Transactions of the Indian Ceramic Society

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Optical and Photoluminescence Properties of

the MgAl2O4:M (M = Ti, Mn, Co, Ni) Phosphors:
Calcination Behavior and Photoluminescence
Mechanism

Shifa Wang , Huajing Gao , Hong Yu , Peiying Li , Yanwu Li , Chaoli Chen ,

Yong Wang , Liang Yang & Zijuan Yin

To cite this article: Shifa Wang , Huajing Gao , Hong Yu , Peiying Li , Yanwu Li , Chaoli Chen ,
Yong Wang , Liang Yang & Zijuan Yin (2020): Optical and Photoluminescence Properties of
the MgAl2O4:M (M = Ti, Mn, Co, Ni) Phosphors: Calcination Behavior and Photoluminescence
Mechanism, Transactions of the Indian Ceramic Society, DOI: 10.1080/0371750X.2020.1817789

To link to this article: https://doi.org/10.1080/0371750X.2020.1817789

Published online: 09 Dec 2020.

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 Trans. Ind. Ceram. Soc., vol. 79, no. 4, pp. 221-231 (2020).
© 2020 Indian Ceramic Society
ISSN 0371-750X (Print), ISSN 2165-5456 (Online)
http://dx.doi.org/10.1080/0371750X.2020.1817789

Optical and Photoluminescence Properties of the

MgAl2O4:M (M = Ti, Mn, Co, Ni) Phosphors: Calcination
Behavior and Photoluminescence Mechanism
Shifa Wang,1, 2, * Huajing Gao,1, 3 Hong Yu,1 Peiying Li,1 Yanwu Li,1 Chaoli Chen,1 Yong Wang,1
Liang Yang4 and Zijuan Yin1
1
School of Electronic and Information Engineering, Chongqing Three Gorges University, Chongqing, Wanzhou, 404000,
China
2
Chongqing Key Laboratory of Geological Environment Monitoring and Disaster Early-warning in Three Gorges Reservoir
Area, Chongqing Three Gorges University, Chongqing, Wanzhou, 404000, China
3
School of Science, Lanzhou University of Technology, Lanzhou 730050, China
4
Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing, 400714, China
[MS received October 23, 2019; Revised copy received July 21, 2020; Accepted August 27, 2020]

ABSTRACT
MgAl2O4:M (M = Ti, M n, Co, Ni) phosphors were successfully prepared by a
modified polyacrylamide gel method. Calcination temperature and metal 4.0
particle has significant effects on the phase transition, optical and color
properties of M gAl 2 O 4 :M phosphors. Ti, M n, Co and Ni metal particles 3.5

Eg (eV)
introduced into the MgAl 2O4 system can produce a variety of colours from
3.0
white, grayish black, blue to turquoise blue. M n, Co and Ni metal particles
added into MgAl 2O4 system can extend their light absorption to visible light
2.5
range, while the Ti metal particles clad into the system did not improve
significantly. Co metal particles appended into the MgAl 2O4 system can cause 2.0
fluorescence quenching of emission peak at 395 nm and enhancement of 600 700 800 900 1000
emission peak at 405 nm, while the Ti and M n metal particles infused into TEMPERATURE (oC)
the system can bring the enhancement of visible emission peak at 425 nm.
The fluorescence quenching of the peak at 395 nm can be ascribed to the
wavelength of Co metal particles matching the surface plasmon absorbance
band of MgAl 2O 4:M phosphor. A reduction in emission intensity at 425 nm
can be assigned to electron transfer from the conduction band (CB) of
MgAl2O4 to the CB of metal particles causing non-radiative decay.
[Keywords: Phosphor, Optical properties, Calcination temperature,
Fluorescence quenching, Non-radiative decay]

Introduction prepared Ti-doped MgAl 2O 4 nanophosphor for white

Magnesium aluminate (MgAl2O4) as a AB 2O4 spinel
type oxide has been widely studied due to its specific
combination of desirable properties like strong radiation
resistance, high thermal and chemical stability, excellent
optical properties, high photocatalytic activity, low
density (3.58 g.cm–3), good mechanical strength at any
inconstant temperature. 1–9 MgAl 2 O 4 as a potential
photoluminescence material, has gradually come into
people’s visions and received wide attention. 3, 10–14
However, MgAl2O4 requires high energy light excitation
to produce luminescence because it is a wide-band gap
semiconductor (E g = 3.923 eV). 3 To enhance the
photoluminescence properties of MgAl2O4, metal ions
doped MgAl2O4 have been developed.15–18 Lim et al.19
*Corresponding author; em ail: wangshifa2006@yeah.net
emission by combustion method. Song et al. 20
synthesized MgAl2O4:Mn2+ phosphor by facile solid state
reaction method, which showed a strong green emission.
In our preliminary works, Mn or (Mn, Ce) activated
MgAl2O4:Mn or MgAl2O4:Mn:Ce phosphor prepared by
modified polyacrylamide gel method exhibited two
emission peaks at 470 and 500 nm.21 Kobylinska et al.22
found that nanocrystalline MgAl2O4:Co 2+ prepared by
modified Pechini method exhibited an emission band in
the range of 630-820 nm. Jouini et al.23 synthesized Ni2+-
doped MgAl2O4 spinel by micro-pulling-down method,
which exhibited an excellent infrared emission.
In addition to doping metal ion to enhance the
luminescence of single phase materials, metal particle
modification has been developed in recent years to
improve the luminescence of single phase materials.

VOL. 79 (4) OCTOBER – DECEMBER 2020 221

Magnetic Fe/ZnO composites synthesized by
hydrothermal method by Yang et al.24 exhibited improved
photoluminescent properties than ZnO. Im et al. 25
prepared Au/ZnO composites that exhibited a strong
ultraviolet emission. Inspired by this, magnesium
aluminate can also be studied by attaching different metal
particles to enhance its photoluminescence properties.
Li et al.26 synthesized thermally stable Pt nanoparticles
on MgAl 2 O 4 support materials which exhibited an
excellent catalytic activity. As Ti, Mn, Co or Ni particles
can realize emission colour tunable of host material
without using rare earth or noble metal elements due to
charge-transfer transitions,27–29 Ti, Mn, Co or Ni particles
and magnesium aluminate were used to prepare
MgAl2O4:M (M = Ti, Mn, Co, Ni) phosphors. However,
the physicochemical properties of MgAl2O4:M (M = Ti,
Mn, Co, Ni) phosphors have not been studied yet.
Therefore, it is interesting to prepare and study the
physicochemical properties of MgAl2O4:M (M = Ti, Mn,
Co, Ni) phosphors.
In this paper, MgAl 2 O 4:M (M=Ti, Mn, Co, Ni)
phosphors have been prepared by a modified
polyacrylamide gel method. The calcination behavior and
effect of different kinds of metals on phase stability, phase
transition, optical and colour properties of MgAl2O4:M
(M = Ti, Mn, Co, Ni) phosphors have been systematically
investigated. In addition, the fluorescence properties of
as-prepared MgAl2O4:M (M = Ti, Mn, Co, Ni) phosphors
have been discussed by confocal Raman system using
a He-Cd laser (325 nm). Mechanism for these
fluorescence changes has been elaborated in the context
of an energy band diagram of metal enhanced
fluorescence for the MgAl2O4:M (M = Ti, Mn, Co, Ni)
phosphor established on the basis of experimental results
and theoretical analysis.
Experimental
Materials
Magnesium nitrate hexahydrate (Mg(NO3)2.6H2O) and
aluminium trichloride hexahydrate (AlCl3.6H 2O) were
purchased from DaMao Chem Ltd, Tianjing. The organic
reagents including citric acid (C 6H8O 7, AR), glucose
(C 6H12O6.H2O, 99%), acrylamide (C 3H 5NO, AR), and
N, N’-methylene-bisacrylamide (C 7H10N2O2, 99%) were
purchased from Kemiou Chem Ltd, Tianjing. Ti, Mn, Co
and Ni powders were purchased from Shanghai Aladdin
Biochemical Technology Co., Ltd and used without further
purification.
Synthesis of MgAl2O4:M Phosphors
The chemical route for preparation of MgAl2O 4:M
(M = Ti, Mn, Co, Ni) phosphors with mass ratio of
MgAl2O4:M = 9:1 by modified polyacrylamide gel method
is shown in Fig. 1. The metal powders (Ti, Mn, Co or Ni)
were dispersed in 20 mL deionized water by ultrasound
and labelled as solution A. Ultrasonic frequency,
ultrasonic power, ultrasonic time and temperature were
40 kHz, 180 W, 30 min and room temperature,
222
Fig. 1 – Chemical route for the preparation of MgAl 2O4:M
(M = Ti, Mn, Co, Ni) phosphors
respectively. Stoichiometric amounts of Mg(NO3)2.6H2O
and AlCl3.6H2O were dissolved in deionized water to obtain
a final solution of 0.015 mol.L–1 total cations and was
labelled as solution B. Subsequently, solution B was
slowly poured into solution A and ultrasonicated for half
an hour. Then, a stoichiometric amount of citric acid as
chelating agent was added into the solution in the mole
ratio of 1.5:1 with respect to the total cations (Mg2+ and
Al3+) to complex the cations. After that, 20 g glucose
was dissolved into the solution, and then acrylamide and
N, N’-methylene-bisacrylamide monomers were added
into the solution. After the organic reagents were
completely dissolved, the solution was transferred to a
magnetic stirrer and heated to 80oC for polymerization
to obtain a gel. The gel was then dried at 120oC for 24 h
in a thermostat drier. The obtained xerogel precursor was
ground into powder and some powder was calcined at
600o, 700o, 800o, 900o and 1000oC for 5 h in air to prepare
the objective products.
Sample Characterization
MgAl2O 4:M (M=Ti, Mn, Co, Ni) xerogel precursor
calcined at different temperatures were analyzed by
X-ray diffractometer (DX-2700) with CuK radiation at a
wavelength of 1.5406 Å operated at 40 kV and 30 mA.
Surface morphology of the synthesized MgAl 2O 4:M
(M = Ti, Mn, Co, Ni) xerogel calcined at 800 oC was
characterized by a field emission scanning electron
microscope (FE-SEM). Fourier transform infrared (FTIR)
spectra in the range of 400-4000 cm–1 were recorded using
a Bruker IFS 66 v/S spectrometer. UV-Vis diffuse
reflectance spectra of the samples were examined through
a Shimadzu UV-2500 UV-Visible spectrophotometer with
an integrating sphere attachment using BaSO4 as the
reference. The colour coordinates (L*, a*, b*), hue angle
(Ho), chroma parameter (c*) and total colour difference
(ECIE*) of MgAl2O4:M (M = Ti, Mn, Co, Ni) xerogel powders
calcined at different temperatures can be obtained from
literature30–32 and Eqns (1)-(3).
Ho = arctan(b*/a*) ..(1)
(a*)22 +(b(b*)
c* = (a*) *)222 ..(2)
* =
ECIE (L*)22 +(a*)
(a*) (a*)2 2+(b(b*)
*)222 ..(3)
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 The UV-Vis absorption spectra of MgAl2O4:M (M = Ti,
Mn, Co, Ni) xerogel powders calcined at different
temperatures can be calculated by the Kubelka-Munk
(K-M) theory. The bandgap energy (E g ) values of
MgAl2O4:M (M = Ti, Mn, Co, Ni) samples were evaluated
by the following equation:33–36
(F(R)h)n = A(h–Eg) ..(4)
where h, , n, E g and A are the Planck constant,
frequency, 2, band gap energy value, and absorption
coefficient, respectively. The fluorescence spectra were
collected at room temperature in a confocal Raman
system using a He-Cd laser (325 nm, RGB laser system,
NovaPro 30 mW, Germany).
crystallinity MgAl2O4 + MnO2. XRD results of MgAl2O4:Mn
xerogel powders calcined at different temperatures
indicate that the Mn powder in the MgAl2O4:Mn sample
promotes the formation of MgAl2O4.
Figure 2c shows the XRD patterns of MgAl2O4:Co
xerogel powders calcined at different temperatures. For
MgAl2O4:Co xerogel powders calcined at 600o-800oC, the
phenomenon is similar to Fig. 2b. When MgAl2O4:Co xerogel
powders are calcined at 900o or 1000oC, a CoO phase
(JCPDS card no. 43-1004) appears. For MgAl2O4:Ni sample
(Fig. 2d), the phenomenon is in line with MgAl2O4:Co
(a)

INTENSITY (a.u.)
Results and Discussion
Structure Analysis
To study the effects of metal particle and calcination
temperature on the phase purity and structure of spinel
type MgAl 2 O 4 oxides, XRD analyses of MgAl 2O 4 :M
xerogel powders calcined at different temperatures were 20 30 40 50 60 70 80
carried out. XRD patterns of MgAl2O4:Ti xerogel powders 2 (degree)
calcined at different temperatures are shown in Fig. 2a.
MgAl2O4:Ti xerogel powder calcined at 600oC exhibits (b)
an amorphous phase, which is similar to the MgAl2O4
xerogel powder calcined at 600oC. For MgAl2O4:Ti xerogel INTENSITY (a.u.)
powder calcined at or above 700oC, the curves are well
agreed with the standard PDF card of MgAl2O4 (JCPDS
card no. 21-1152) and rutile TiO2 (JCPDS card no. 21-1276).
The result implies that the Ti powder in the MgAl2O4:Ti
sample is easily oxidized at high temperature.
Figure 2b shows the XRD patterns of MgAl2O4:Mn 20 30 40 50 60 70 80
xerogel powders calcined at different temperatures. 2 (degree)
MgAl2O4:Mn xerogel powder calcined at 600oC shows
(c)
an obvious MgAl2O4 phase. For MgAl2O4:Mn xerogel
powders calcined at 700o-900oC, only MgAl2O4 phase can
INTENSITY (a.u.)

be found. Mn-modified MgAl2O4 did not give rise to any

change in XRD peak shapes and positions compared to
pure MgAl2O4.3 For MgAl2O4:Mn xerogel powders calcined
at 1000 oC, a new phase of MnO 2 (JCPDS card no.
50-0866) can be observed. In addition, the intensity of
diffraction peaks and crystallinity of MgAl2O4 were further
enhanced. A similar phenomenon can also be observed 20 30 40 50 60 70 80
2 (degree)
through previous reports.37, 38 The Mn particle is easy to
be wrapped inside the precursor of MgAl2O4 due to the (d)
low content of Mn particle. The thick MgAl2O4 coating
INTENSITY (a.u.)

layer prevents oxidation of Mn particles during low

temperature sintering, and it is difficult to detect the
internal information of samples by XRD. Therefore, no
phase associated with Mn ion was observed during low
temperature sintering process. W hen MgAl 2 O 4 :Mn
xerogel is sintered at high temperature, organic impurities
in the MgAl2O4 precursor are removed and Mn particles
20 30 40 50 60 70 80
are oxidized to MnO2. Phase transformation sequence 2 (degree)
of MgAl2O4:Mn xerogel powders during calcining is as Fig. 2 – XRD patterns of MgAl2O4:M xerogel powders calcined
follows: low crystallinity MgAl 2O 4 + Mn particles  at different temperatures: (a) MgAl 2O 4:Ti, (b) MgAl 2O4:Mn,
moderate crystallinity MgAl2O4 + Mn particles  high (c) MgAl2O4:Co and (d) MgAl2O4:Ni

VOL. 79 (4) OCTOBER – DECEMBER 2020 223

sample. A new NiO phase with the standard PDF card
no. 47-1049 appears in the MgAl2O4:Ni xerogel powders
calcined at 900o or 1000oC. It can be noted that no new
peak appears in the XRD pattern of MgAl 2 O 4 :Ni.
Comparison of all MgAl2O4:M xerogel powders calcined
at 600oC shows that MgAl2O4:Ti is amorphous and the
rest are crystalline MgAl2O4. The intensity of XRD peak
and the crystallinity of MgAl2O4 phase increases with
increasing calcination temperature.
Infrared Spectroscopy
FTIR spectral analysis was performed to study the
metal oxidation process, spinel oxide formation and the
peak at 770 and 538 cm –1 can be ascribed to Co-O
stretching and MO-H bending regions, respectively.
Based on the results of XRD analysis, the absorption
peak at 770 cm–1 can be attributed to the generation of
Co(OH)2. FTIR spectra of MgAl2O4:Ni xerogel powders
calcined at different temperatures are shown in Fig. 3d.
The absorption peaks at 709 and 526 cm–1 can also be
attributed to the Mg-O stretching vibration, and the AlO6
group of spinel MgAl2O4, respectively. The new peak at
428 cm–1 in the MgAl2O4:Ni xerogel powders calcined at
1000oC can be assigned to the Ni-O band in NiO.55 As
(a)

RELATIVE TRANSMITANCE
functional groups of as-prepared samples. Figure 3 shows
the FTIR spectra of MgAl2O4:M (M = Ti, Mn, Co, Ni)
xerogel powders calcined at different temperatures. For

(a.u.)
all samples, two absorption peaks observed at 3441 and
1640 cm–1 are assigned to stretching and bending modes
of adsorbed water, respectively.39–41 Figure 3a shows the
FTIR spectra of MgAl2O4:Ti xerogel powders calcined at
different temperatures. Three absorption peaks at 2925,
4000 3500 3000 2500 2000 1500 1000 500
693 and 519 cm–1 always appeared in the sample, except WAVE NUMBER (cm–1)
the absorption peak of adsorbed water. The absorption
(b)
peaks at 2925, 693 and 519 cm–1 can be ascribed to –CH

RELATIVE TRANSMITANCE
stretching vibration in –CH and –CH2,42 Mg–O stretching
vibration,43, 44 and AlO6 group of spinel MgAl2O4,45, 46
respectively. The peak of AlO6 group at 519 cm–1 is blue
(a.u.)

shifted ~23 cm –1 compared with the literature;3 this is

caused by the interaction of MgAl2O4 and TiO2. According
to the literature,47 the low energy bands at 786 and 564
cm–1 can be attributed to the stretching vibration of Ti-O
bond in titania. Therefore, the absorption peaks at 519 4000 3500 3000 2500 2000 1500 1000 500
cm–1 can also be ascribed to the stretching vibration of WAVE NUMBER (cm–1)

Ti-O bond in titania. In addition, organic peaks at 2834, (c)

RELATIVE TRANSMITANCE

1408 and 1117 cm –1 disappear after high temperature

calcination, while a new absorption peak appears at 826
cm–1, which can be attributed to the stretching vibration
(a.u.)

of Ti-O bond in titania. These absorption peaks at (2834,

1408) and 1117 cm–1 can be ascribed to carbonate ions48
and C–O stretching vibration,49 respectively.
For MgAl 2 O 4 :Mn sample (Fig. 3b), a similar
phenomenon can be observed. Mahmoudian et al. 50
reported that MnO2 nanotubes prepared by a simple 4000 3500 3000 2500 2000 1500 1000 500
WAVE NUMBER (cm–1)
single-step hydrothermal process exhibited two absorption
peaks at 720 and 540 cm –1 corresponding to the (d)
RELATIVE TRANSMITANCE

stretching vibrations of Mn-O-Mn and Mn-O bonds,

respectively. The absorption peaks at 801 and 510 cm–1
can also be assigned to the stretching vibrations of
(a.u.)

Mn-O-Mn and Mn-O bonds in MnO2. Figure 3c shows

the FTIR spectra of MgAl2O4:Co xerogel powders calcined
at different temperatures. Zhou et al.51 found that well-
aligned CoO nanowire possessed an absorption peak at
557 cm–1 corresponding to Co-O stretching in CoO. In
4000 3500 3000 2500 2000 1500 1000 500
this case, the peak at 538 cm–1 can be assigned to Co-O WAVE NUMBER (cm–1)
stretching in CoO. The absorption peak at 770 cm–1 is Fig. 3 – FTIR spectra of MgAl2O4:M xerogel powders calcined
probably due to Co 3 O 4 existing in the MgAl 2 O 4:Co at different temperatures: (a) MgAl 2O 4:Ti, (b) MgAl 2O4:Mn,
sample.52 According to the literature,53, 54 the absorption (c) MgAl2O4:Co and (d) MgAl2O4:Ni

224 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

can be seen from Fig. 3, when the MgAl2O4:M xerogel
powders were calcined at 600oC, no peak was observed
in the low wave number range for MgAl2O4:Ti sample,
while absorption peaks of Mg-O and Al-O were observed
for other samples. The result also confirms that Ti powder
suppresses the formation of MgAl2O4, while Mn, Co and
Ni powders accelerate the formation of MgAl2O4.
Surface Morphology
Figure 4 shows the SEM images of MgAl 2O 4:M
xerogel powders calcined at 800oC. When Ti particles
are introduced into MgAl 2 O 4 system, their surface
morphology is similar to honeycomb (Fig. 4a). It is
noteworthy that the MgAl 2O4 synthesized by similar
method exhibits highly dispersed nanoparticles.3 It can
be seen that the influence of metal particles on the
surface morphology of samples are very significant. The
SEM image of MgAl2O4:Mn xerogel powders calcined at
800oC (Fig. 4b) shows a shape similar to the back of a
mushroom. A layered honeycomb morphology can be
observed for MgAl2O4:Co xerogel powders calcined at
800oC (Fig. 4c). For MgAl2O4:Ni xerogel powders calcined
at 800oC, an instant noodle shape can be observed (Fig.
4d). Although different metal particles have different effects
on the morphology of samples, all metal particles promote
the agglomeration and bonding of MgAl2O4 particles.
(a) (b)
(c) (d)
Fig. 4 – SEM images of MgAl2O4:M xerogel powders calcined
at 800oC: (a) MgAl2O4:Ti, (b) MgAl2O4:Mn, (c) MgAl2O4:Co and
(d) MgAl2O4:Ni
Real Photos
Figure 5 shows the real photos of MgAl2O4:M xerogel
powders calcined at different temperatures. As can be
seen from Fig. 5, the colour of samples changes
significantly with the increase of calcination temperature.
For MgAl2O4:Ti xerogel powder calcined at 600oC, an ash
black colour can be observed due to the amorphous
phase (Fig. 5a). W ith the increase of calcination
temperature, the samples turned bright white, the sample
sintered at 800oC being the brightest white. Figure 5b
shows the real photos of MgAl2O4:Mn xerogel powders
calcined at different temperatures. When the Mn metal
VOL. 79 (4) OCTOBER – DECEMBER 2020
(a) (b)
(c) (d)
Fig. 5 – Real photos of MgAl 2O4:M xerogel powders calcined
at different temperatures: (a) MgAl 2O 4:Ti, (b) MgAl 2O4:Mn,
(c) MgAl2O4:Co and (d) MgAl2O4:Ni; 1, 2, 3, 4 and 5 represent
600o, 700o, 800o, 900o and 1000oC, respectively
particles are introduced into the MgAl2O4 system, the
main colour of the sample is grayish black. A brown yellow
colour can be found for the MgAl2O4:Mn xerogel powders
calcined at 600oC, which is ascribed to the interaction of
low crystallinity MgAl2O4 and small amount of organic
impurities. When Co metal particles are introduced into
the MgAl2O4 system, the colour of the sample is blue
(Fig. 5c). At low calcination temperature, the colour is
light green or light blue due to the interaction of organic
impurities, metal particles and MgAl 2 O 4 with low
crystallinity. After Ni metal particles are introduced into
MgAl2O4, turquoise blue coloured samples are obtained
(Fig. 5d). It can also be seen that the colour of MgAl2O4:Ni
samples change significantly with the increase of
calcination temperature.
Optical Properties
To study the optical and colour properties of
MgAl2O4:M samples, UV-Vis diffuse reflectance spectra
of MgAl2O4:M samples were measured by a UV-Visible
spectrophotometer. Figure 6a displays the UV-Vis diffuse
reflectance spectra of MgAl 2O 4:Ti xerogel powders
calcined at different temperatures. For MgAl2O4:Ti xerogel
powders calcined at 600oC, the lowest reflectance was
observed due to the amorphous phase, which is
consistent with the literature. 3 The reflectance for all
samples decreased first and then increased continuously
with the increase of wavelength. The colour coordinates,
hue angle, total colour difference and chroma of MgAl2O4:Ti
xerogel powders calcined at different temperatures are
presented in Table I. The L* and ECIE* values of MgAl2O4:Ti
increased with increasing calcining temperature, the a*,
b* and c* values showed the opposite trend, while a
random behavior is observed for the Ho value. This trend
is similar to MgAl 2O 4 synthesized by gamma-ray
irradiation assisted polyacrylamide gel method. 3 The
white component (L*) value for MgAl 2O 4:Ti xerogel
powders calcined at 700o-1000oC was more than 94, but
only 38.176 for that calcined at 600 oC. The result
indicates that MgAl2O4:Ti xerogel powder calcined at 700o-
225
1000oC exhibits a bright white, while the powder calcined Table I : Colour coordinates and E g values of MgAl 2O4:Ti
at 600oC shows a light black colour (Fig. 5a). The L* xerogel powders calcined at different temperatures
value for MgAl2O4:Ti xerogel powders calcined at 800oC
Calcined Colour coordinates Eg
is larger than other samples, which means the sample at value
possesses the brightest white. (oC) L* a* b* c* Ho ECIE * (eV)
Figure 6b shows the UV-Vis absorption spectra of
MgAl 2 O 4 :Ti xerogel powders calcined at different 600 38.176 5.647 13.674 14.794 67.561 40.942 2.141
temperatures. For MgAl2O4:Ti xerogel powders calcined 700 94.807 0.115 4.503 4.504 88.537 94.914 3.556
at 600oC, a wide absorption band in the wavelength range
800 97.243 0.099 3.840 3.841 88.523 97.319 3.797
of 200 to 850 nm can be found, which is similar to
MgAl2O4.3 For MgAl2O4:Ti xerogel powders calcined at 900 95.684 0.127 7.504 7.505 89.030 95.978 3.759
700o-1000oC, four absorption peaks at (244/241/230/226), 1000 96.463 –0.210 5.105 5.109 –87.644 96.598 3.738
270, 385 and 460 nm can be observed. These absorption
peaks at (244/241/230/226), 270, 385 and 460 nm can
be assigned to F center,56 anion vacancies F+ center,56 of MgAl2O4:Ti samples were obtained from the intercept
band-band transition of TiO 2,57 and O 2–-Al3+ charge of the straight line of (F(R)h)2 vs (h) and are presented
transition, 58 respectively. The presence of TiO 2 in in Table I. Eg values of MgAl2O4:Ti sample increased first
MgAl2O4:Ti sample was confirmed by UV-Vis analysis. and then decreased with increasing calcination
The result is consistent with the XRD result. temperature. The increase of Eg value is possibly due to
Figure 6c shows the Eg values of MgAl2O4:Ti xerogel the decrease of organic impurities in the MgAl2O4:Ti
powders calcined at different temperatures. The Eg values sample with increasing calcination temperature. When
the calcination temperature is further increased, the
crystallinity of MgAl2O4:Ti sample increases, leading to
(a)
100 the decrease of Eg value of MgAl2O4:Ti sample.
Figure 7a shows the UV-Vis diffuse reflectance spectra
REFLECTANCE (%)

80
of MgAl2O4:Mn xerogel powders calcined at different
60 temperatures. The spectra of MgAl 2 O 4:Mn xerogel
powders calcined at different temperatures show similar
40
features: in the ultraviolet region, the reflectance
20 decreased with increasing wavelength, while the
reflectance in the visible region showed the opposite trend.
0
200 300 400 500 600 700 800
Table II presents the colour coordinates, hue angle, total
WAVELENGTH (nm) colour difference and chroma of MgAl2O4:Mn xerogel
1.6
(b)
powders calcined at different temperatures. As can be
1.4 seen from Table II, the L*, a* and E CIE* values of
ABSORBANCE (a.u.)

1.2 MgAl2O4:Mn decreased first and then increased with

1.0 increasing calcination temperature, while a random
0.8
behavior is observed for b*, c* and H o values. For
MgAl2O4:Mn xerogel powders calcined at 600oC, the higher
0.6
a* and b* values than those of other samples led the
0.4
sample to appear brown yellow (Fig. 5b). The black
0.2
component (L*) increased with increasing calcination
0.0
200 300 400 500 600 700 800
temperature in the temperature range of 700o-1000oC. This
WAVELENGTH (nm) result can correspond with the real photos one by one.
4.0 Figure 7b depicts the UV-Vis absorption spectra of
(c)
MgAl2 O 4:Mn xerogel powders calcined at different
3.5
temperatures. All MgAl2O4:Mn samples exhibit extended
light absorption capacity to the visible region, which
Eg (eV)

means the photocatalytic activity of MgAl2O4 could be

3.0
enhanced under simulated solar irradiation. Further study
on the photocatalytic activity and photocatalytic
2.5 mechanism of MgAl2O4:Mn sample for photocatalytic
degradation of organic dye is still in progress and will be
2.0 reported elsewhere. The Eg values of MgAl2O4:Mn xerogel
600 700 800 900 1000
TEMPERATURE (oC) powders calcined at different temperatures are shown in
Fig. 6 – (a) UV-Vis diffuse reflectance spectra, (b) UV-Vis Fig. 7c and Table II. Although the Eg value of MgAl2O4:Mn
absorption spectra and (c) E g values of MgAl 2O4:Ti xerogel sample changed with the change of calcination
powders calcined at different temperatures temperature, it does not change as much as that of

226 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 40 temperatures. In two different wavelength ranges of 200-
(a)
35 500 and 500-850 nm, the reflectance for all samples
REFLECTANCE (%)
30 decreased first and then increased continuously with
25 increasing wavelength. The colour coordinates of
20 MgAl2 O 4 :Co xerogel powders calcined at different
15
temperatures (Table III) exhibit a random behavior. For
10
MgAl2O4:Co xerogel powder calcined at 800oC, the blue
component (a*) is the largest of all samples, which means
5
the sample shows the brightest blue as shown in Fig.
0
200 300 400 500 600 700 800 5c. UV-Vis absorption spectra of MgAl2O4:Co xerogel
WAVELENGTH (nm) powders calcined at different temperatures are shown in
1.4 Fig. 8b. In the UV region, two absorption peaks at 233
(b) and 350 nm can be observed corresponding to F center
1.2 of MgAl2O4,3 and the presence of Al3+ ion in octahedral
ABSORBANCE (a.u.)

sites,59 respectively. In the visible region, three obvious

1.0
absorption peaks at 550, 588 and 631 nm can be assigned
0.8 to the spin allowed transitions for 4A 2(F)4 T1(P) and
4
A2(F)2T(G) in Co2+.60–62 The Eg values of MgAl2O4:Co
0.6
xerogel powders calcined at different temperatures are
0.4 shown in Fig. 8c and Table III. The curves for MgAl2O4:Co
xerogel powders calcined at different temperatures can
200 300 400 500 600 700 800
WAVELENGTH (nm) be linearly fitted into 2 lines with the intercepts at (2.126,

100
(c) (a)
2.75 90
REFLECTANCE (%) 80
70
2.50 60
Eg (eV)

50
40
2.25
30
20
2.00 10
0
600 700 800 900 1000 200 300 400 500 600 700 800
TEMPERATURE (oC) WAVELENGTH (nm)

Fig. 7 – (a) UV-Vis diffuse reflectance spectra, (b) UV-Vis 1.6 (b)
absorption spectra and (c) Eg values of MgAl 2O4:Mn xerogel
ABSORBANCE (a.u.)

1.4
powders calcined at different temperatures
1.2
1.0
Table II : Colour coordinates and E g values of MgAl 2O4:M n
0.8
xerogel powders calcined at different temperatures
0.6
Calcined Colour coordinates Eg 0.4
at value 0.2
(oC) L* a* b* c* Ho ECIE * (eV) 0.0
200 300 400 500 600 700 800
600 45.499 6.793 16.373 17.726 67.467 48.830 2.243 WAVELENGTH (nm)
3.75
700 45.410 3.919 14.874 15.382 75.239 47.944 2.008 (c)
3.50
800 46.009 5.288 15.345 16.231 70.986 48.788 2.298 3.25
900 46.582 5.428 13.744 14.777 68.449 48.870 2.783
Eg (eV)

3.00

1000 49.833 6.125 15.952 17.087 68.995 52.681 2.699 2.75

2.50
2.25
MgAl 2O 4:Ti sample, which may be caused by the
2.00
introduction of Mn metal particles accelerating the
600 700 800 900 1000
formation of MgAl2O4 phase and the interaction between TEMPERATURE (oC)
MgAl2O4 and Mn oxides.
Fig. 8 – (a) UV-Vis diffuse reflectance spectra, (b) UV-Vis
Figure 8a shows the UV-Vis diffuse reflectance spectra absorption spectra and (c) E g values of MgAl 2O4:Co xerogel
of MgAl2O4:Co xerogel powders calcined at different powders calcined at different temperatures

VOL. 79 (4) OCTOBER – DECEMBER 2020 227

 Table III : Colour coordinates and E g values of MgAl 2O4:Co xerogel powders calcined at different temperatures

Calcined Colour coordinates Eg values (eV)

at
(oC) L* a* b* c* H* ECIE *

600 55.328 –5.170 14.401 15.301 –70.252 57.405 2.126 2.689

700 72.247 –10.985 4.091 11.722 –20.426 73.192 2.439 3.460
800 49.301 –20.585 –2.395 20.724 6.636 53.480 2.660 3.559
900 60.100 –10.694 –2.941 11.091 15.377 61.044 2.311 3.409
1000 58.863 –12.580 –6.716 14.260 28.096 60.566 2.561 3.531

2.439, 2.660, 2.311, 2.561 eV) and (2.689, 3.460, 3.559,
3.409, 3.531 eV), respectively, corresponding to the E g
values of CoO63 and MgAl2O4.3
Figure 9a shows the UV-Vis diffuse reflectance spectra
of MgAl 2O4:Ni xerogel powders calcined at different
temperatures. For all the samples, five reflection peaks
at <200, 350, 520, 650 and >850 nm can be observed.
(a)
100
REFLECTANCE (%)
For MgAl2O4:Ni xerogel powder calcined at 1000oC, two
new reflection peaks at 450 and 600 nm can be found
due to high crystallinity. Table IV shows the colour
coordinates of MgAl2O4:Ni xerogel powders calcined at
different temperatures. As can be seen from Table IV,
the absolute values of b* and H o decreased with
increasing calcination temperature, while a random
behavior is observed for L*, a*, c* and ECIE* values. Figure
9b shows the UV-Vis absorption spectra of MgAl2O4:Ni
xerogel powders calcined at different temperatures. The

80 absorption peaks at 210 and 274 nm can be ascribed to

F center and anion vacancies F+ center, respectively.56
60
Two absorption bands at 388 and 644 nm can be ascribed
40 to the spin-allowed transitions of 3A 2(3F)3T1(3P) and
3
A2(3F)3T1(3F), respectively.23 In addition, the intensity
20
of absorption band for the MgAl2O4:Ni xerogel powder
0 calcined at 600oC is the strongest among all the samples
200 300 400 500 600 700 800 due to low crystallinity and a few organic peaks in the
WAVELENGTH (nm)
sample. Figure 9c and Table IV show the Eg values of
1.2 (b)
MgAl 2O 4:Ni xerogel powders calcined at different
temperatures. It can be seen that the E g value of
ABSORBANCE (a.u.)

1.0
MgAl2O4:Ni sample increased first and then decreased
0.8 with increasing calcination temperature.
0.6
Table IV : Colour coordinates and Eg values of MgAl 2O4:Ni
0.4 xerogel powders calcined at different temperatures
0.2
Calcined Colour coordinates Eg
0.0 at value
200 300 400 500 600 700 800
(oC) L* a* b* c* Ho ECIE * (eV)
WAVELENGTH (nm)

4.2 600 90.312 –7.335 14.555 16.299 –63.254 91.771 3.738

(c)
4.1
700 91.630 –7.571 3.464 8.326 –24.586 92.007 4.108
800 93.619 –7.168 2.856 7.716 –21.724 93.936 4.006
4.0
Eg (eV)

900 93.059 –7.748 2.016 8.006 –14.585 93.403 3.871

3.9 1000 91.614 –8.580 1.758 8.758 –11.579 92.032 3.766

3.8
It can be seen from Tables I, II, III and IV, that Eg values
3.7 of MgAl 2O 4:M xerogel powders calcined at different
600 700 800 900 1000
TEMPERATURE (oC) temperatures are relatively consistent, while the colour
Fig. 9 – (a) UV-Vis diffuse reflectance spectra, (b) UV-Vis
coordinates exhibit an erratic behavior due to specular
absorption spectra and (c) E g values of MgAl 2O4:Ni xerogel reflection, potential effect of aggregation and Ti, Mn, Co or
powders calcined at different temperatures Ni substitution contradicting the postulates of ligand field

228 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

theory.64 Based on the analysis of optical properties, it
can be concluded that the introduction of Mn, Co or Ni
metal particles into MgAl2O4 system can extend their light
absorption capacity to visible light range, while introduction
of Ti metal particles did not improve the light absorption
capacity significantly.
Photoluminescent Properties
The photoluminescent properties of MgAl 2O 4:M
samples were studied at room temperature in a confocal
Raman system using a He-Cd laser (325 nm) and are
presented in Fig. 10. Figure 10a shows the fluorescence
spectra of MgAl2O4:Ti xerogel powder calcined at 800oC.
16000
15000
(a)
INTENSITY (a.u.)
The spectra shows a broad emission band in the
wavelength range of 385-445 nm, which can be resolved
using three Gaussian peaks at 395, 405 and 425 nm.
The peaks can be ascribed to the FMg center or exciton
recombination, 25, 65 electronic transition from defect-
associated trap states,25 and the defect energy level,65, 66
respectively. Compared with the literature,3 the Ti metal
particles introduced into MgAl2O4 system change the
intensities of UV emission peak at 395 nm and visible
emission peak at 425 nm and the position of visible
emission peak at 405 nm. The fluorescence spectra of
MgAl2O4:Mn xerogel powder calcined at 800oC (Fig. 10b)
can also be resolved using three Gaussian peaks at 395,
408 and 425 nm. The relative intensity of peak at 425 nm
for MgAl2O4:Ti or MgAl2O4:Mn sample is higher than that
of MgAl2O4 sample.3 However, the fluorescence spectra

14000
of MgAl2O4:Co xerogel powder calcined at 800oC (Fig.
13000
10c) can be resolved using only two Gaussian peaks at
12000
395 and 425 nm. The ultraviolet emission band centered
11000
at 395 nm is dramatically quenched due to Co metal
10000 particles attachment, which means that Co metal
9000 particles in MgAl 2O 4 act as quencher. The effect is
380 390 400 410 420 430 440 450 possibly due to absorption of emitted UV fluorescence
WAVELENGTH (nm)
by the Co metal particles. In addition, the intensity ratio
9000
(b) of peaks at 405 and 425 nm for the MgAl2O4:Co sample
8000
is higher than that of MgAl 2O 4 :Ti and MgAl 2 O 4:Mn
INTENSITY (a.u.)

7000
samples. When Ni metal particles are introduced into
6000
MgAl2 O 4 system, the emission band of MgAl 2O 4 :Ni
5000
sample is similar to MgAl2O4:Co sample except that the
4000
UV peak is not quenched, as shown in Fig. 10d.
3000
2000 Photoluminescent Mechanism
1000 To understand the photoluminescent mechanism of
370 380 390 400 410 420 430
WAVELENGTH (nm) MgAl2O4:M phosphor, the energy band diagram of metal-
10000 enhanced fluorescence for the MgAl2O4:M (M = Ti, Mn,
(c)
9000
Co, Ni) phosphor is shown in Fig. 11. For the MgAl2O4
semiconductor materials, the conduction band (CB) and
INTENSITY (a.u.)

8000 valence band (VB) potentials can be obtained on the

7000
basis of literature. 67–73 Upon irradiation, one electron
transition occurs from the VB of MgAl2O4 onto the level
6000 of organic impurities due to E g>exc. Subsequently, the
5000 electron (e–) will be driven by continued transition from
the level of organic impurities to the CB of MgAl2O4.25, 74, 75
390 400 410 420 430 440 450
WAVELENGTH (nm) The CB electrons of MgAl2O4 drops down to the lower
12000
(d)
11000
INTENSITY (a.u.)

10000

9000

8000

7000

380 390 400 410 420 430 440 450

WAVELENGTH (nm)
Fig. 10 – Fluorescence spectra of M gAl 2O 4:M xerogel
powders calcined at 800 oC: (a) MgAl2O4:Ti, (b) MgAl 2O4:Mn, Fig. 11 – Energy band diagram of metal-enhanced
(c) MgAl2O4:Co and (d) MgAl2O4:Ni fluorescence for the MgAl2O4:M (M = Ti, Mn, Co, Ni) phosphor

VOL. 79 (4) OCTOBER – DECEMBER 2020 229

energy level by loss of energy under vibration relaxation
conditions. The electrons in the lower energy level can
radiatively decay back to the VB of MgAl2O4 via excitonic
recombination to emitting UV light (3.14 eV vs 295 nm).
On the other hand, the electrons can transfer to low-
lying MgAl2O4 defect levels or oxygen vacancy level and
then radiatively decay to the VB of MgAl2O4 to emitting
visible light (3.06 and 2.92 eV). Some of these UV
emission bands at 395 nm can be absorbed by the metal
particles such as Co metal particles, and this process
leads to reduced intensity or fluorescence quenching of
UV emission peak as the wavelength of Co metal particles
matches with the surface plasmon absorbance band of
MgAl2O4:M phosphor, as observed in Fig. 10c. Bhatti
et al.76 and Yang et al.24 reported that magnetic Fe/ZnO
composites exhibit a fluorescence quenching of UV
emission peak due to the Fe ions in ZnO that act as a
quencher. Transfer of electrons from the CB of MgAl2O4
to the CB of metal particles such as Co and Ni metal
particles will cause non-radiative decay and a reduction
in intensity of visible emission peak at 425 nm, as
observed in Figs. 10c and 10d.
Conclusions
A modified polyacrylamide gel method has been
successfully used to prepare MgAl2O4:M (M = Ti, Mn,
Co, Ni) phosphors. The effects of calcination temperature
and the different kinds of metals on the phase stability,
phase transition, surface morphology, light absorption
capacity, colorimetric, and luminescent properties of
MgAl2O4:M (M = Ti, Mn, Co, Ni) phosphors have been
systemically investigated. XRD result and FTIR spectra
have provided the evidence for phase evolution of different
metal particles in the MgAl2O4 system. SEM images of
MgAl2O4:Ti, MgAl2O4:Mn, MgAl2O4:Co and MgAl2O4:Ni
phosphors show honeycomb, mushroom, layered
honeycomb, and instant noodle like morphology,
respectively. Optical properties and real photos show that
MgAl2O4:Ti, MgAl2O4:Mn, MgAl2O4:Co and MgAl2O4:Ni
phosphors are white, grayish black, blue and turquoise
blue, respectively. Fluorescence quenching of UV
emission peak at 395 nm for MgAl2O4:Co phosphor has
been explained in terms of the wavelength for Co metal
particles matches the surface plasmon absorbance band
of MgAl 2 O 4 :M phosphor. Enhancement of visible
emission peak at 425 nm for MgAl2O4:Co and MgAl2O4:Ni
phosphors can be ascribed to the transfer of electrons
from the CB of MgAl2O4 to the CB of metal particles to
cause non-radiative decay.
Acknowledgements: This work was supported by the Talent
Introduc tion Projec t (09924601), Major Cultivation Projects
(18ZDPY01) and Research Project of Higher Education Teaching
Reform (JGZC1903) of Chongqing Three Gorges University, the
Chongqing Natural Science Foundation (cstc2019jcyj-msxmX0310,
cstc2018jcyjAX0599) and the Science and Technology Research
Program of Chongqing Education Commission of China (KJQN201901,
KJZD-M201901201).
230
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