Digest Journal of Nanomaterials and Biostructures Vol. 16, No. 1, January - March 2021, p.

271 - 282

SYNTHESIS AND CHARACTERIZATION OF Ce DOPED ZnO

TWO-DIMENSIONAL NANOSHEETS FOR VISIBLE LIGHT
PHOTOCATALYTIC DEGRADATION OF MB

Q. SHEN, M. H. XU*, G. XIANG PAN, S. L. LAI, Y. H. TONG

Department of Materials Engineering, Huzhou University, Huzhou 313000,
P. R. China

Ce doped ZnO fish-scale shaped two-dimensional nanosheets photocatalysts

(Ce-ZnO) were successfully prepared via hydrothermal method. The Ce-ZnO
nanostructures were characterized by SEM, EDS, XRD, and UV-Vis DRS
techniques. Ce ions were successfully incorporated into the lattice position of ZnO
with Ce molar ratio lower than 1%. The photocatalytic capacity of Ce-doped ZnO
nanosheets for removal of methylene blue (MB) were evaluated by batch
experiment under visible light irradiation. The results revealed that the 1% mole
ratio of Ce doped ZnO sample exhibited the highest photocatalytic efficiency for
methylene blue (MB), where 96.48% of MB was degraded at 60 min.

(Received November 15, 2020; Accepted March 8, 2021)

Keywords: Photocatalysis, Ce, Doped, ZnO, Two-dimensional nanosheets,

Methylene blue

1. Introduction

Organic contaminants in waste water not only pollute the ecological environment,
but also endanger the public health of mankind. People have spent great efforts on removing
the organic compounds from the waste water. Semiconductor photocatalytic degradation of
water treatment has been recognized as a promising technology because it is effective,
low-cost, environment-friendly and able to utilize the solar energy directly [1, 2]. ZnO is a
superior semiconductor material for photocatalysis. ZnO has unique advantages, such as,
high electron mobility and adjustable morphology. However, the bandgap of ZnO is
relatively big (3.37eV) and only ultraviolet light can be absorbed, which accounts for only
4% of the solar spectrum [3]. In addition, fast recombination of photogenerated election/hole
and low photocatalytic stability are common drawbacks of ZnO [4-6]. Therefore, researchers
have made a lot of efforts to improve the photocatalysis capability of ZnO by various
methods.
Doping is an important approach for ZnO modification. The introduction of mental
atoms into the lattice of ZnO can adjust the band gap and improve the utilization of solar
light as well as tailor ZnO nanostructures [7-15]. Mental elements, such as Cu [7, 8], Fe [9],
La [10], Al [11], Gd [12], Sb [13] and Ag [14] have been reported for doping of ZnO. As one
of rare earth metals, Cerium(Ce) has attracted much attention due to its outstanding
advantages: 4f electron transition and abundant energy levels [16, 17]. Doping of Ce in ZnO
achieves great improvement of the photocatalytic activity. Flower-like mesoporous Ce-ZnO
nanosheets [16] was prepared by a one-step wet chemical method. 1% Ce doped ZnO
exhibited highest photocatalytic activities with 85.1% removal of RhB under irradiation of
stimulated sunlight and the photocatalytic performance increased to 89.5% after annealing at
500°C. Chang et al. [18] synthesized Ce dopd ZnO nanorods with excellent visible-light
catalytic activity by using hydrothermal method. Doping of Ce increased surface oxygen
vacancies and leaded to red-shift for visible light absorption of ZnO. Sukriti [19] fabricated
Zn1-xCexO nanostructures via co-precipitation method. The nanostructures changes from

*
Corresponding author: xumh123@163.com
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nanocubes to nanobars and nanohexanes with the increase of doped Ce3+ concentration. The
band gap of Ce doped ZnO shifted from 3.17eV to 2.72eV and The Zn0.94Ce0.6O showed
94.11% degradation of Methylene blue (MB). Jiang [20] reported that the photocatalytic
methyl orange (MO) degradation efficiency of Ce-doped ZnO hollow sphere reached 99%
under irradiation of 500W Xenon lamp. However, the preparation methods mentioned above
are either multi-step or high-energy-costing. Meanwhile, it is of great importance to explore
simpler and cheaper synthesis methods of Ce-ZnO nanostructures with higher photocatalytic
performance. The purpose of this work is to develop a facile approach for Ce-doped ZnO
preparation. Methylene blue (MB) is selected as organic containments. The degradation
process and mechanism were investigated as well.

2. Experimental

2.1. Materials and chemicals

Zn(Ac)2.2H2O, Ce(NO3)2.6H2O, urea and cetyltrimethylammonium bromide (CTAB)
were obtained from Shanghai Aladdin Biochemical Technology Co. Ltd. (Shanghai, China).
All the reagents used in the present investigation were of analytical grade with no further
purification.

2.2. Synthesis of Ce doped ZnO

The precursors of Ce-ZnO were synthesized by hydrothermal method. Zn(Ac)2·2H2O
and Ce(NO3)2.6H2O were used as the zinc source and cerium source. Urea and CTAB were
added as precipitant and surface active agent. Ce-ZnO was obtained after calcination. For the
typical detailed procedure, Zn(Ac)2·2H2O (0.2469 g), Ce(NO3)2.6H2O (0.0488 g), urea
(0.2704g) and CTAB (0.0474 g) were dissolved into 75 mL distilled water. Then mixed
solution was stirred for 30 min and transferred to autoclave with polytetrafluoroethylene liner,
followed by reacting for 4 hours at 80°C. Then the solution was further raised to 120°C and
heated for another 3 hours. The reaction product was collected, washed with distilled water,
dried and calcined at 300°C for 2 hours. Ce doped ZnO samples with different molar ratios of
Ce (0.2%, 0.5%, 1%, 5% and 10%) were prepared by changing the content of cerium and
repeated the above methods. The samples were denoted as x-Ce-ZnO, where x represents the
doping molar ratio of Ce to Zn. For example, the sample was denoted as 0.2%-Ce-ZnO,
where molar ratio of Ce to Zn was 0.002.

2.3. Characterization
The morphologies of the Ce-ZnO samples were observed by Hitachi S3400N
Scanning electron microscopy (SEM) at an accelerating voltage of 15 Kv, equipped with
IXRF energy spectrum analysis (Tec comp. Ltd. China).
X-ray powder diffraction (XRD) patterns were collected in the 2θ range of 5-80° with
CuKα radiation (Cu Kα, λ=0.1545 nm, pipe voltage 36 kV, pipe current 20 mA) (Beijing
Purkinje General Instrument Co., Ltd., China). Solid-state UV–Vis diffuse reflectance spectra
was recorded at room temperature in air by means of a Shimadzu UV-2550 spectrometer
equipped with an integrating sphere attachment using BaSO4 as background. UV-Vis spectra
of liquid were measured by UV-2600 type ultraviolet visible spectrometer (Shimadzu, Japan).

2.4. Photocatalysis and analysis

The photocatalytic performance of Ce-ZnO two-dimensional nanosheets
photocatalysts were assessed by photodegradation of MB solution under visible light
irradiation with a 150W halogen lamp. Before the photocatalytic experiment, a mixture of
70 mL MB solution (10 mg/L) and catalyst (10 mg) was vigorously stirred for 30 min to
establish an adsorption/desorption equilibrium in the dark. The light source and magnetic
stirrer were then opened to do the photocatalytic batch experiments. At given time intervals,
2 mL aliquots were sampled and filtered to remove the solid phase. The filtrates were tested
by measuring the absorbance at 665 nm for MB with UV–Vis spectrophotometer.
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3. Results and discussion

3.1. XRD patterns

Fig. 1 illustrates the XRD patterns of pure ZnO nanosheets and Ce doped ZnO
nanosheets. The XRD pattern of synthesized ZnO was indexed as the pure hexagonal phase
of wurtize-type ZnO (JCPDS NO.36-1451) [21, 22]. The diffraction peaks are corresponding
to (100), (002), (101), (102), (103) and (200) planes, which is marked in Fig. 1(a). The
diffraction peaks of ZnO are broadened gradually and reduced in intensity with increase of
Ce doping content, indicating the crystallinity of the ZnO phase is reduced. Doping of Ce
causes lattice distortion and defect sites of Zn, weakening the lattice signal of ZnO. No new
characteristic diffraction peak is found in the XRD spectrum of Ce-ZnO with 0.2%, 0.5%,
and 1% doping. It indicates that no new crystalline was introduced and no phase transition
occured. A partial XRD pattern of the Ce doped ZnO nanosheets at a 2θ of 30-34° are shown
in Fig. 1(b). It shows clearly that the diffraction peak of the (001) plane of Ce-doped ZnO
samples slightly deviates to little angle. It reveals that Ce has substituted some of Zn
position in ZnO lattice and causes an expansion of (001) lattice spacing due to larger atomic
radius of Ce element [23]. When the content of Ce is larger than 5%, additional peaks appear
at 2θ=28.7o in the diffraction patterns of 5%-Ce-ZnO and 10%-Ce-ZnO. The diffraction peak
is corresponding to the (111) plane of the cubic CeO2 crystal. Ce doping saturation of ZnO
lattice has been reached with 5% Ce content and new phase of cubic CeO2 is formed in 5%
-Ce-ZnO and 10%-Ce-ZnO nanosheets.

Fig. 1. X-ray diffraction patterns of the samples with different amount of cerium.

3.2. SEM images and EDS analysis

The SEM images of ZnO and Ce-doped ZnO samples are shown in Fig. 2. The
morphology of Ce-ZnO samples in Fig. 2(a) exhibits the shape of fish scale-like
two-dimensional layered nanosheets. When the sample is locally enlarged, as shown in Fig.
2(b), these nanosheets are about several micrometer in diameter and dozens nanometer thick.
The samples keep the similar two-dimensional layered structure when small amount (0.2%,
0.5% and 1%) of Ce were doped, as shown Fig. 2(c), (d) and (e), respectively. Compared with
Fig. 2(b), the amplified image of 1%-Ce-ZnO sample in Fig. 2(f) shows that the surface of the
naosheets becomes polyporous. Such kind of structure provided abundant active surface area
for photocatalytic reaction. The images of 5%-Ce-ZnO (Fig. 2(g)) and 10%-Ce-ZnO (Fig.
2(g)) samples show that the nanosheets collapses into smaller pieces. The layered structures
decrease in sizes and become progressively less obvious with the increasing impurity content,
which further confirms the decrease of crystallization peak strength in the XRD patterns.
274

Fig. 2. SEM images of ZnO and Ce doped ZnO ( a, b: ZnO , c, d: 0.2 %- Ce-ZnO;
e: 0.5%-Ce-ZnO, f:1%-Ce-ZnO, g:5%-Ce-ZnO, h:10%-Ce-ZnO).
 275

C
C
SEM C
OO O
SEM
SEM

2μm
2μm
2μm

EM
SEM CC OO
Zn
C O Ce P
Zn
Zn Ce
Ce PtPt

2μm2μm

n Zn CeCe PtPt
Ce Pt

Fig. 3. Elemental mapping of 1 %-Ce-ZnO two-dimensional nanosheets.

Fig. 4. EDS element spectrum of 1%-Ce-ZnO.

Fig.3 display the SEM image and corresponding C, O, Zn, Ce and Pt elements
mapping of 1%-Ce-ZnO sample. The elements Zn, O and Ce distributes evenly all over the
sample area. This validated that the Ce have been doped into ZnO successfully. No Ce
element segregation have been detected. C and Pt are from the background and Pt sputtering
process during SEM sample preparation, respectively. Fig. 4 shows the EDS element
spectrum of 1%-Ce-ZnO sample. The EDS element detecting demonstrates the existence of
276

Zn, Ce and O. The Ce/Zn molar ratio in the table is calculated to be 1.05%
(0.125/11.883*100%). This is consistent with the added amount in the experiment.

3.3 UV–Vis DRS analysis

Diffuse Reflectance UV–visible spectra (DRS) of pure ZnO and Ce doped ZnO
nanosheets at different Ce contents (0.2%, 0.5%, 1%, 5% and 10% Ce/ZnO molar ratios) are
shown in Fig. 5. All the reflectance spectra show a similar shape (Fig. 5a). With the increase
of Ce doping amount, The Ce-doped-ZnO exhibitd a slightly enhanced absorption spectrum
to longer wavelength within the range of visible light. It is well known that optical
absorption properties are associated with its optical energy gap (Eg).

Fig. 5. UV–Vis diffuse reflectance spectra of ZnO and Ce doped ZnO (a), plots of the (ahv) 2
versus hv of ZnO and Ce doped ZnO (b).

The band gap energies (Eg) were calculated by plotting (ahv) vs photon energies (hv)
as shown in Fig. 5(b), where a, h and v represent the absorption coefficient, Planck’s
constant and light frequency, respectively [24-26]. The Eg of pure ZnO, 0.2%-Ce-Zn,
0.5%-Ce-Zn, 1%-Ce-Zn, 5%-Ce-Zn and 10%-Ce-Zn were determined as 3.15, 3.14, 3.13,
3.16 and 3.18eV, respectively. The Eg value decreased firstly and then increased with
increase of the Ce molar ratio in a small range. The broadening of absorption spectrum
toward visible light and the decrease of Eg samples validated the formation of Ce-ZnO
heterostructure [27, 28], which resulted in the enhancement of photocatalytic activity of the
Ce doped ZnO nanosheets.

3.4 Photocatalytic Activity of Ce-ZnO

The photocatalytic performance of ZnO and Ce-ZnO nanosheets has been evaluated.
The degradation results of methylene blue (MB) (10 mg/L) under visible light radiation are
shown in Fig. 6. After 60min of photocatalysis reaction, the residual rate of MB for pure
ZnO, 0.2%-Ce-ZnO, 0.5%-Ce-ZnO, 1%-Ce-ZnO, 5%-Ce-ZnO and 10%-Ce-ZnO nanosheets
were 20.49%, 15.14%, 8.64%, 3.52%, 25.36% and 27.48%, respectively. In the first 30
minutes of the reaction, the MB content dropped down dramatically and the degradation rate
of MB with 1%-Ce-ZnO experiment reached 94.89%. Then the removal rate of MB
increased to 96.48% gradually at 60min, which is the highest among six experiment groups.
The photocatalytic performance of 0.2%-Ce-ZnO, 0.5%-Ce-ZnO and 1%-Ce-ZnO was better
than that of pure ZnO. This is because dopant-induced red shift and increased absorption of
visible light spectrum. On the other hand, the polyporous structure of Ce-doped ZnO
nanosheet also increased the active surface area significantly. However, the samples of
5%-Ce-ZnO and 10%-Ce-ZnO possessed less photocatalytic activity than pure ZnO. The
heterostructures breaks down with excessive content of Ce. Moreover, aggregation of
collapsed nanostructures may occur, which result in little surface area of the CeO-ZnO
samples. Table.1 shows the photocatalytic efficiency and related paraments of Ce-doped
ZnO nanostructures under visible light irradiation from researches [19, 29-31]. Compared
with the data from the previous investigation of Ce-doped ZnO nanostructures, the Ce-ZnO
 277

nanosheets synthesized in our work exhibit extraordinarily high photocatalytic performance

as well as rapidity of degradation.

Fig. 6. Photocatalytic activity of MB degradation with pure ZnO and Ce-doped ZnO.

Table 1. the photocatalytic efficiency (MB degradation) of Ce-doped ZnO nanostructures

under visible light irradiation.

Amount of Light Degradation

Photocatal Concentration referen
structure Photocatal irradiati efficiency(% ph
yst of dye (ppm) ce
yst (g/L) on )
Ce-ZnO 250w 96.11% in
Flower-liked
(1%, 3%, 10 0.4 Hg 140 min for - [29]
nanorods
5%, 8%) lamp 1% Ce-ZnO
Spherical Solar 94.33% in
Ce-ZnO 1 1 - [30]
nanoparticles light 120min
Zn1-xCexO 300W 94.11% in
Nanobars and
(x=0,0.02, 20 0.2 visible 60min for 12 [19]
nanohexanes
0.04,0.06) lamp X=0.06
Go-Ce-Zn 350 W
Irregular 99.17% in
O 10 0.6 xenon - [31]
nanoparticles 90min
(7.4%) lamp
Ce-ZnO
150w 96.48% in
(0.2%, Layered Present
10 0.14 halogen 60 min for -
0.5%, 1%, nanosheets study
lamp 1% Ce-ZnO
5%, 10%)

3.5 Effect of pH value

The effect of pH value on 1% Ce-ZnO catalytic oxidation of MB for 60min is shown
in Fig.7. When the pH values are 3, 5, 7, 9 and 11, the remaining rates of MB in the solution
are 30.69%, 4.79%, 3.52%, 4.16%, and 9.85%, respectively. The photocatalytic effect of
1%-Ce-ZnO on MB is weaker under strong acid conditions (pH=3), which may be due to the
acid corrosion induced damage of Ce-ZnO heterostructure. The photocatalytic remaining
rates of MB are less than 10% when pH value is in the range of 5 to 11, which further
indicates that Ce-ZnO could be used in a wide pH range.
278

Fig. 7. Effect of pH on Photocatalytic Degradation of MB by 1% Ce-ZnO.

3.6. Catalyst stability

To check the stability of the catalyst, recycle experiments of photocatalytic reaction
for 30 min were carried out and the results are presented in Fig. 8. After each run, the
catalysts were collected by centrifugation followed ultrasonic cleaning with distilled water.
The photocatalytic remaining rates of MB are 6.74%, 9.5%, and 11.8%, respectively. It is
observed that the photocatalytic degradation of MB by 1% Ce-ZnO is basically maintained
and the catalyst retains its original activity for three recycle experiments, indicating
excellent stability.

Fig. 8. 1% Ce-ZnO photocatalyst recycles study.

3.7. UV–Vis absorption spectra of MB in photocatalytic reaction

The intermediate products of MB in the photocatalytic degradation experiment
group of 1% Ce-ZnO were tested with UV-2600 type ultraviolet visible spectrometer
(SHIMADZU Japan) and the results are shown in Fig. 9. As the reaction time prolonged, the
maximum absorption peak of MB solution (λ = 664 nm) decreases gradually. Meanwhile,
the maximum absorption peak shifts to 654-647 nm. The characteristic peak of 654-647nm
is corresponding to azure A. This is because the demethylation reaction of MB took place
during at the beginning of photocatalytic degradation of MB. A methyl is removed from MB
molecules to form azure A, so that the blue shift occurs. The results of photocatalytic
degradation of MB are in agreement with those reported in the literature [32, 33]. The
degradation curve of 60min indicated that MB has been totally oxidized eventually with no
absorption peak.
 279

Fig. 9. UV–Vis absorption spectra of MB in photocatalytic reaction.

3.8. Photocatalytic mechanism

The degradation of MB is considered to be that the hydroxyl radical produced acts
on MB. It is also considered that the degradation of MB is associated with hole electrons
(e−/h+) [34]. In order to study the active oxide species in the photocatalytic oxidation
degradation of MB, the holes trapping agent ethylene diamine tetraacetic acid disodium salt
(EDTA-2Na) and a hydroxyl radical trapping agent isopropanol (IPA) were added to the
1%-Ce-ZnO reaction system [33, 35]. Therefore, in the reaction system, the photocatalytic
degradation experiment was carried out according to the initial concentration of MB and the
molar ratio of IPA (or EDTA-2Na) to MB was 200:1. The results are shown in Fig. 10. The
residual rate of MB is 3.52% in the 1%-Ce-ZnO photocatalytic oxidation system after 60
min. while the residual rate of MB is 76.07% and 83.6%, respectively, when IPA and
EDTA-2Na are added to the system mentioned above. This indicates that when adding IPA
and EDTA-2Na, the degradation of MB is hindered. As a result, h+ and ·OH are the active
oxidation species in the photocatalytic process of MB.

Fig. 10. Effect of different capture agents on catalytic degradation of MB.

Based on the theory of solid band and the mechanism of semiconductor

photocatalysis, we speculate the possible mechanism of photocatalytic degradation of MB.
Photogenerated electrons (e–) and holes (h+) are generated on the surface of the
photocatalyst Ce-ZnO during irradiation (Eq. (1)). The photo induced h+ oxidizes the H2O
molecule, which is in the reaction system, into ·OH species (Eq. (2)). The photo induced e-
interacts with the O2 molecule, adsorbed on the surface of the catalyst, to form superoxide
anion ·O2- (Eq.(3)). In addition, ·O2- and H+ react to form the proxygene ion HO2- (Eq.(4)),
and the generated HO2- and H+ react to form H2O2 (Eq.(5)), H2O2 produces ·OH under light
conditions (Eq. (6)). The ·OH generated in the system acts on the oxidation of MB
molecules into small molecules (Eq. (7)).

Ce-ZnO + hv →ZnO( e– + h+) (1)

280

h++ H2O →·OH + H+ (2)

e–+O2 → ·O2– (3)

·O2–+ H+ → HO2- (4)

HO2- + H+→ H2O2 (5)

H2O2 + hv →2·OH (6)

·OH + MB →Degradation products (7)

When IPA is added to the reaction system, the ·OH is captured. Since the
degradation process of MB is inhibited, the residual rate of MB in the solution increases
remarkably. When the EDTA-2Na is added, the Reaction (2) is hindered, which would
hinder the degradation of MB as well. Although the h+ is captured, the Reaction (1) can be
made to the right side, which leads to the production of a large amount of e– at the surface
and inside of the catalyst. The photo induced e– and O2 in the solution to produced ·O2–
according to Reaction (3). The ·O2– and H+ in the solution are to produce the intermediate
substance HO2–, according to Reaction (4). The above HO2– subsequently to produce ·OH
according to the Reactions (5) and (6), so the ·OH generated by the e– action can continue to
act on the MB. Thus, the extent of obstruction of photocatalytic experiment of MB with
EDTA-2Na is not obvious as that with IPA. This is consistent with the experimental results.

Fig. 11. The possible mechanism for photocatalytic degradation of MB with Ce-ZnO.

According to the above discussion, combined with the analysis of UV-Vis

absorption spectra, the possible mechanism for photocatalytic degradation of MB with
Ce-ZnO is proposed (as shown in Fig. 11). Under visible light irradiation, the Ce-ZnO
heterostructure is excited and electrons in valence band transfer to the conduction band to
produce e– and h+. These e– and h+ can move freely in the catalyst. Since the polyporous
nanosheets structure provides sufficient active surface area, the e– and h+ can easily migrate
in the surface. Then e– reacts with O2 in the solution to produce ·O2–. The above·O2– and H+
in the solution finally produce ·OH. On the other hand, h+ in the valence band reacts with
H2O to generate ·OH. These active species mentioned above then act on MB, cause it to
undergo demethylation, and oxidize it to small molecules, so as to achieve the purpose of
decolorization and degradation of MB.

4. Conclusion

The Ce-doped ZnO two-dimensional nanosheets were successfully prepared by

hydrothermal method. The XRD patterns demonstrated that the ZnO nanosheets kept highly
crystallinity and Ce ions were successfully incorporated into the lattice position of ZnO. The
morphology of ZnO layered nanosheets with low Ce doped content (<1%) showed a
 281

fish-scale liked polyporous structure, whereas the sheets collapsed to smaller pieces when
the Ce doping mole ratio increase to 5%. 1%-Ce-ZnO nanosheets exhibited the highest
degradation efficiency for removal of MB due to the formation of Ce-ZnO heterostructure
and the increase of active surface area. The MB degradation rated reached 96.48% after
60min visible light irradiation.1%-Ce-ZnO nanosheets kept high photocatalytic performance
at a wide pH range of 5-11. The mechanism investigation photocatalytic degradation of MB
showed the photocatalytic degradation reaction initiated from the demethylation of MB and
the h+ and ·OH acted as key active species during the oxidation of MB. The Ce doped ZnO
nanosheets in this work showed high photocatalytic performance of degradation of organic
pollutants, high rapidity and superior recyclability. These make the Ce-ZnO nanosheets to be
a powerful tool to deal with the wastewater containing organic contaminants.

Acknowledgements

This work is supported by Zhejiang Provincial Natural Science Foundation of China

(LQ19E040001 and LQ20E040001). The work is also supported by Research fund of
Huzhou University (2019XJKJ33).

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