Chemical Engineering Journal 400 (2020) 125913

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Mineralization and toxicity reduction of the benzophenone-1 using 2D/2D T

Cu2WS4/BiOCl Z-scheme system: Simultaneously improved visible-light
absorption and charge transfer efficiency
⁎
Runren Jianga, Guanghua Lua,b, , Matthew Nkooma, Zhenhua Yana, Donghai Wua, Jianchao Liua,
Tianjian Danga
a
Key Laboratory of Integrated Regulation and Resources Development of Shallow Lakes of Ministry of Education, College of Environment, Hohai University, Nanjing
210098, PR China
b
Water Conservancy Project & Civil Engineering College, Tibet Agriculture & Animal Husbandry University, Linzhi 860000, PR China

H I GH L IG H T S

• Cu2WS /BiOCl displayed high photocatalytic activity in the degradation of BP1.

4

• Assess toxicity combined with intermediates prediction and biological tests.

• Apparent indexes of zebrafish are more sensitive than gene expression.
• The intimates 2D/2D interface possess faster charge transfer than 3D/2D system.
• 2D/2D Z-scheme charge transfer is proposed based on in-depth mechanism study.

A R T I C LE I N FO A B S T R A C T

Keywords: Developing excellent photocatalysts to mineralize pollutants and reduce toxicity is an urgent problem in current
Photocatalytic degradation environment purification research. Here, we synthesized a novel 2D/2D Cu2WS4/BiOCl Z-scheme system by a
2D/2D facile solvent mixing method and characterized the samples by various analytical methods. Compared with 3D/
Z-scheme 2D, the close contact surface of the 2D/2D catalyst endows it with extremely fast charge transfer and a large
Toxicity assessment
number of active sites, a Z-scheme system process strong electronic interaction and efficient charge separation,
Benzophenone-1
resulting in the high photocatalytic performance of the 2D/2D Cu2WS4/BiOCl Z-scheme system. As expected,
The 15% 2D/2D Z-scheme Cu2WS4/BiOCl possessed the highest rate constant 1.14 × 10−1 min−1 in the de-
gradation of benzophenone-1 (BP1), which are 8, 5 and 4 times greater than that of BiOCl (1.36 × 10−2 min−1),
Cu2WS4 (2.27 × 10−2 min−1) and 15% 3D/2D Cu2WS4/BiOCl (2.6 × 10−2 min−1), respectively. Meanwhile,
the practicability of Cu2WS4/BiOCl was studied by the influence of relevant real water matrix on photocatalytic
degradation of BP1. In addition, the result of density functional theory calculations demonstrated that the 2D/2D
Cu2WS4/BiOCl system has faster charge transferability and closer integration than that of the 3D/2D system,
which further confirms that the close 2D interface is conducive to charge transfer at the interface. Nine potential
degradation products were identified as intermediates, and extremely significant toxicity reduction during the
degradation process was confirmed by an ECOSAR prediction and zebrafish acute toxicity test. Compared with
gene expression, the hatching rate and survival rate of zebrafish embryo are more sensitive and considered to be
better choices for toxicity assessment.

1. Introduction use, persistence, toxicity, and bioaccumulation [1–3]. Thousands of

tons of ultraviolet filters are produced throughout the world each year,
Ultraviolet filters in personal care products (PCPs) are known to be and ultimately, enter the environment through manufacturing pro-
contaminants of emerging environmental concern due to their extensive cesses, effluents discharges, bathing, laundry, and leaching from

⁎
Corresponding author at: Key Laboratory of Integrated Regulation and Resources Development of Shallow Lakes of Ministry of Education, College of Environment,
Hohai University, Nanjing 210098, PR China.
E-mail address: ghlu@hhu.edu.cn (G. Lu).

https://doi.org/10.1016/j.cej.2020.125913
Received 28 November 2019; Received in revised form 5 June 2020; Accepted 13 June 2020
Available online 17 June 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
R. Jiang, et al.
Scheme 1. The synthesis process of 2D/2D Z-scheme Cu2WS4/BiOCl system.
discarded products [4]. To date, ultraviolet filters have been frequently
detected in the atmosphere, water bodies, sediment, plants, animals and
even human bodies [5–8]. Benzophenones (BPs) are the most com-
monly used group of ultraviolet filters because of their high photo/
biostability and solubility, which lead to extremely high concentrations
in aquatic environments [9]. Meanwhile, the endocrine disrupting ac-
tivity and carcinogenic effects of BPs result in increasing concern re-
garding the disposal of BPs sewage [10,11]. However, BPs can hardly
be removed by traditional wastewater treatment methods, which may
lead to the production of even more toxic intermediates [4,11]. Con-
sidering the risk to the environment from degradation products, it is
vitally important to explore a simple and efficient method to evaluate
toxicity changes during the degradation process. Recently, prediction
models based on the quantitative structure-activity relationship (QSAR)
and ecological structure activity relationships (ECOSAR) were used to
perform toxicological assessments of degradation intermediates
[12–14]. Nevertheless, due to the complexity of the degradation in-
termediates and their coexistence with the parent compound, the pre-
dicted results cannot reflect the real toxicity changes of the mixed
system during the process of pollutant degradation. Therefore, it is
necessary to combine simple model prediction and convenient biolo-
gical testing to assess toxicity changes.
Photocatalytic technology can utilize clean and sustainable solar
energy to mineralize pollutants and has been deemed to be an effective
way to remove pollutants from water [15,16]. Until now, various
semiconductor materials, such as Ti- and Bi-based photocatalysts, have
been used in the degradation of BPs [17,18]. Specifically, two-dimen-
sional (2D) BiOCl has a unique layer structure with [Bi2O2]2+ slabs
interweaved and double slabs of Cl ions and has become a research
hotspot due to its excellent electronic properties and low toxicity [19].
However, pure 2D BiOCl can barely achieve good photocatalytic per-
formance due to its limited charge transfer and light absorption abilities
[13,20]. Due to this weakness of pure 2D BiOCl, construction of a 2D
BiOCl based Z-scheme system may be an effective way to enhance the
optical absorption and the separation of photogenerated electrons and
holes of 2D BiOCl. In detail, in the Z-scheme system, the electrons
(lower reduction ability) in the conduction band of a semiconductor
will combine with the holes (lower oxidation ability) in the valence
band of 2D BiOCl [21]. Of note, the accumulated electrons in 2D BiOCl
and the holes in the semiconductors endow them with stronger reduc-
tion and oxidation properties, respectively. Thus, the 2D BiOCl based Z-
scheme system can lead to enhanced absorption of visible light and
better redox ability by separating redox sites on different semi-
conductor catalysts, which can effectively strengthen the photo-
degradation activity. More importantly, the interfacial charge separa-
tion and migration processes of the Z-scheme photocatalyst are easily
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Chemical Engineering Journal 400 (2020) 125913
affected by the contact mode of two catalysts [22]. Among the many
different forms of contact, the unique face-to-face contact of the 2D/2D
system compared to other systems can not only shorten the transmis-
sion distance for crossing charge boundaries but also provides a larger
contact surface and more active sites [20,22,23]. Furthermore, our
previous report described a 2D/2D SnNb2O6/Bi2WO6 Z-scheme system
prepared by a facile hydrothermal method, which remarkably enhanced
the photocatalytic degradation activity [24]. Therefore, the construc-
tion of BiOCl based Z-scheme with a 2D/2D structure may be an ideal
way to further promote interfacial charge transfer and the visible light
response.
Cu2WS4, as a typical 2D transition-metal sulphide, has emerged as
an ideal candidate owing to its narrow bandgap (2.4 eV) and unique
tetragonal crystal layered structure [25]. Compared with three-dimen-
sional (3D) Cu2WS4 nanocubes, 2D Cu2WS4 has accessible active sites
and a higher density of defects as well as a higher distinguished cata-
lytic activity [26]. More importantly, 2D Cu2WS4 would be useful for
constructing a BiOCl based Z-scheme with a suitable bandgap and large
contact surface. Hence, if the Z-scheme system formed between 2D
BiOCl and 2D Cu2WS4, a fast charge transfer, abundant active sites and
favourable light absorption would be realized by integrating the ad-
vantages of the catalysts.
In this work, the 2D/2D Cu2WS4/BiOCl Z-scheme system was first
synthesized via a simple and effective method, as shown in Scheme 1,
and characterized by X-ray powder diffraction (XRD), X-ray photo-
electron spectroscopy (XPS), scanning electron microscopy (SEM), and
transmission electron microscopy (TEM). A typical benzophenone de-
rivative ultraviolet filter benzophenone-1 (BP1) was used to evaluate
the photocatalytic performance. Meanwhile, the mineralization of BP1
was analysed by 3D EEMs and the removal rate of total organic carbon
(TOC). Potential degradation intermediates were identified by LC-MS/
MS, and their toxicities were estimated by ECOSAR. Furthermore, the
toxicity change of the mixed system during the degradation process was
deeply explored by an acute toxicity test performed on zebrafish em-
bryos. Based on the morphology, energy band structure, specific surface
area, photoelectrochemical properties, density functional theory (DFT)
calculations and results of radical trapping experiments, the positive
effects of the 2D/2D microstructure and Z-scheme system on the elec-
tronic interaction, charge separation and photocatalytic performance
are discussed in detail.
2. Materials and methods
2.1. Chemicals and materials
Bi(NO3)3·5H2O (AR, 99%), Na2WO4·2H2O (AR, 99.5%), and
R. Jiang, et al.
thioacetamide (AR, 98%) were purchased from Aladdin Industrial Inc
(Shanghai, China). Ethylene Diamine Tetraacetic Acid disodium (EDTA-
2Na) (AR), ascorbic acid (VC) (AR), mannitol (AR), NaCl (AR, 99.5%),
Na2CO3 (AR, 99.8%), ethanol (AR, 99.7%), Na2SO4 (AR), Na3PO4 (AR,
98%) and CuCl·2H2O (AR, 97%) were purchased from Nanjing
Chemical Reagent Co. Ltd. (Nanjing, China). Benzophenone-1 (BP1)
(LC, 99%) was from J&K Scientific (Shanghai, China). The isopropanol
(IPA) (AR, 99.7%) and hydrochloric acid (AR, 36–38%) were received
from Sinopharm Chemical Reagent Co Ltd. (Beijing, China). Ultrapure
water was produced by a Millipore Milli-Q integral water preparation
system (Milford, MA, USA). Detailed equipment information and test
methods are placed in the Supplementary information (SI).
2.2. Preparation of the photocatalyst
2.2.1. Synthesis of Cu2WS4
The 2D Cu2WS4 nanosheets were synthesized by a simple hydro-
thermal route according to the literature and made a modification [27].
CuCl·2H2O (8 mmol), Na2WO4·2H2O (4 mmol) and thioacetamide
(10 mmol) were dissolved in the solution of 70 mL ethanol (AR, 99.7%)
and water (1:1). Then, the brick red suspension was formed after stir-
ring for 30 min at room temperature. Finally, the above mixed sus-
pension was transferred to a 100 mL Teflon-lined stainless-steel auto-
clave, and heating at 160 °C for 30 h. After the program ended and
cooling to room temperature, then centrifuged and washed repeatedly
with ultrapure water and ethyl alcohol. The powder dried at 60 °C for
10 h to obtain the 2D Cu2WS4 nanosheets. In addition, the 3D Cu2WS4
nanocubes were synthesized with 40 mL ethanol and water (1:1) dis-
solved solution and other conditions remain unchanged.
2.2.2. Synthesis of 2D BiOCl nanosheets and Cu2WS4/BiOCl systems
The 2D BiOCl nanosheets were systemized by a facial method [28].
The Bi(NO3)3·5H2O (2 mmol), mannitol (0.1 mol) was added to 60 mL
of ultrapure water and continue stirring for 20 min. Then 10 mL satu-
rated NaCl aqueous solution was added into the solution and stirred for
30 min at room temperature. Finally, the water solution was transferred
to a 100 mL Teflon-lined stainless-steel autoclave, and heating at 160 °C
for 3 h. After the program ended, the obtained precipitates were cen-
trifuged and washed repeatedly with ultrapure water and alcohol. The
powder dried at 60 °C for 10 h to obtain BiOCl composite. In addition, a
series of 2D/2D Cu2WS4/BiOCl systems were synthesized by mixing
1 mmol BiOCl and a certain amount of Cu2WS4 solution, the mixture
solution was treated with sonication for 3 h to form a homogeneous
dispersion and then were kept stirring overnight (Scheme 1). The final
products were collected by centrifugation and washed with ethanol
three times and then dried in an oven at 60 °C for 12 h. If we use 2D
Cu2WS4 in the standard synthesis, the obtained products will be the 3D/
2D Cu2WS4/BiOCl composites.
2.3. Photocatalytic activity evaluation
The photocatalytic activity evaluation experiments were conducted
with a circulating water system under visible light irradiation (UV cut-
off filter λ greater than 420 nm) from a 250 W Xe lamp the degradation
device is placed in Fig. S1. Prior to irradiation, 100 mL of BP1 solution
(1 mg/L) with the photocatalysts (20 mg) was mechanically stirred for
1 h in the dark. A 2 mL suspension was sampled every 15 min and
filtered by a 0.22 μm filter membrane to remove the particles. The
filtrate was measured by ultraperformance liquid chromatography
system (Waters Acquity UPLC, USA) coupled to a triple quadrupole
mass spectrometer (Waters AcquityXevo TQ) with electrospray ioniza-
tion. Moreover, detailed equipment information and test methods can
be found in the Supplementary information (SI).
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Chemical Engineering Journal 400 (2020) 125913
2.4. Toxicity test
Embryos of zebrafish were used to evaluate toxicity before and after
degradation. Blastula stage (24 h post-fertilisation (pf)) embryos of
zebrafish (Danio rerio, AB strain) developed normally and were received
from Nanjing EzeRinka Biotechnology Co., Ltd. The embryos were
randomly distributed into six groups containing different exposure so-
lutions: dechlorinated carbon-filtered water (control), BP1 solution
(1 mg/L) before photodegradation (0 min), and degraded solution at
10 min, 20 min, 30 min, and 40 min. All the exposure solutions were
renewed daily to maintain the concentrations of the target compounds
and water quality. Eighteen eggs were placed in a 6-well cell culture
cluster (125 × 85 × 23 mm) containing 10 mL solutions as 6 parallel
samples. All of the treated eggs were kept in an incubator at 28 ± 1 °C
and a 16:8h light/dark photoperiod. During the exposure, dead em-
bryos were immediately removed and the hatching rates and survival
rates were recorded at 48 hpf and 96 hpf, respectively. Malformation
was observed using a stereomicroscope. Fifty larvae (96 hpf) from each
exposure group were pooled together, washed with ultrapure water and
immediately frozen at −80 °C for the subsequent measurements of gene
expression levels. The qRT-PCR data are expressed as threshold cycle
(Ct) values, and the mRNA levels were calculated using the 2−ΔΔCt
method [29]. Detailed protocols are available in the Supplemental
material. The gene-specific primers of all the genes were designed based
on zebrafish sequences available at NCBI. The actin gene was selected
as the internal standard, and specific information is provided in Table
S1.
3. Results and discussion
3.1. Physicochemical properties of photocatalysts
3.1.1. Morphology and microstructure analysis
The morphologies and microstructures of the as-prepared samples
were investigated using SEM images, and the results are shown in
Fig. 1a–c. As shown in Fig. 1a and b, according to the SEM images,
Cu2WS4 and BiOCl are both 2D square nanosheets with a clear and
smooth surface and lateral sizes of approximately 500–1000 nm and
100–300 nm, respectively. Notably, the Cu2WS4 nanosheets are covered
with BiOCl in Fig. 1c, indicating the successful preparation of the 2D/
2D Cu2WS4/BiOCl systems. The morphological features of pure the 3D
Cu2WS4 and 15% 3D/2D Cu2WS4/BiOCl system are displayed in Fig. S2.
It is observed that Cu2WS4 has a 3D decahedron structure and that the
2D BiOCl nanosheets are equally distributed on the surface of 3D
Cu2WS4. In addition, TEM and HRTEM were applied to further examine
the micromorphology of 2D Cu2WS4 and 2D BiOCl. From the HRTEM
image shown in Fig. 1d, notable lattice fringes with a 0.275 nm inter-
planar spacing were found in to the (1 1 0) atomic planes of 2D BiOCl
[30]. Meanwhile, the SAED pattern further proves the results of the
atomic planes, where the angle of adjacent diffraction spots is 45° and
the diffraction spots are ascribed to the (1 1 0) and (2 0 0) planes of
tetragonal BiOCl, respectively. Hence, the synthesized tetragonal BiOCl
nanosheets are made up of highly exposed (0 0 1) facets. Moreover,
according to the HRTEM image shown in Fig. 1e, the distinct crystal
spacing of 0.272 nm can be indexed to the (2 0 0) zone axis of 2D
Cu2WS4. Simultaneously, according to the SAED pattern of 2D Cu2WS4,
the diffraction spots are indexed as the (2 0 0) and (2 0 2) planes. Thus,
this set of SAED diffraction spots can be well-indexed to the (0 0 1)
plane of I-42 m Cu2WS4. As shown in Fig. 1f, the detailed micro-
structure of the Cu2WS4/BiOCl system was further clarified by TEM and
HRTEM. The TEM images show that the BiOCl nanosheets are uni-
formly distributed on the large surface of Cu2WS4, which agrees with
the SEM results. Noticeably, the close interface of the Cu2WS4/BiOCl
system can be clearly observed in the HRTEM images, which not only
shortens the distance of charge transfer to improve the efficiency of
charge transfer across the 2D/2D interfacial domain but also has a large
R. Jiang, et al.
Fig. 1. SEM images of 2D BiOCl (a), 2D Cu2WS4 (b), and 15% 2D/2D Cu2WS4/BiOCl (c); TEM and HRTEM images and selected area electron diffraction (SAED) of 2D
BiOCl (d), 2D Cu2WS4 (e), 15% Cu2WS4/BiOCl (f); and HAADF-STEM elemental mapping images of 15% Cu2WS4/BiOCl (g).
number of active sites to hinder the aggregation of photogenerated
electrons and holes. On both sides of the distinct interface, Cu2WS4 and
BiOCl have exposed (2 0 2) and (1 1 0) crystal planes with an interplanar
spacing of 0.37 nm and 0.24 nm, respectively. The SAED image also
reveals the excellent crystallinity of the Cu2WS4/BiOCl system. More-
over, HAADF-STEM elemental mapping (Fig. 1g) reveals the existence
of Cu, W, S, Bi, Cl, and O in the Cu2WS4/BiOCl system and shows that
the BiOCl nanosheets are uniformly distributed on the large surface of
Cu2WS4. The elements of BiOCl and Cu2WS4 are well-overlapped, fur-
ther confirming the formation of an intimate 2D/2D system [31]. More
importantly, the clear element interfaces further confirm the intimate
2D/2D interface, which can be beneficial to charge carrier migration
and separation under the interfaces between two phases and, conse-
quently, improve the photocatalytic performance.
3.1.2. Crystal phase and chemical composition analysis
The crystallographic structures of the materials were characterized
by XRD. As shown in Fig. 2a, all the peaks of the as prepared samples
have good qualitative consistency with the pattern of BiOCl (JCPDS NO.
85-0861) [19] and Cu2WS4 (JCPDS NO. 01-074-3742) [27]. The intense
peaks of 2D BiOCl at 25.9°, 32.5°, and 33.5° were attributed to the
(1 0 1), (1 1 0), and (1 0 2) planes, respectively. Meanwhile, the clearly
distinguishable peaks of 2D Cu2WS4 at 17.6°, 18.5°, and 37.5° were
attributed to the (0 0 2), (1 0 1), (2 0 2) planes, respectively. These
crystallographic planes agree with the results of the interplanar spacing
in the HRTEM images. As expected, 2D/2D Cu2WS4/BiOCl has two
parts, and its peaks are identical to those of 2D Cu2WS4 and 2D BiOCl,
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Chemical Engineering Journal 400 (2020) 125913
which indicates the successful assembly of the 2D/2D Cu2WS4/BiOCl
system. In addition, it was observed that the intensity of the Cu2WS4
peaks in the composite gradually increased as the proportion of 2D/2D
Cu2WS4/BiOCl increased from 5% to 25%. Concurrently, the XRD
spectrum revealed the differences in 3D, 2D Cu2WS4 and the 15% 3D/
2D, 2D/2D Cu2WS4/BiOCl system (Fig. S3). Noticeably, the intensity
ratio of the (1 1 0)/(1 0 2) planes of 2D Cu2WS4 was higher than that of
3D Cu2WS4, which agrees with a previously reported result [28]. The
lower intensity ratio of the (1 1 0)/(1 0 2) planes is also displayed in the
3D/2D Cu2WS4/BiOCl system. Additionally, Raman spectroscopy was
used to further study the structure of the as-prepared materials. As seen
from the Raman spectrum shown in Fig. 2b, the peaks located at 61 and
145 cm−1 of pristine 2D BiOCl are assigned to the A1g mode and A1g
internal Bi-Cl stretching mode, respectively [32]. At the same time, the
peaks located at 132 cm−1, 258 cm−1, and 451 cm−1 correspond to the
A1 mode, B1 mode, and E mode of the Cu2WS4 samples, respectively
[33]. Furthermore, for the 2D/2D Cu2WS4/BiOCl composite with the
15% weight fraction of the 2D Cu2WS4 loaded on 2D BiOCl, the fea-
tured peaks of Cu2WS4 can be obviously observed, which further veri-
fies the successful formation of the 2D/2D Cu2WS4/BiOCl system.
The surface chemical states of the photocatalyst were studied
through XPS techniques, and the whole-range spectra are shown in Fig.
S3. The XPS survey spectrum revealed the co-existence of Bi, O, Cl, Cu,
W and S in the 2D/2D Cu2WS4/BiOCl system, which agrees with the
chemical composition of the sample. Meanwhile, the intensities of the
Bi and Cl peaks in the 2D/2D Cu2WS4/BiOCl system were lower than
those in 2D BiOCl due to the uniform distribution of 2D BiOCl on 2D
R. Jiang, et al.
Fig. 2. XRD patterns (a), Raman spectra (b) of the prepared samples.
Fig. 3. High-resolution XPS spectra of the Bi 4f (a), Cl 2p (b), O 1s (c), Cu 2p (d), W 4f (e), and S 2s (f).
Cu2WS4. The Bi 4f peaks of 2D BiOCl shown in Fig. 3a exhibited two
peaks at 158.1 eV and 163.4 eV, which shifted to a lower binding en-
ergy for the 2D/2D Cu2WS4/BiOCl. The peaks shown in Fig. 3b are at
196.82 eV and 198.43 eV and are assigned to the Cl 2p of BiOCl [13].
Meanwhile, the BiOCl curve of O 1s is deconvoluted into two peaks at
529 eV and 531.8 eV (Fig. 3c), which correspond to the Bi-O bond and
surface hydroxyl groups (O–H) in the sample, respectively [34]. In
addition, for the Cu 2p spectrum shown in Fig. 3d of Cu2WS4, the
central peaks at 932.8 eV and 952.6 eV were assigned to Cu 2p3/2 and
Cu 2p1/2, respectively. The W 4f spectrum (Fig. 3e) of Cu2WS4 was
distinguished by two peaks at 32.56 eV and 33.71 eV, corresponding to
the W 4f7/2 and W 4f5/2, transitions, respectively [27]. The larger mi-
gration of W element may be due to the increase of electron cloud
density and the enhancement of electron binding ability. Moreover, the
one main signal at 226 eV of the S 2s spectrum comes from Cu2WS4, as
shown in Fig. 3f [35]. Interestingly, all the peaks in the 2D/2D Cu2WS4/
BiOCl system shift to a higher binding energy compared with pure
BiOCl. By contrast, negative shifts of the binding energy occurred in the
2D/2D Cu2WS4/BiOCl system compared to Cu2WS4. This phenomenon
may be due to the difference in charge density between the 2D/2D
interface [36,37]. The charge will be transferred between Cu2WS4 and
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Chemical Engineering Journal 400 (2020) 125913
BiOCl once the 2D/2D system is established [38]. Noticeably, the
electron density weakened at Cu2WS4 and was enhanced at BiOCl in the
2D/2D system. Thus, there is a weak internal electric field at the in-
terface of 2D/2D Cu2WS4/BiOCl, and therefore, the photogenerated
electrons will migrate from 2D Cu2WS4 to 2D BiOCl under the force of
the electric field.
3.2. Evaluation of the catalyst performance and toxicity during the process
3.2.1. Photodegradation of BP1
Photodegradation of BP1 (1 mg/L) on all the catalysts was per-
formed under visible light. Before light irradiation, adsorption-deso-
rption equilibrium was achieved with a 30 min dark stirring process. As
observed in Fig. 4a, BP1 can barely be degraded without catalysts under
visible light irradiation over 40 min. As expected, 15% Cu2WS4/BiOCl
exhibits the highest photocatalytic performance, with a 99% degrada-
tion efficiency over 40 min, which is much higher than that of pure
Cu2WS4 (56%) and BiOCl (39%) (Table S2). In addition, all the different
ratios of Cu2WS4/BiOCl showed better photocatalytic activity com-
pared to pure BiOCl, which may due to the formation of 2D/2D
Cu2WS4/BiOCl systems. Meanwhile, the pseudo first-order reaction
R. Jiang, et al.
Fig. 4. Photocatalytic degradation of BP1 under visible light irradiation (a), pseudo-first-order reaction kinetics (b), TOC removal (c), 3D EEMs of the BC solution
after 0 min (d), 20 min (e), 40 min (f).
Fig. 5. The effects of catalyst concentration (a), anions (b) on photodegradation.
kinetic model was used to further study the degradation kinetics of BP1,
and the rate constants are listed in Fig. 4b. Cu2WS4/BiOCl (15%) had
the highest rate constant, 1.14 × 10−1 min−1, which was 8 times
greater than that of BiOCl (1.36 × 10−2 min−1) and 5 times greater
than that of Cu2WS4 (2.27 × 10−2 min−1). As shown in Fig. S4, the
photocatalytic activities of 3D Cu2WS4 and 3D/2D Cu2WS4/BiOCl were
investigated to affirm the influence of the contact method on the 2D/2D
system. 3D Cu2WS4 exhibits a slight decrease in the photodegradation
of BP1 compared with 2D Cu2WS4. Additionally, 15% 3D/2D Cu2WS4/
BiOCl had a 61% degradation efficiency and a 2.6 × 10−2 min−1 rate
constant over 40 min, which are much lower than those of 15% 2D/2D
Cu2WS4/BiOCl. Consequently, the contract model of the system does
affect the photocatalytic performance and the intimate 2D/2D system
allows a shorter charge transfer distance and more interfacial active
sites of Cu2WS4/BiOCl, resulting in a strong photodegradation activity
in BP1. Moreover, the removal rates of TOC were measured after
40 min of visible light irradiation (Fig. 4c). More than 80% of TOC can
be mineralized by 15% Cu2WS4/BiOCl. Additionally, the mineralization
processes of BP1 was further investigated by 3D EEMs. There is no
obvious fluorescence signal in the pure BP1 solution in Fig. 4d.
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Chemical Engineering Journal 400 (2020) 125913
However, four peaks appear in Fig. 4e after 20 min of photodegrada-
tion, which may be due to the fluorescence that formed after the de-
composition of BP1. Finally, as shown in Fig. 4f, the intensities de-
creased and disappeared, indicating that the decomposed substance can
be further mineralized after 40 min of visible light irradiation. Ad-
ditionally, the stability and reusability of the 2D/2D Cu2WS4/BiOCl
system was tested by cycle experiments, and the results are shown in
Fig. S5a. The slight decrease in the rate from 99% in the first run to 95%
after four cycles of experiments demonstrates that 15% Cu2WS4/BiOCl
has relatively good stability. More importantly, the XRD pattern of the
used photocatalyst after four cycles is shown in Fig. S5b. The results
show that the crystal structure of the catalysts did not change, in-
dicating that the 2D/2D Cu2WS4/BiOCl system has superior stability
and recyclability.
3.2.2. Effect of the water matrix on BP1 removal
Photodegradation activity of the pollutant is strongly depends on
the photocatalyst dosage, thus experiments were designed to explore
the effects of 15% Cu2WS4/BiOCl dosage on the BP1 degradation. The
concentration of Cu2WS4/BiOCl was set from 0.05 to 1.0 g/L and while
R. Jiang, et al.
maintained other experimental parameters unchangeable. As depicted
in Fig. 5a, the BP1 adsorption capacity increased as the catalyst con-
centration increased during the dark stirring process. However, the
increased in BP1 degradation efficiency with increasing the catalyst
dosage up to 0.2 g/L, beyond that degradation efficiency was remain
almost unchanged, which may owe to the reduced light penetration
into the catalyst in the presence of an excessively high catalyst con-
centration [13]. Thus, 0.2 g/L Cu2WS4/BiOCl could be regarded as the
optimum dosage based on the balance of cost and removal efficiency.
The inorganic anion is another important factor in practical sewage
application during the photocatalytic process. In this study, effects of
several common anions (10 mM) on photodegradation were shown in
Fig. 5b. Obviously, Cl− and SO42− doesn't induce notable changes,
while CO32− and PO43− caused the greatest inhibition of Cu2WS4/
BiOCl photodegradation of BP1. As is reported, CO32− and PO43− can
consume the photogenerated holes to formation the HCO3−, HPO42−
and H2PO4−, which can preferentially deplete %OH and produce CO32−
and PO43− [39–41].
3.2.3. Possible degradation pathways of BP1
The degradation intermediates were identified by liquid chroma-
tography-tandem mass spectrometry (LC-MS/MS), as shown in Fig. S6.
Fig. 6. Proposed pathway for the photocatalytic degradation of BP1 in Cu2WS4/BiOCl regarding the (a) obtained (b) acute and (c) chronic toxicity of BP1 and its
degradation products using the ECOSAR program.
7
Chemical Engineering Journal 400 (2020) 125913
The possible intermediate products (P) are shown in Fig. 6a according
to the reported literature and m/z of fragmentation. Initially, hydro-
xylated-BP1 2,4,4′-trihydroxybenzophenone (P1) and 2,4,6,4′-tetra-
hydroxybenzophenone (P2) forms through a hydroxyl radical attack
produced by the 2D/2D Cu2WS4/BiOCl system. Meanwhile, the P1
molecule is easily reduced to generate 2,4-dihydroxyphenyl-3,4-ben-
zoquinone ketone, (P3). The aromatic ring opening decarbonylation
and esterification product 2,4,6-trihydroxyphenyl-3-cyclopentanediol
(P4) is further formed by photocatalytic oxidation. Meanwhile, 2,4-di-
hydroxybenzaldehyde (P5) is obtained by the decomposition of P1, P3,
and P4. P2 can be further decomposed into 4-hydroxybenzaldehyde
(P6) and phloroglucinol (P8). After decomposition of P3, the fragment
can be reduced to 1-hydroxy-3-cyclohexene (P9). Then, P6 and 2-hy-
droxybenzaldehyde (P7) can be obtained by dehydroxylation of P5.
Finally, these smaller organic molecules can be further decomposed
into carbon dioxide and water according to the TOC removal and 3D
EEMs analysis results.
3.2.4. Toxicity prediction of degradation intermediates
ECOSAR software was used to confirm the toxicity of the inter-
mediates [13]. The estimation of the median lethal (LC50) and chronic
value (ChV) of BP1 in fish and its intermediates are listed in Table S3,
R. Jiang, et al.
and the ChV is the geometric mean value of the maximum inactive
concentration and minimum active concentration. Noticeably, BP1 is
the most toxic chemical compared with all the intermediates in of BP1
the acute and chronic toxicity evaluations. As shown in Fig. 6b, except
for P4, all the degradation intermediates have lower acute toxicity than
BP1, and the toxicities of P3 and P7 were slightly increased compared
with their previous intermediates, but were still less toxic than BP1. The
acute toxicity of the intermediate products gradually decreased fol-
lowing the predicted pathways (Fig. 6a). Concurrently, the same results
are found for chronic toxicity, as shown in Fig. 6c. The gradually de-
crease of the toxicity of the intermediate products implies that the
toxicity of the degraded solution of BP1 is decreased after 40 min of
photocatalytic degradation by the 2D/2D Cu2WS4/BiOCl system.
However, the degradation solution is a complex mixed system in which
the contents of each pollutant are unknown and constantly change
during the process of degradation. Therefore, the predicted results
cannot reflect the real toxicity change of the mixed system in the pro-
cess of pollutant degradation. It is necessary to further test the toxicity
change of the complex mixed system by a convenient biological ex-
periment.
3.2.5. Toxicity of BP1 and its degradation products on zebrafish embryos
To further determine the joint toxicity effects of degraded solutions
(mixed system), biological tests are necessary [42,43]. Among many
model organisms, the vertebrate species zebrafish (Danio rerio) has
become one of the most popular model organisms in developmental
(eco)toxicology due to its rapid development, easy maintenance in the
laboratory, large number of offspring, transparency of embryos and
access to experimental manipulation [44]. Hence, short-term toxicity
tests using zebrafish embryos were carried out at different time points
Fig. 7. Normal larvae of the control group at 96 h (a); pericardial oedema (b) tail deformity (c), and spinal curvature (d) of the test group at 96 h; the hatching rate at
48 h, and the survival rate at 96 h (e); gene expression levels (fold change relative to the control) of sod1, sod2, cat, ho1 after exposure to BP1 and its degradation
products for 96 h (f). Vertical bars represent ± SD, * above bars indicates significant differences (* p < 0.05, ** p < 0.01).
8
Chemical Engineering Journal 400 (2020) 125913
during the degradation process of BP1. As shown in Fig. 7a–d, mal-
formations, including pericardial oedema, tail deformity, and spinal
curvature of zebrafish (96 hpf), were recorded under a stereomicro-
scope. Meanwhile, the numbers of malformations of each group are
shown in Table S4. In contrast with the control group, the malformation
rates gradually decrease during the degradation process and do not
significantly differ from the control after 30 and 40 min of degradation.
In addition, the hatching rate of 48 hpf zebrafish is shown in Fig. 7e.
Obviously, the zebrafish embryos in the control group exhibited the
highest hatching rates, and the hatching rate increase indicates a de-
crease in the toxicity of the degraded solution. As expected, the same
results are found for the survival rate, which increased with the de-
gradation time. The above results revealed that the toxicity of the de-
gradation solution was reduced during degradation by 2D/2D Cu2WS4/
BiOCl. The endocrine disrupting activity and carcinogenic effects of
BP1 cause a variety of “stresses” or “shocks”, resulting in the rapid
activation of defence mechanisms [45]. More importantly, the genome
must respond in a programmed manner for the organism to survive.
Among the numerous stress response mechanisms, antioxidant proteins
and regulating oxidative stress are among the earliest to respond
[46,47]. Therefore, the effects of exposure to BP1 and its degraded
solution on the mRNA levels of various genes encoding antioxidant
proteins (sod1, sod2, cat) and regulating oxidative stress (ho1) of zeb-
rafish embryos were determined by PCR. As shown in Fig. 7f, the
transcripts of the sod1, sod2, cat and ho1 genes were significantly in-
hibited after exposure to BP1 for 72 hpf. Meanwhile, reduced inhibition
of relative gene expression appeared with the increase of the de-
gradation time and remained unchanged after degradation for 10 min.
Obviously, antioxidant proteins and the regulation of oxidative stress
genes are important ways for an organism to resist external pollution,
R. Jiang, et al.
Fig. 8. UV–Vis absorbance spectra (a), band gap widths (b), nitrogen adsorption-desorption isotherms (c); BJH pore diameter distributions (d), TPR (e) and EIS (f)
measurements of as-prepared samples.
but are not sensitive enough to be indicators of a toxicity change. On
the contrary, the hatching and survival rates of zebrafish were more
sensitive to pollution and showed significant differences after 30 min of
degradation. Therefore, considering the cost and complexity, the
hatching rate and survival rate of zebrafish are better choices for
toxicity assessments. In summary, the photocatalyst 2D/2D Cu2WS4/
BiOCl can degrade BP1 and mineralize it into low-toxicity or non-toxic
products.
3.3. Mechanism study
3.3.1. Mechanism of enhanced photocatalytic activity
As shown in Fig. 8a, UV–vis diffuse reflectance spectra (DRS) were
used to assess the light absorption of the photocatalysts. As a visible-
light-active photocatalyst, Cu2WS4 had a strong absorption band from
the ultraviolet to visible light region. BiOCl displayed a relatively weak
light absorption intensity with an absorption threshold of 420 nm. With
the gradually increasing Cu2WS4 concentration, the 2D/2D Cu2WS4/
BiOCl system exhibited increased optical absorption compared with
pure 2D BiOCl, which may due to the constructive interaction of het-
erogeneous interfaces between 2D Cu2WS4 and 2D BiOCl [48]. Si-
multaneously, the optical band gap energies (Eg) of Cu2WS4 and BiOCl
are shown in Fig. 8b, and the estimated optical band energies are 1.70
and 3.29 eV, respectively. In addition, the specific surface area is an
important factor of photocatalytic activity owing to the high specific
surface area of photocatalysts equipped with abundant active sites and
adsorption sites absorbing more reactant molecules [49,50]. As shown
in Fig. 8c and d, the nitrogen adsorption-desorption isotherms and pore
diameter distributions were investigated using Brunauer-Emmett-Teller
surface area (SBET) and Barrett–Joyner–Halenda (BJH). The SBET values
of pristine Cu2WS4 and BiOCl were independently evaluated to be 6.20
and 11.4 m2/g, respectively, while the SBET value of 15% 2D/2D
Cu2WS4/BiOCl was 8.03 m2/g. The SBET value of 2D/2D Cu2WS4/BiOCl
was higher than that of Cu2WS4 and lower than that of BiOCl, which
may result from the overlap of 2D BiOCl and 2D Cu2WS4. Meanwhile,
the same results were found for the BJH analysis, as shown Fig. 8d, and
the pore size distribution of all the samples was approximately
2–10 nm. In fact, the above photodegradation experiments revealed
9
Chemical Engineering Journal 400 (2020) 125913
that 2D/2D Cu2WS4/BiOCl and 2D Cu2WS4 had better photocatalytic
activity than 2D BiOCl, which indicated SBET and BJH are not re-
sponsible for the excellent photocatalytic performances of the 2D/2D
Cu2WS4/BiOCl system. Moreover, time photocurrent responses (TPR)
and electrochemical impedance spectroscopy (EIS) measurements were
applied to study the carrier transfer of the photocatalysts [51,52]. 2D/
2D Cu2WS4/BiOCl (7.39 × 10−6 μA/cm2) had the highest photocurrent
intensity, approximately 7.0 and 3.5 times higher than those of the
isolate Cu2WS4 (1.87 × 10−6 μA/cm2) and BiOCl (1.07 × 10−6 μA/
cm2) (Fig. 8e). Hence, 2D/2D Cu2WS4/BiOCl can provide more pho-
togenerated electrons and a higher photocurrent, leading to faster
charge transfer between the tight interfaces of the 2D/2D nanosheets.
In addition, the fact that the photocurrents remained constant after five
cycles of the samples further proved the strong stability of the 2D/2D
Cu2WS4/BiOCl system. Additionally, the Nyquist plot of 2D/2D
Cu2WS4/BiOCl displayed a smaller radius than those of pristine Cu2WS4
and BiOCl, as shown in Fig. 8f, suggesting the lower charge transfer
resistance of this system. In addition, the photo-luminescence (PL) in-
tensity also presented a lower recombination rate of the photoexcited
charge carriers in the 2D/2D Cu2WS4/BiOCl system (Fig. S7). There-
fore, the faster charge transfer and lower recombination of the holes
and electrons in the 2D/2D Cu2WS4/BiOCl system are due to the
shortened transmission distance for the charges and abundant activity
sites between the intimate 2D/2D interfaces. Through the above ana-
lyses, we drew the conclusion that the enhanced light absorption and
ultrafast charge transfer between the 2D/2D Cu2WS4/BiOCl interfaces
are the main reason for the improved photodegradation efficiency of
this system on BP1.
3.3.2. Contrasting the differences between the 3D/2D and 2D/2D Cu2WS4/
BiOCl systems
As is known, one of the most important factors that affects the
photocatalytic performance of a composite catalyst system is the con-
tact mode of the catalysts [24]. In the present study, the 2D/2D
Cu2WS4/BiOCl system displayed higher photocatalytic activity for the
degradation of BP1 than 3D/2D Cu2WS4/BiOCl (Fig. 4a), although the
specific reasons for the performance differences are unclear. Therefore,
the three-dimensional charge-density differences of the 3D/2D and 2D/
R. Jiang, et al. Chemical Engineering Journal 400 (2020) 125913

Fig. 9. Comparison of HOMO, LUMO, interface energy, and charge transfer of 3D/2D (a) and 2D/2D (b) Cu2WS4/BiOCl systems.

Fig. 10. ESR spectra of DMPO-%OH and DMPO-%O2− s (a), various degradation rates of BP1 after the introduction of scavengers (b) and possible photocatalytic
mechanism (c).

10
R. Jiang, et al.
2D Cu2WS4/BiOCl systems were calculated by DFT to clarify the
transfer of charges of the two systems. The highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are
shown in Fig. 9a and b. Both the HOMO and LUMO are located at
Cu2WS4 in the 3D/2D Cu2WS4/BiOCl system, which indicates that the
electrons and holes are all in Cu2WS4. Hence, the 3D/2D Cu2WS4/BiOCl
system would possess low redox activity because the electrons and
holes more readily recombine. By contrast, the HOMO and LUMO of the
2D/2D Cu2WS4/BiOCl system are distributed in Cu2WS4 and BiOCl,
respectively. Then, the photogenerated electrons and holes are sepa-
rated, which is in line with the binding energy shifts of the XPS results.
In addition, the schematic illustrations of the charge transfer between
the 3D/2D and 2D/2D Cu2WS4/BiOCl system are presented in Fig. 9c
and d. In the 3D/2D Cu2WS4/BiOCl system, charges accumulate at 2D
Cu2WS4, while in the 3D/2D Cu2WS4/BiOCl system, electrons and holes
are located at 2D BiOCl 2D Cu2WS4. Thus, the low carrier recombina-
tion rate due to the isolated photogenerated electrons and holes allows
the 2D/2D Cu2WS4/BiOCl system to have higher photocatalytic activity
compared with the 3D/2D Cu2WS4/BiOCl system. Meanwhile, the in-
terfacial energies of the 3D/2D and 2D/2D Cu2WS4/BiOCl systems were
calculated using Eq. (1) [25]:
ΔEinter = (EBiOCl Cu2 WS4 − −EBiOCl − −ECu2WS4 ) S (1)
where S is the interface area and EBiOCl Cu2WS4 , EBiOCl and ECu2WS4 denote
the total energy of 2D/2D BiOCl/Cu2WS4 interface, BiOCl nanosheet
and Cu2WS4 nanosheet, respectively, and the results are listed in Table
S5. The 2D/2D Cu2WS4/BiOCl system is easier to combine than the 3D/
2D Cu2WS4/BiOCl system due to the lower interfacial energy. Thus, it is
indicated that the 2D/2D Cu2WS4/BiOCl system has stronger stability
than 3D/2D Cu2WS4/BiOCl.
3.3.3. Possible photocatalytic mechanism
Based on the above systematic investigations, we drew the conclu-
sion that the wider optical absorption capacity and faster separated
photogenerated electrons and holes via the intimate 2D/2D systems are
the main reason for the improved photodegradation efficiency of 2D/
2D Cu2WS4/BiOCl towards BP1. To better understand the possible
photocatalytic mechanism of 2D/2D Cu2WS4/BiOCl, electron spin re-
sonance (ESR) and radical trapping experiments were performed. As
shown in Fig. 10a, the 2D/2D Cu2WS4/BiOCl system exhibits stronger
peaks of DMPO-%O2− than pure BiOCl, which implies more %O2− ra-
dicals are produced during the degradation process. Simultaneously,
the acuity DMPO%OH peaks of 2D/2D Cu2WS4/BiOCl suggest the
powerful oxidation ability of the system, while the DMPO%OH peaks do
not appear in isolated BiOCl. It should be noted that VC, EDTA-2Na and
IPA are used as scavengers in the trapping experiments to capture %O2−,
holes, and %OH, respectively [27]. As shown in Fig. 10b, the degrada-
tion rates of BP1 decreased to 32% and 65% with the addition of VC
and IPA, respectively, which agrees with the ESR results. Surprisingly,
only a slight decrease in the degradation rate was observed in the so-
lution with EDTA-2Na. These results identify that %O2− radicals are the
most reactive species in the removal of BP1 pollution. To determine the
transfer direction of the photogenerated electrons and holes, the XPS
valence band and Mott-Schottky (M-S) plots were used to determine
band potentials, as shown in Figs. S8 and S9, respectively. It was found
that the conduction band (CB) and valence band (VB) of BiOCl and
Cu2WS4 were −1.91 eV/1.38 eV and −0.03 eV/1.67 eV, respectively.
Not surprisingly, BiOCl cannot produce %OH (OH−/%OH = 2.3 eV vs.
normal hydrogen electrode) [53], which was also proven by the ESR
results. Since the CB of Cu2WS4 is −0.03 eV (O2/%O2− = −0.33 eV vs.
normal hydrogen electrode) [54], %O2− can only be produced at the CB
of BiOCl. If a traditional heterojunction is established, electrons would
transfer from BiOCl to Cu2WS4 and holes would migrate from Cu2WS4
to BiOCl, which is contrary to the results of the XPS and DFT analyses.
Thus, the traditional heterojunction is not suitable for the 2D/2D
Cu2WS4/BiOCl system. Moreover, under this path of charge transfer,
11
Chemical Engineering Journal 400 (2020) 125913
electrons and holes are enriched at the CB (−0.03 eV) of Cu2WS4 and
VB (1.38 eV) of BiOCl, which means no %O2− and %OH radicals could be
generated. Based on these results, a Z-scheme 2D/2D Cu2WS4/BiOCl
photocatalytic mechanism for BP1 degradation is proposed, as shown in
Fig. 10c. In the 2D/2D Cu2WS4/BiOCl Z-scheme, electrons are trans-
ferred from Cu2WS4 to BiOCl and combine with the holes in the in-
timate 2D/2D interface; meanwhile, more holes and electrons will
occur after the combining process and accumulate in isolated Cu2WS4
and BiOCl, respectively. As expected, the accumulated electrons in the
CB (−1.91 eV) of BiOCl could produce %O2−, and the large amount of %
O2− can be further reduced to %OH active species. Hence, the Cu2WS4
and BiOCl in the Z-scheme 2D/2D Cu2WS4/BiOCl system are similar to
the structure of a gear, which can effectively increase one another to
achieve extended light absorption and ultrafast charge separation, re-
sulting in very fast mineralization and decreased BP1 toxicity.
4. Conclusions
In conclusion, the 2D/2D Cu2WS4/BiOCl Z-scheme system was
successfully prepared by a facile solvent mixing method. The 2D
stacking structure and intimate heterojunction interface were verified
by morphology analysis and DFT calculations; ESR and radical trapping
experiments were used to verify the Z-scheme charge transfer me-
chanism. As expected, the unique 2D/2D Z-scheme system not only
provides a large contact surface, which shortens the distance of charge
transfer and process abundant reactive sites, but also provides an ul-
trafast charge transfer efficiency. In addition, Cu2WS4 with a narrow
bandgap can improve the visible light absorption of BiOCl. The 15%
2D/2D Z-scheme Cu2WS4/BiOCl had the highest rate constant,
1.14 × 10−1 min−1, for the degradation of BP1, which was 8 times
greater than that of BiOCl), 5 times greater than that of Cu2WS4 and 4
greater times that of 15% 3D/2D Cu2WS4/BiOCl. Moreover, the pho-
todegradation efficiency of BP1 by 15% 2D/2D Z-scheme Cu2WS4/
BiOCl was reduced by CO32− and PO43−. Meanwhile, the TOC removal
rate was 83% in the mineralization process of BP1. More importantly,
potential degradation products and their toxicity reduction processes
were proposed through combining the results of LC–MS/MS analysis
with ECOSAR predictions. Meanwhile, the extremely significant toxi-
city reduction of BP1 to its degradation products was further confirmed
by a zebrafish acute toxicity test, and compared with gene expression,
the hatching rate and survival rate are better choices for toxicity as-
sessment. Furthermore, compared with 3D/2D Cu2WS4/BiOCl, the 2D/
2D system has a faster charge transfer capability and a lower combined
rate of electrons and holes, which further confirmed that the close 2D
interface is conducive to charge transfer at the interface. Finally, the
mechanism of ultrafast charge transfer of the Z-scheme between in-
timate 2D/2D interfaces was proposed base on the above results.
Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This study was supported by the National Natural Science
Foundation of China (Grant 51879228), the National Science Funds for
Creative Research Groups of China (Grant 51421006), the Fundamental
Research Funds for the Central Universities (Grant B200203007), the
World-Class Universities (Disciplines) and Characteristic Development
Guidance Funds for the Central Universities, and the Priority Academic
Program Development of Jiangsu Higher Education Institutions.
R. Jiang, et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.125913.
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