ECS Journal of Solid State Science and Technology, 2020 9 126005

2162-8777/2020/9(12)/126005/7/$40.00 © 2020 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited

Nanosized Magnesium doped Copper Chromites Spinel Particles

Synthesis and Characterization
Kiran Batool,1 Malika Rani,1 Ayesha Younus,2 Arshad Mehmood,3 Sikander Azam,4,5,z
Bakhtiar Ul Haq,6 Rubia Shafique,1 Naseem Akhtar,1 Wilayat Khan,7 and
Thamraa Alshahrani8,z
1
Department of Physics, The Women University Multan, Multan, Punjab, Pakistan
2
Department of Physics, University of Agriculture Faisalabad, Faisalabad Pakistan
3
National Institute of Lasers & Optronics, Nilore, Islamabad, Pakistan
4
Division of Computational Physics, Institute for Computational Science, Ton Duc Thang University, Ho Chi Minh City,
Vietnam
5
Faculty of Electrical and Electronics Engineering, Ton Duc Thang University, Ho Chi Minh City, Vietnam
6
Advanced Functional Materials & Optoelectronics Laboratory (AFMOL), Department of Physics, Faculty of Science, King
Khalid University, Abha, Saudi Arabia
7
Department of Physics, Bacha Khan University, Charsada, Pakistan
8
Department of Physics, College of Science, Princess Nourah Bint Abdulrahman University, Riyadh, Saudi Arabia

Magnesium doped copper chromites spinel nanoparticles (Cu1−xMgxCr2O4) where x = 0.2, 0.4, 0.6, and 0.8 is synthesized by sol-
gel method and characterized by different techniques like EDS, SEM, Raman spectroscopy, and Photoluminense. Various
parameters affecting the sample techniques like temperature and Concentrations. The crystal phase of CuCr2O4 is tetragonal having
a space group is 121/amd. We calcined at 750 °C temperature. Its lattice parameters are 6.0341 and 7.7888, which is very close to
the reported ones. XRD tells us about the crystal size and dislocation density of samples. Four peaks observed in UV spectra of
CuCr2O4 that occurs at different regions, bandgap obtained for the parent sample is 5.02 eV, and when we doped Magnesium then
the bandgap changes and becomes 4.17 eV. Similarly, SEM results show that pure copper chromite structure is tetragonal and after
doping the other compounds the structure changes according to characteristics of Nanoparticles. In PL spectra four peaks are
obtained one at 347 nm, 380 nm, 500 nm and the other is at 600 nm. According to Raman, shift property two peaks are obtained
with different wavelengths like 1306 cm−1 and 1465 cm−1. ED’s results clearly show that copper chromites Nanoparticles
successfully synthesized and when we doped Magnesium in copper chromite, the best results are observed.
© 2020 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited. [DOI: 10.1149/2162-8777/
abce00]

Manuscript submitted October 31, 2020; revised manuscript received November 24, 2020. Published December 7, 2020.

Nanocrystalline transition metal oxide (NTMOs) with morpho-
logical structure have attracted tremendous attention during the last
decade because of their remarkable catalytic, optical, magnetic, and
electrical properties which offer potential application in many fields
of science and engineering.1–3 For example catalytic application of
some transition metals and their oxides such as Al (OH)3.Cr (OH)3,4
CeO2,5 Nd2O3.6 Moreover, copper chromites have been used as
catalysts for different industrial processes such as hydrogenation,
oxidation, alkylation, and dehydrogenation; and so on and thus find a
wide range of commercial applications.1–3,7
Among the NTMOs catalyst, spinel copper chromites (CuCr2O4)
is an effective catalyst for use with composite solid propellants, used
for propulsion of rockets, because it imparts a pressure independent
catalytic effect on the burning rate of oxidizers such as ammonium
perchlorate.8–14
Usually, transition metal properties do not depend only on their
chemical composition but also on their structure, phase, shape, size,
and size distribution. Different methods have been proposed for the
synthesis of Nano Transition Metal Oxides (NTMOs), such as
hydrothermal, microwave, precipitation, melting, etc. but unfortu-
nately, not all these methods are applicable for controlling the shape
and size distribution of nanoparticles. Therefore, here we are using
the most effective method, which requires low calcination tempera-
ture, which is called the sol-gel method. This method was reported to
have an advantage for the production of monodispersed particles
with a controlled mean size to improve different properties of
nanostructure such as catalyst activity.15–18 Therefore this method is
one of the most preferred candidates.
Now the formation of nanoparticles copper chromates, chromates
are basic mineral of chromium and chromium is found in Iran near
Baluchistan and Kerman provinces with about 40% Cr2O3. Spinel
copper chromates is used as a catalyst for oxidation of carbon mono
z
E-mail: sikander@tdtu.edu.vn; thmalshahrani@pnu.edu.sa
oxide due to narrowband semiconductor (Lu et al., 2002). The
catalyst is also energetic in pollution reduction, for a sample, in
carriage tire out, where it is employed to accomplish whole rust of
CO and other hydrocarbons to CO2. In addition to multipurpose
marketable applications of CuCr2O4 as a catalyst, its applications are
found in airborne convertor for propellants solid used in flying
weaponries and galaxy vehicles. Therefore, CuCr2O4 is an important
material of great stipulate.
The mean of the existent study was to build up an eco-friendly
affable sol-gel to organize Nano-sized copper chromates particles. In
the present work, the first phase is to synthesized nanoparticles
copper chromates through an undemanding precipitations path with
the sol-gel method.
We synthesized copper chromates by the sol-gel method (Hench
& West, 1990), which is a very easy and friendly environment. So I
doped Magnesium in the parent sample with concentrations X = 0.2,
0.4, 0.6, 0.8 by sol-gel method, and compared the XRD result with
parent sample CuCr2O4.
Experimental
Materials.—Copper nitrate trihydrate (Cu (NO3)2.3H2O, 99.5%),
Chromium nitrate nonahydrate (Cr (NO3)3. 9H2O, 99.0%),
Magnesium Nitrate and citric acid anhydrous (c6H8O7, MW:
210.14 or 192.12, 99.9%) all are purchased from Merck.
Ammonia and Water used in this experiment were deionized and
doubly distilled.
Preparation of Cu1−xMgxCr2O4 by Sol-gel technique.—In a
typical synthesis procedure, the copper chromites single nucleotide
polymorphisms (SNPs) with a Cu/Cr molar ratio of nanoparticles
were prepared by the sol-gel method followed by a temperature-
programmed process.
In the first step, calculated amounts in grams of copper nitrate and
appropriate amount in grams of chromium nitrate and Magnesium
 ECS Journal of Solid State Science and Technology, 2020 9 126005
nitrate were dissolved in 50 ml distilled water (deionized water) to
produce a clear solution. Then, an appropriate amount of citric acid
was dissolved into an aqueous solution where the molar ratio of citric
acid to the total amount of metallic ions was 2:1 producing a
transparent mixed sol. The mixture was stirred continuously until the
homogenous starting precursors were obtained.
PH adjust at 7 by adding ammonia dropwise continuously. After
adjusting PH the temperature kept between 90 to 95 C or raised to at
100 °C. Then the mixture is stirred for almost 30 min. After 20 min,
the solution will turn dark green transparent gel. This gel was dried
in a furnace at a temperature of 750 °C for 4 h. after calcination
temperature; the dark black color powder was obtained. after
grinding the sol-gel into an agate motor pestle. This powder was
stored for further characterization. Fig 1 shows the procedure to
synthesize compound systematically in detail. In Table I concentra-
tion of parent and the doped compound is given in which way we
synthesized parent copper chromites and when doped magnesium in
it with various concentrations like (0.2, 0.4, 0.6 and 0.8).
Results and Discussions
XRD analysis.—XRD, the analysis gives us information about
the crystal structure and phases of a sample. The XRD pattern of
CuCr2O4 is shown in Fig. 2. The value of 2θ for the XRD pattern is
ranging from 20 to 80. Therefore, the main peaks of our XRD results
at 750 °C are 30, 30.5, 35, 35.5, 40.5, 45.5, 50.5, and 55.5. We
obtain a single phase of our sample at 750 °C temperature. The
crystal structure of our sample is tetragonal which showed that the
sample attained a high purity. Its space group is 141/amd. At 750 °C,
we obtain the (124) phase with a single phase of copper chromite.
The a and c lattice parameters of samples analyzed at 750 °C are
6.0341Å and 7.7888Å respectively. These c and lattice parameters of
our samples are closely related to the reported ones. Its ratio c/a is
1.290. similarly when Mg-doped in Copper chromites then major
peaks appear at 30, 30.5, 35, 35.5, 40.5, 45.5, 50.5, and 55.5. These
doped Magnesium Xrd (b) results showed that when we doped,
magnesium with various concentrations the peaks of copper chro-
mites are suppressed and magnesium peaks are dominant. This
presents the novelty of my work. The c and lattice parameters of the
doped sample, which were analyzed at 700 °C, are 8.328–8.412Ă
respectively. Its c/a ratio is 1.0100. Wavelength is 1.541874 Ă of
copper chromites and doped magnesium copper chromites. Fig 2
Figure 1. Schematic figure of manufacturing CuCr2O4, Cu1−xMgxCr2O4 Nanoparticles.
shows the various concentrations of doped Magnesium in copper
chromites by the sol-gel method and these graph shows when we
increase the concentration of magnesium in copper chromites peaks
of copper become less and doped magnesium peaks become sharp.
SEM analysis.—By using scanning electron microscopy surface
morphology of synthesized Cu–Cr–O nanoparticles has been investi-
gated. Under different conditions, SEM images are formed as shown in
Fig. 3. With low homogeneity, particles have a quasi-spherical
structure. When we increase the temperature, a relative increase in
size and change in particle size was observed. Moreover, by increasing
the temperature at 750 °C the particles become more disordered and
less spherical, among the particle’s accumulation increased. From the
results, it can be observed that particles have good appropriate
separations, good homogeneity, and quasi-spherical shape. It was
also observed that Cu/Cr molar ratio has an important effect on the
particle size and shape. After doping Mg in copper chromites with
various concentrations shown in Fig. 4 with ratios 0.2, 0.4, 0.6, 0.8.
In CuCr2O4, it is in stack form and after etching Mg layer copper
chromites nanoparticles form, and it is clearly shown after Magnesium
doped particles are attached to the surface of nanoparticles.
EDX analysis.—Sometimes energy dispersive spectroscopy is
called energy dispersive analysis. This graph clearly shows that a
single phase of copper chromites has formed. In the given Table II
ratios of Cu, Cr, and O are given according to their weight and
atomic ratios. From the EDS graph, it is shown that no extra
impurity peaks appear. We have obtained a single phase of copper
chromites. After doping of magnesium when we increase the
concentration of magnesium then peaks of copper suppress and
peaks of magnesium are dominant and it is a novelty of my work.
Raman spectroscopy.—Fig 5 shows the Raman spectra for
CuCr2O4 when doped Cu1−xMgxCr2O4 spinel in the region between
1200 to 1600 all the spectra show common feature a strong peak
around 1465 cm−1 and group of modes between 1200 to 1600 C. less
intense structure is detectable at near about 1500 in each sample
Photoluminescence.—It is worth monitoring that the physical
property of Nanoparticles changes when their dimensions get down
the nanometer scale known as the quantum size effect. For example,
quantum confinement increases the bandgap energy of CuCr2O4 that
 ECS Journal of Solid State Science and Technology, 2020 9 126005

Figure 2. XRD pattern of CuCr2O4 and Cu1−xMgxCr2O4 (a) x = 0.2 (b) x = 0.4 (c) x = 0.6 (d) x = 0.8.
 ECS Journal of Solid State Science and Technology, 2020 9 126005

Table I. Parent and doped compounds concentrations.

Sr.NO Nanoparticle Composition Designation

1 Cu0.Mg0.0Cr2O4 CCr
2 Cu0.8Mg0.2Cr2O4 CMgCr-1
3 Cu0.6Mgr0.4Cr2O4 CMgCr-2
4 Cu0.4Mg0.6Cr2O4 CMgCr-3
5 Cu0.2Mg0.8Cr2O4 CMgCr-4

has been observed from Photoluminence. The Photoluminence

originates from the recombination of the surface state. Figure 6
Photoluminence spectrum of Nanoparticle shows that excitation
wavelength 347 nm at room temperature. The spectrum exhibit two
emission peaks one is located around 380 nm in (UV region)
corresponding to near bandgap excitonic emission. Moreover, other
is located around 500 nm attribute to the presence of singly ionized
the Cu vacancies. Furthermore, the spectrum also reveals a narrow
size distribution of Nanoparticles in the luminesce powder full width
and half maximum (FWHM) only a few in nanometer.

Conclusions
Outcomes revealed that copper chromites spinel structure was
magnificently manufactured by conventional sol-gel method using
chromium, Magnesium, and copper nitrates as precursors under thermal
decomposition. This method shows promising potential in the synthesis
Figure 3. An (X = 0). of Cu1-mg MgxCr2O4 for scale-up production. Calcination temperature

Figure 4. SEM images of Cu1−xMgxCr2O4 (x = 0.2, 0.4, 0.6, 0.8).

 ECS Journal of Solid State Science and Technology, 2020 9 126005

Figure 5. EDS results of CuCr2O4 Nanoparticles.

Figure 6. EDS results of Cu1−xMgxCr2O4 (x = 0.2, 0.4, 0.6, 0.8).

Table II. Ratios of different compounds in the EDS graph. 750 °C is necessary for obtaining spinel copper chromites shows by
XRD analysis. Xrd data of the sample proved the formation of Nano-
Element Weight% Atomic % composite CuMgCr2O4 at a calcination temperature of 700 °C. SEM
images showed that the spherical particle has a diameter of 33 nm.
Ok 14.55 37.36 From PL spectra Nanostructure shows bandgap 5.02 eV and when we
Cr k 51.51 40.96 doped Magnesium in it band gap decreases and becomes 4.17 ev,
Cu k 33.94 21.95 which is associated with bandgap transition.
 ECS Journal of Solid State Science and Technology, 2020 9 126005
Figure 7. Raman Spectroscopy of parent Cu and Mg-doped in copper Chromite.
Figure 8. PL spectra of parent Cu and Mg-doped in Copper Chromites.
Acknowledgments
The authors extend their sincere appreciation to the Deanship of
Scientific Research at Princess Nourah Bint Abdulrahman University
through the Fast-track Research Funding Program.
ORCID
Sikander Azam https://orcid.org/0000-0001-5923-1127
Bakhtiar Ul Haq https://orcid.org/0000-0001-9058-2080
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