Materials Science in Semiconductor Processing 131 (2021) 105835

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Materials Science in Semiconductor Processing

journal homepage: http://www.elsevier.com/locate/mssp

Investigation of photocatalytic properties based on Fe and Ce Co-doped

ZnO via hydrothermal method and first principles
Nan Qing Yang , Jin Li *, Ya Nan Wang , Jie Ma
School of Physical Science and Technology, Xinjiang University, Urumqi, 830046, Xinjiang, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, Fe and Ce co-doped ZnO (Zn1-2xFexCexO, x = 0, 0.01, 0.03, 0.04) was prepared through hydro­
Co-dope ZnO thermal synthesis, followed by annealing. The samples were characterized by X-ray diffraction, X-ray photo­
Photocatalytic electron spectroscopy, scanning electron microscopy, UV–vis spectroscopy, and photoluminescence
First principles
spectroscopy, and the photocatalytic efficiency of the samples on the organic dye, methylene blue, under
simulated sunlight was studied. Based on first principles, the influence of doping on the band structure of the
samples was studied. The experimental results show that co-doping ratios affect the performance of ZnO. When
the doping concentration was 3 at%, the red shift of the UV–vis spectrum of the material was the most obvious,
and the PL of the material was inhibited. Compared with pure ZnO, the degradation rate increased from 72.6% to
98.5%. As the doping concentration increased, the photocatalytic performance of the materials began to
decrease. Simulations showed that the incorporation of small amounts of Fe and Ce reduced the band gap of ZnO
and introduced a shallow donor level in the band gap, effectively inhibiting the recombination of carriers,
thereby improving the photocatalytic performance of the material. When the doping ratio was increased from 3%
to 4%, the band gap became wider. These results indicate that Fe and Ce co-doped ZnO has potential applications
in the photocatalytic degradation of organic pollutants and provides a method for improving photocatalytic
performance by inhibiting carrier recombination.

1. Introduction Therefore, in recent years, researchers have focused on improving the

Large amounts of organic pollutants are often discharged. These
pollutants seriously damage the environment and pose a significant
threat to human health [1–4]. Since Frank et al. successfully degraded
cyanide through semiconductors in 1977, the photocatalytic degrada­
tion of organic pollutants by semiconductors has gradually become a hot
research topic [5–7]. ZnO is a semiconductor with a band gap at 3.37 eV
and an exciton binding energy of 60 meV, allowing for exciton emission
at room temperature [8]. ZnO has many advantages, such as being
cheap, non-toxic, and easy to prepare; thus, metal-doped ZnO photo­
catalysts have been widely researched [9–12]. There are several
methods for preparing ZnO nanomaterials, such as solid phase [13],
sol-gel [14] and hydrothermal processes [15]. Among them, hydro­
thermal preparation is widely used because it results in a crystalline
powder and prevents the agglomeration of hard particles, while also
allowing for increased control over the nanostructures. However, ZnO
has limited practical applications due to its wide band gap, low utili­
zation rate of sunlight, and high electron-hole recombination rate.
photocatalytic performance of ZnO through modifications [16].
Impurities can be introduced into semiconductors to create energy
levels within the band gap; semiconductor doping has thus been studied
experimentally and theoretically [17–19]. The incorporation of transi­
tion elements into metal oxides increases the number of crystal defects,
thereby increasing the surface available for photoelectric reactions [20].
Giahi et al. used the sol-gel method to prepare Fe-doped
ZnO–TiO2nanopowders. The optimal doping ratio was identified, and
it was found that compared with pure ZnO and ZnO–TiO2, the Fe-doped
samples showed significantly improved photodegradation efficiency
[21]. Through a combination of precipitation and calcination processes,
sea urchin-like Fe-doped ZnO was prepared with various proportions of
dopant; it was found that the crystal structure changed with increased Fe
content. At 5% doping, the ZnO nanoparticles had a smaller particle size,
more uniform dispersion, and better photocatalytic activity [22]. For
monodoped semiconductors, photogenerated carriers tend to recombine
at the doping sites, which limits the rate of photocatalytic reactions. To
prevent this, co-doping is usually employed [23,24]. Alam et al.

* Corresponding author.
E-mail address: xjlijin@163.com (J. Li).

https://doi.org/10.1016/j.mssp.2021.105835
Received 21 October 2020; Received in revised form 2 March 2021; Accepted 23 March 2021
Available online 14 April 2021
1369-8001/© 2021 Published by Elsevier Ltd.
N.Q. Yang et al.
prepared Y and V co-doped ZnO nanoparticles by a surfactant-assisted
sol-gel method, which effectively separated the electron-hole pairs,
thereby greatly improving the photocatalytic efficiency [25]. Shah et al.
performed solar light degradation on norfloxacin using an
as-synthesized Bi3+ and Fe2+ co-doped ZnO with the addition of HSO−5
and studied the toxic side effects and the degradation pathway [26].
Singh et al. prepared Ce- and Co-doped ZnO nanoparticles with clear
emission spectra by the sol-gel method, followed by annealing [27].
Density functional theory based on first principles is widely used to
predict and analyze the properties of materials [28–30]. Cao et al.
studied the electronic and electromagnetic properties of Mn and Fe
co-doped ZnO based on first principles [31]. Jia et al. studied the effect
of Ce doping on the magnetic and optical properties of ZnO through first
principles [32].
In this study, Fe and Ce co-doped ZnO photocatalytic materials were
prepared by a hydrothermal method and subsequent annealing. Based
on first principles density functional theory (DFT), the structure and
energy bands of Fe and Ce co-doped ZnO were simulated, and the
photocatalytic mechanism of the doped materials was studied by
comparing the experimental and simulation results. Studies have shown
that Fe and Ce co-doped ZnO exhibits high potential for photocatalysis
and provides theoretical considerations for methods of suppressing
electron-hole pair recombination to improve photocatalytic
performance.
2. Experimental procedure
2.1. Preparation
All chemical reagents were purchased from Shanghai Aladdin
Biochemical Technology Co., Ltd. All reagents were of analytical grade
and no further purification was required. To prepare the Zn1-2xFexCexO
(x = 0, 0.01, 0.03, 0.04) composites, Fe(NO3)3⋅9H2O, Ce(NO3)3⋅6H2O,
and LiOH⋅H2O were used as the Fe, Ce, and base sources, respectively.
Varying ratios of Fe(NO3)3⋅9H2O and Ce(NO3)3⋅6H2O (0, 0.03, 0.09,
0.12 mmol) and 3 mmolg of Zn(NO3)2⋅6H2O were added to 50 mL of
deionized water and stirred for 1 h. Then, 0.004 g of CTAB was added as
a surfactant and stirring was continued for 2 h to mix the reagents
uniformly. The mixed solution was poured into a Teflon-lined stainless-
steel autoclave of 100 mL capacity and heated at 150 ◦ C for 2 h. After
natural cooling, the sample was removed, washed with deionized water
and pure ethanol 3 times, and placed in a vacuum drying oven at 80 ◦ C
for 8 h. After cooling, the sample was ground, placed in a muffle furnace,
and sintered at 600 ◦ C for 2.5 h to obtain the final sample.
2.2. Photocatalytic experiments
Photocatalytic experiments were carried out with a photochemical
reaction device (Nanjing Xujiang Mechanical Power Plant). A 350 W Xe
lamp was used as the light source, and the degradation target was a 10
mg/L methylene blue (MB) solution. Prepare four parts of a 50 mL so­
lution to be degraded, and 30 mg of photocatalysts were added to obtain
an evenly mixed solution. After 60 min in dark conditions, the solvent
and sample were at an absorption equilibrium. The Xe lamp was then
turned on to start the photocatalytic reaction, and 3–4 mL of the solution
was sampled every 30 min to measure the absorption peak of the MB
solution by UV–vis spectroscopy. The degradation rate, a, was calculated
by the formula:
C0 − C
a= × 100%
C0
where C0 is the initial absorbance and C is the absorbance after the
reaction.
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Materials Science in Semiconductor Processing 131 (2021) 105835
2.3. Characterization
X-ray diffraction (XRD) spectra were obtained using an X-ray
diffractometer (Bruker D8 Advanced) with a copper target. X-ray
photoelectron spectroscopy (XPS) was performed using a Thermo Fisher
Scientific ESCALab 250XI Type XPS instrument. Scanning electron mi­
croscopy (SEM) was performed using an LEO1430VP. The MB absorp­
tion spectrum was obtained using a UV–vis spectrometer
(PERKINELMER Lambda 650). Photoluminescence (PL) spectra were
obtained using a Hitachi Model F-4600 PL spectrometer.
3. Results and discussion
The XRD patterns of pure ZnO and Fe/Ce co-doped ZnO and its
enlarged (101) face as shown in Fig. 1. As can be seen from Fig. 1(a),
sharp peaks are observed when 2θ =
31.73◦ ,34.36◦ ,36.21◦ ,47.46◦ ,56.53◦ ,62.75◦ ,66.29◦ and 67.85◦ , these
diffraction peaks can be indexed to (100), (002), (101), (102), (110),
(103), (200) and (112) planes of ZnO. Through Jade, all the peaks of
samples were in good agreement with the PDF card information
numbered 89–0510. All samples obtained had a wurtzite crystal struc­
ture, indicating that Fe and Ce did not form new phases, and there were
no free Fe and Ce molecules. According to Fig. 1(b), after doping, the
diffraction peak of the (101) plane is slightly shifted. This shows that
doping altered the ZnO lattice.
The incorporation of Fe and Ce into ZnO was confirmed by XPS.
Fig. 2(a) shows a high-resolution scan of the four main elements of
Zn0.94Fe0.03Ce0.03O. The high-resolution scanning peak of Zn 2p is
concentrated at 1021 eV (Zn 2p3/2), which can be attributed to the
formation of Zn2+ in the ZnO lattice. The O 1s peaks were not further
analyzed as this study focuses on exploring the effects of Fe and Ce. The
scan of Ce 3d (Fig. 2(b)) contains peaks marked u and u′ , which corre­
spond to Ce4+ and Ce3+, respectively. This indicates that a small amount
of Ce3+ and Ce4+ co-exist in the Zn0.94Fe0.03Ce0.03O lattice [33,34].
Fig. 2(c) shows the scan of Fe 2p. The wide peaks around Fe 2p3/2 can be
fitted by a gaussian distribution, resulting in two peaks at 709.43 and
711.92 eV, corresponding to Fe2+ and Fe3+, respectively. This indicates
that Fe2+ and Fe3+ also co-exist in the Zn0.94Fe0.03Ce0.03O lattice. Due to
the radii of Ce3+, Ce4+, Fe2+, Fe3+ all being larger than that of Zn2+, as
well as the internal stress between the ions, the XRD peaks have
migrated [35,36].
The surface morphologies of Fe and Ce co-doped ZnO with varying
dopant proportions were characterized by SEM (Fig. 3). As shown in
Fig. 3(a), pure ZnO has an approximately hexagonal structure with
relatively uniform, albeit large particles (diameter ~100–250 nm). An
SEM image of the sample with a doping ratio of 1% is shown in Fig. 3(b).
Compared with pure ZnO, the particle size in the composite sample is
reduced, and its morphology is mainly composed of nanoparticles and
nanosheets with widths of ~20–100 nm. Fig. 3(c) and (d)are SEM im­
ages at doping concentrations of 3 at% and 4 at%, respectively.
Compared with Fig. 3(b), these samples consist of an increasing number
of uniform nanoparticles with a particle size of ~50–100 nm. However,
nanoparticles and nanosheets still coexist in these samples; this lattice
disorder may be caused by the different valence states of the doped ions
in the crystal, leading to differences in morphology. Fig. 4(a) –(d) show
the EDS spectra of Zn1-2xFexCexO (x = 0, 0.01, 0.03, 0.04). The results
show that the actual atomic percentages of Fe/Ce in the samples are
0%,0%; 0.92%,0.88%; 3.01%, 2.74%; and 3.51%, 3.62% respectively.
Fig. 5(a) presents the UV–vis absorption spectra of the samples. The
absorption edge of ZnO is at 389 nm, and the absorption edge of the
samples with doping concentrations of 1 at%, 3 at% and 4 at% are at
396, 403, and 393 nm, respectively. These absorption edges have un­
dergone a certain degree of red shift, with the red shift of the sample
with a doping ratio of 3 at% being the most obvious. At the same time,
because of the incorporation of Fe and Ce, the d-d transition occurs in
the process of light absorption, which leads to an obvious absorption
N.Q. Yang et al. Materials Science in Semiconductor Processing 131 (2021) 105835

Fig. 1. XRD spectra of samples: (a) pure ZnO,Zn0.98Fe0.01Ce0.01O,Zn0.94Fe0.03Ce0.03O and Zn0.92Fe0.04Ce0.04O; (b)enlarged (101) crystal plane.

Fig. 2. XPSimages of(a)Zn0.94Fe0.03Ce0.03O; (b) Ce 3d; (c) Fe 2p.

peak at 500 nm in the doped sample [37]. These will help improve the
photocatalytic performance of the photocatalyst. The band gaps of all
samples can be obtained by UV–vis spectroscopy combined with the
Kubelka-Munk formula:
(αhυ)2 = A(hυ − Eg )
where α, h, ν, Eg, and A are the absorption coefficient, Planck constant,
frequency, band gap energy, and a constant, respectively. As shown in
Fig. 5(b), the band gap energy of ZnO is 3.18eV, and the band gap en­
ergies at doping concentrations of 1 at%, 3 at%, and 4 at% are 3.13,
3.08, and 3.15 eV, respectively. The results show that Fe and Ce co-
doping with Fe and Ce can reduce the band gap energy of ZnO. Ac­
cording to the Burstein–Moss effect, an increase in the doping ratio
causes the carrier concentration to increase. When electrons are already
present in the conduction band (CB), more energy is needed for electrons
to transition from the valence band (VB) to the CB [38].
The PL spectra of pure and doped ZnO were compared in the range of
360–625 nm with a UV excitation wavelength of 325 nm at room tem­
perature. Fig. 6 shows that the luminescence intensity of pure ZnO is the
highest, indicating that the lifetime of photogenerated carriers is low,
and many electron-hole pairs recombine in a short time. The

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 N.Q. Yang et al.
Fig. 3. SEM image of(a) pure ZnO; (b) Zn0.98Fe0.01Ce0.01O; (c) Zn0.94Fe0.03Ce0.03O; (d) Zn0.92Fe0.04Ce0.04O.
luminescence intensity of the doped samples is lower than that of the
pure sample, with the lowest intensity occurring at a doping concen­
tration of 3 at%. This result indicates that Fe and Ce co-doping signifi­
cantly inhibits the recombination of electron-hole pairs, and the life of
photo-generated carriers is significantly improved, which is conducive
to the carriers more thoroughly reacting with pollutants, thereby
improving the photocatalytic performance of the material.
In the presence of light, when the received energy is greater than the
band gap of the sample, the electrons in the VB are excited to the CB to
form electron-hole pairs. To analyze the photocatalytic performance
changes caused by the dopant concentration, each sample was tested for
its MB photodegradation efficiency. As shown in Fig. 7(a) and (b),
because the certain absorbability of the photocatalyst, part of MB ad­
heres to the surface of the photocatalyst after 60 min of full stirring
under dark conditions, and adsorption/desorption equilibrium was
reached. When a photocatalyst was involved in the photodecolorization
process, the absorbance decreased with increasing irradiation time.
After 210 min of illumination, the absorbance of the MB solution with
pure ZnO was 0.274, and that of the sample with a doping concentration
of 3 at% was 0.015. The photodegradation rate curve and photo­
degradation kinetic curves of the photocatalysts with respect to MB
solution are shown in Fig. 7(c) and (d), respectively. The photocatalytic
degradation of organic pollutants follows quasi-first-order kinetics, and
its ln (Ct/C0) is linearly related to the reaction time, that is, ln (Ct/C0) =
kT, where Ct is the concentration of organic dyes at time t. Taking the
blank group as the control group, it can be seen that pure ZnO possesses
significantly lower photocatalytic activity than its Fe and Ce co-doped
counterparts. Meanwhile, the absorbance of the samples decreased at
different rates initially, indicating that the absorbance of each sample
was different. The surface of the samples with good absorbance could
absorb more organic dyes, which allowed for a more complete photo­
catalytic reaction. This indicates that the photodegradation activity of
ZnO was significantly improved with the addition of 3 at% Fe and Ce.
It can be seen from the above results that the photocatalytic per­
formance of the doped sample has obvious changes, and when the
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Materials Science in Semiconductor Processing 131 (2021) 105835
doping ratio is changed from 3% to 4%, the characteristics of the sample
have different changes from before. In order to explore the mechanism
of the change of photocatalytic performance of the sample, a 3 × 3 × 2
ZnO supercell was constructed, including 36 Zn atoms and 36 O atoms,
and then two Zn atoms in ZnO were replaced by a Fe atom and a Ce
atom, and the doping concentration was 0.03, namely Zn0.94Fe0.03
Ce0.03O. The model of Zn0.92Fe0.04Ce0.04O was constructed by a 3 × 2 ×
2 ZnO supercell, including 22 Zn atoms and 24 O atoms, one Fe atom and
one Ce atom. All calculations are carried out by Vienna Ab-initio
Simulation Package (VASP) software based on density functional the­
ory (DFT), and performed using the generalized-gradient approximation
of the Perdew-Burke-Ernzerhof (GGA-PBE) [39] exchange correlation
functional. The maximum force on each atom is 0.01 eV/Å,maximum
energy change between two ionic steps is10− 5 eV and maximum stress is
0.1 GPa. K-point mesh employs a dense of3 × 3 × 2.
The geometric structure optimizations of pure ZnO, Zn0.94Fe0.03
Ce0.03O, and Zn0.92Fe0.04Ce0.04O models were performed, and the en­
ergy band structures of the doped models were determined. The models
of geometric optimization of all samples are shown in Fig. 8(a)–(c). The
bond lengths of Zn–O, Fe–O and Ce–O were 1.98, 1.99, and 2.03 Å,
respectively. The energy band structures of the samples are shown in
Fig. 8(d)–(f). It can be seen that the band gap of ZnO, Zn0.94Fe0.03
Ce0.03O, and Zn0.92Fe0.04Ce0.04O are 0.809, 0.784, and 0.821 eV,
respectively. Doping causes the Fermi level to enter the CB due to the
addition of electrons to the impurities, indicating that the doped mate­
rial is an n-type semiconductor. The shallow donor level generated by
impurities appears in the band gap. Because of the underestimation of
the band gap by the GGA model, the calculated band gap is smaller than
the experimental value, but the variation of the band gap is consistent
with the experimental one [40]. Although the band gap can be corrected
by + U, the U value cannot be determined in advance, making this
method more time-consuming [41–43]. Therefore, we believe that
GGA-PBE is a more efficient method for further research on co-doped
ZnO.
The calculated results show that the band gap of Zn0.94Fe0.03Ce0.03O
N.Q. Yang et al. Materials Science in Semiconductor Processing 131 (2021) 105835

Fig. 4. EDSspectra of (a) pure ZnO; (b) Zn0.98Fe0.01Ce0.01O; (c) Zn0.94Fe0.03Ce0.03O; (d) Zn0.92Fe0.04Ce0.04O.

Fig. 5. (a) UV–vis absorption spectra and (b) band gap energy of pure and doped ZnO.

is lower than that of pure ZnO, which is consistent with the experimental
results from the UV–vis spectra. Meanwhile, because the electrons in the
shallow donor energy level can easily excited into the CB and accept the
photogenerated carriers in the VB, they can effectively separate the
electron–hole pairs. This explains why the peak intensity of the PL
spectrum in the experiment decreased significantly. However, when the
doping ratio increases to 4 at%, the band gap increases, and is even
higher than that of pure ZnO. When an n-type semiconductor is heavily
doped, the Fermi level enters the CB. Because of the high carrier con­
centration, more energy is needed to make electrons transition from the
VB to the CB when the CB is not empty, leading to an increased width of
the material band gap. This result is also in agreement with the exper­
imental results.
A schematic diagram of the photocatalytic mechanism of
Zn0.94Fe0.03Ce0.03O is shown in Fig. 9. According to the experimental
and simulated results, when Zn0.94Fe0.03Ce0.03O is exposed to light, the
electrons in the VB are excited to the CB, forming electron-hole pairs.
Subsequently, oxygen molecules combine with electrons on the surface
of the catalyst to produce •O−2 with strong oxidizing ability, which oxi­
dizes the organic pollutants to generate small organic molecules of H2O

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N.Q. Yang et al. Materials Science in Semiconductor Processing 131 (2021) 105835

Fig. 6. PL spectra of pure ZnO, Zn0.98Fe0.01Ce0.01O, Zn0.94Fe0.03Ce0.03O and Zn0.92Fe0.04Ce0.04O.

Fig. 7. Photocatalytic performance of samples: (a) absorbance patterns of MB solution with 210 min light with ZnO; (b) absorbance patterns of MB solution with 210
min light with Zn0.94Fe0.03Ce0.03O; (c) photodegradation rate curves of MB solution with blank group and photocatalyst; (d) photodegradation kinetics curves of MB
with blank group and photocatalyst.

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N.Q. Yang et al.
Fig. 8. Models of (a) pure ZnO; (b) Zn0.94Fe0.03Ce0.03O; (c) Zn0.92Fe0.04Ce0.04, band structures of (d) pure ZnO; (e) Zn0.94Fe0.03Ce0.03O; (f) Zn0.92Fe0.04Ce0.04.
and CO2. At the same time, holes trap electrons in hydrated hydroxide
ions in the VB to form •OH, which also has strong oxidizing ability and
reduces pollutants to small molecular organics or water and carbon di­
oxide through •OH. Compared with pure ZnO, Fe and Ce doping will
produce a shallow donor level, introduce intermediate states to capture
electrons, and hinder the recombination of photogenerated carriers so
that organic pollutants can fully react with •O−2 and •OH, improving the
photocatalytic effect. At the same time, due to the incorporation of
impurities, lattice distortion is caused, and more defects and dislocations
are produced in the crystal. Moreover, because some Fe and Ce replace
the Zn atoms in ZnO, Fe–O, and Ce–O couples are produced, which
provide catalysts with more catalytically active sites [44,45], improving
the photocatalytic performance of the material.
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Materials Science in Semiconductor Processing 131 (2021) 105835
4. Conclusions
In summary, Fe and Ce co-doped ZnO photocatalytic materials were
prepared by a hydrothermal method and annealing treatment, and the
energy band structure and photocatalytic mechanism of the doped ma­
terials were studied by DFT based on first principles. The experimental
results show that the UV–vis absorption spectra of the doped materials
have red shift, the peak intensity of the PL spectrum is significantly
reduced, and the photocatalytic degradation efficiency is significantly
improved. The degradation rate of pure ZnO is 72.6%, which increased
to 98.5% with the addition of 3 at% of each dopant. The calculated re­
sults show that the band gap of the material is reduced after doping with
a small amount of Fe and Ce, and the doped material is an n-type
semiconductor. The shallow donor level generated by impurities inhibits
the recombination of electron-hole pairs, thereby improving the
N.Q. Yang et al.
Fig. 9. Schematic diagram of the photocatalytic mechanism
Zn0.94Fe0.03Ce0.03O.
photocatalytic activity of the material. When the doping ratio is
increased to 4 at%, the band gap widens owing to the Burstein–Moss
effect. Based on the combined results of experiments and calculations, it
is evident that the Fe and Ce co-doped ZnO photocatalytic material has
high potential for use in the photocatalytic degradation of organic pol­
lutants, and provides a method for inhibiting the recombination of
electron-hole pairs.
CRediT authorship contribution statement
Nan Qing Yang: Conceptualization, Methodology, Writing – original
draft, Writing – review & editing. Jin Li: Supervision, Project adminis­
tration. Ya Nan Wang: Validation, Investigation. Jie Ma: Formal
analysis.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (No. 11764040), Excellent Young Science and
Technology Talents Program of Xinjiang Uygur Autonomous Region
(2019Q011), and the Natural Science Foundation of Xinjiang (No.
2017D01C022).
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