. The PL emission bands for the ZnAl2O4 nanoparticles, synthesised by microwave reduction
using sesamum plant extract showed the broad emission bands at 492, 530 and 545 nm [27]. Whereas the ZnAl2O4
nanoparticles synthesised by microwave assistance using pomegranate fruit peel extract showed the broad emission
bands at 335, 422 and 472 nm, this blue shift is due to the quantum size effect, and a slight difference in the average
crystallite size and intra-band gap errors like oxygen vacancies because of the use of pomegranate fruit peel extract
in the synthesis procedure. A broad UV band and weak visible bands in the region confirmed the good crystallinity
of the as synthesised spinel sample by microwave assistance method.
 R.Yuvasravana, P.P.George, N.Devanna / Materials Today: Proceedings 4 (2017) 10664–10671 10669

Fruit peel extract of pomegranate consists of polyphenols such as gallic acid, punicalagin and ellagic acid
as reported by Wenjuan Qu et.al. [28]. The polyphenol molecules exhibit antioxidant property, similar molecular
mechanism can be anticipated to be responsible for the formation of nano ZnAl2O4 spinels. These fruit peels are
naturally available, non-polluting and non-toxic, thus fruit peel extract as active ingredient, enables synthesis of
nanoparticles at low cost. In microwave assistance, precursor materials are thermally decomposed with the help of
microwave radiation, to synthesis the spinel nanoparticle, thus it is economical, rapid, and accessible nowadays. In
the current study, the microwave-assisted green synthesis technique, metal nitrates are dissolved and mixed well
with fruit peel extract and the solution is placed in household microwave for combustion process. Microwave
radiation, dehydrates and decomposes the solution into flake like residue, washed and annealed to give ZnAl2O4
nano spinals. Fruit peel material is completely decomposed and removed in the form of carbon related by-products,
either in microwave or at the annealing process, resulting in pure and 85% yield of zinc aluminates nano spinels.

Figure-5: (a) Band gap energy plot of ZnAl2O4 spinels. (b) PL spectra of ZnAl2O4 spinels.

4. Conclusions:

In this work ZnAl2O4 nanoparticles are synthesised under microwave assistance by using pomegranate fruit
peel extract as reducing and stabilising agent and obtained anticipated results. At room temperature the pomegranate
fruit peel extract promotes the formation of nanoparticles with a fast kinetics and no other harmful chemicals are
used except that of metal nitrate salts and fruit peel extract. This microwave assistance method is more reliable, can
be performed in simple and easy steps and gets the results within a short time. The formation of ZnAl2O4
nanoparticles is been supported by PXRD, FTIR and SEM and the crystalline sizes of ZnAl2O4 nanoparticles is in
the range of 11.2 nm, as calculated from PXRD measurements. The band gap values calculated from reflectance
spectra of UV-VIS-NIR diffuse reflectance spectrophotometer, ranges between 3.9 – 4.0 eV which explains the nano
dimensions of ZnAl2O4 nanoparticles. In microwave combustion process, with in short duration of time the reaction
mixture in the oven gets heated to higher temperature spontaneously by takes energy from the microwave field.
Hence by, this work presents a smooth and comfortable method for the preparation of bimetal oxide spinels like zinc
aluminates with a promising and good crystalline structure. This fabrication procedure can be further applied in the
preparation of other bimetal oxides.
10670 R.Yuvasravana, P.P.George, N.Devanna / Materials Today: Proceedings 4 (2017) 10664–10671

5. Experimental:

5.1. Materials:

Zinc and aluminium nitrates are the precursor material, (97% purity Merck chemicals, India) and are used
as obtained without any further refinement. The pomegranate (Punica granatum.) fruits were collected from local
fruit market, Madanapalle, Andhrapradesh.

5.2. Preparation of the Plant Extract:

The pomegranate (Punica granatum.) fresh peels are washed thoroughly with distilled water to remove
unwanted dust and they are dried in shade to make sure that they look fresh at the time of extract preparation. 20g of
pomegranate fruit peel was weighed, cut into slices and added to 100 ml distilled water in a 250 ml Erlenmeyer flask
and boiled on a gas burner for 15 minutes, cooled and filtered using filter paper, the filtrate thus obtained is used as
aqueous fruit peel extract for synthesis of nanoparticles.

5.3. Synthesis of Metal Aluminates:

Stoichiometric mass proportions of Zinc nitrate and Aluminium nitrates in 1:2 ratio are dissolved in 50 ml
distilled water in 250 ml beakers. Then 5 ml of fruit peel extract was added to the nitrate solution, and stirred for 15
minutes using a magnetic stirrer. The solution is then irradiated under microwave radiation using a house hold
microwave oven for about 5 minutes, with break at every 60 sec to avoid wastage of the solution by spilling.
Initially solution underwent boiling, dehydration and decomposition by releasing gases leaving dry flakes like solid
behind. This dry solid is washed several times with water and ethanol for its purity and annealed in muffle furnace at
700 oC for about 3 hours.

Acknowledgements: Authors thanks the Management, Madanapalle Institute of Technology and Science, Angallu,
Madanapalle, Andhra Pradesh, for encouraging to complete this research work. Dr. P. P. George is thankful to the
UGC Major Research project (UGC-MRP- Major Chem. - 2013- 25694). R. Yuvasravana is thankful to VIT,
Vellore, for PXRD measurements, SV University, Tirupathi, for SEM measurements, BITS-Pilani, Hyderabad
campus for FTIR, UV-Vis and PL spectroscopy respectively.

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