Chemical Engineering Journal 429 (2022) 132105

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Chemical Engineering Journal

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Construction of direct Z-scheme SnS2@ZnIn2S4@kaolinite heterostructure

photocatalyst for efficient photocatalytic degradation of
tetracycline hydrochloride
Yuchan Li a, Bin Yu b, Zhenqi Hu c, *, Hong Wang a, *
a
School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou, Jiangsu 221116, PR China
b
College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, PR China
c
School of Environment and Spatial Informatics, China University of Mining and Technology, Xuzhou, Jiangsu 221116, PR China

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

Keywords: The accumulation of antibiotics in water system and the consequent detrimental effects have drawn worldwide
Degradation attention extensively. There is an urgent need to develop rapid and efficient degradation methods of antibiotics.
SnS2@ZnIn2S4@kaolinite In this work, a highly efficient SnS2@ZnIn2S4@kaolinite (SZK) photocatalysts were successfully synthesized by
Photocatalysis
hydrothermal method. In comparison with bare photocatalysts, the SnS2@ZnIn2S4@kaolinite (SZK) hetero­
Tetracycline hydrochloride
structure demonstrated greatly improved adsorption-photocatalytic degradation capability for removal of
tetracycline hydrochloride (TCH). Under visible light illumination, the apparent reaction rate of SZK hetero­
structure reached 0.0231 min− 1, which was around 20.81 times and 2.37 times higher than that of SnS2 and
ZnIn2S4, respectively. It has been proved that •O2− and 1O2 are the main active species participating the
degradation process. Based on HPLC-MS analysis, the possible photodegradation pathways of TCH have been
proposed. The superior removal performance is mainly ascribed to the enhanced adsorption ability, elevated
light harvesting and the increased separation efficiency originated from the synergistic effect of the components.
Our study provides new insights with the utilization of natural minerals for visible light photocatalytic degra­
dation of antibiotics in wastewater treatment.

1. Introduction the treatment of antibiotic wastewater.

Indiscriminate use of antibiotics has led to their accumulation and
biotransformation in water environment, which constitutes a serious
environmental problem triggering extensive studies in recent decades
[1–2]. As a broad-spectrum antibiotic drug, tetracycline hydrochloride
(TCH) has been widely applied in human therapy, animal farming and
agriculture to prevent and treat bacterial infection related diseases. With
the discharge of wastewater from hospitals and farms, excessive TCH
may lead to the selection of drug-resistant bacteria [3]. Once drug-
resistant bacteria enter the food chain, it will pose a serious threat to
human health and ecosystem [4]. At present, the concentration of TCH
in surface water and groundwater have reached μg/L [5,6]. Conven­
tional wastewater treatment methods including membrane filtration
[7], biological degradation [8] and adsorption [9], etc. cannot satisfy
the demand for rapid and effective degradation of antibiotics. Therefore,
it is urgent to develop efficient and environmental benign method for
Among advanced oxidation processes (AOPs), photocatalytic oxida­
tion as a rapidly expanding technology, is expected to become a low-
cost, environment-friendly and efficient wastewater treatment technol­
ogy attributed to its mild reaction conditions and strong oxidation
ability [10–12]. Development of appropriate photocatalysts is the key
for photocatalytic degradation of pollutants. Among various semi­
conductor photocatalysts, ZnIn2S4 as a typical ternary metal sulfide
semiconductor material shows excellent responsibility to visible light
due to its suitable band gap [13,14]. However, the application of pure
ZnIn2S4 in visible-light photocatalysis is limited because of its high
recombination of photogenerated holes and electrons [15]. It has been
proposed to improve ZnIn2S4 photocatalytic activity by forming heter­
ostructures with other semiconductors, which preserves visible light
absorption while improving carrier separation performance [16–18].
Zhang et al. synthesized ZnIn2S4 nanosheet-coated CdS nanorod heter­
ostructures to reduce Cr(VI) under visible light irradiation [19]. Sun

* Corresponding authors.
E-mail addresses: huzq1963@163.com (Z. Hu), hongwang@cumt.edu.cn (H. Wang).

https://doi.org/10.1016/j.cej.2021.132105
Received 21 May 2021; Received in revised form 16 August 2021; Accepted 25 August 2021
Available online 2 September 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
Y. Li et al.
et al. prepared hierarchical ZnIn2S4/CdIn2S4 microspheres to degrade
methyl orange and rhodamine B [18]. Wang et al. reported a ternary 3D
ZnIn2S4-MoS2 microsphere/1D CdS nanorod heterostructure with high
activity for high H2 evolution [20]. However, these heterojunctions all
contain Cd element which is a heavy metal with severe toxicity. Thus,
there is necessity to explore nontoxic and low-cost semiconductor ma­
terials to construct heterojunctions with excellent properties.
Tin disulfide (SnS2) has a fascinating band gap of ~2.35 eV which is
capable of effective absorption of visible light [21]. SnS2 can not only
serve as a superior photocatalytic hydrogen evolution catalyst [22,23],
but also shows excellent photocatalytic activity to degrade pollutants
[24,25]. Meanwhile, the non-toxic nature, inexpensiveness and visible
light responsiveness of SnS2 make it a suitable photocatalyst for
wastewater treatment [21–23]. However, as pure SnS2 is prone to photo-
corrosion [25] and suffers from the problem of difficult separation of
photogenerated electrons and holes, its photocatalytic performance
cannot satisfy the needs of practical applications. Therefore, we con­
structed the SnS2@ZnIn2S4 heterojunction to promote the charge sepa­
ration and enhance the photocatalytic activity. To improve the
recyclability and performance of photocatalysts, natural non-metallic
minerals are often used as carriers to disperse the photocatalysts,
given their widely existence, low cost, synergistic effect and ease of
recovery [26–28]. Kaolinite (Al2Si2O5(OH4)) is an abundant mineral
material containing lamellar aluminosilicate structure, which facilitates
the dispersion of nano-catalysts to achieve better performance [29]. On
this basis, it has good prospect to couple the SnS2@ZnIn2S4 hetero­
junction with kaolinite to build recyclable and efficient visible-light-
responsive photocatalysts for degradation of pollutants.
Type-II SnS2@ZnIn2S4 heterostructure has been proposed for visible
light photocatalytic reduction of Cr(VI) previously [30]. As the charge
carrier migration of the direct Z-scheme photocatalyst is more efficient
than that of the type-II heterojunction photocatalysts, direct Z-scheme
SnS2@ZnIn2S4 heterojunctions should be constructed towards better
photocatalytic performance [31]. Moreover, the in-situ growth of
SnS2@ZnIn2S4 heterostructure on natural kaolinite will not only enlarge
the surface area to induce more active sites for degradation of organic
pollutants, but also strengthen the electron transfer as well as assist the
preconcentration of pollutants by adsorption [32].
In this work, a direct Z-scheme SnS2@ZnIn2S4@kaolinite hetero­
structure photocatalyst was first synthesized to better utilize solar en­
ergy as well as regulate the path of photogenerated charge carriers for
the treatment of antibiotic wastewater. The photocatalytic degradation
performance of the prepared SnS2@ZnIn2S4@kaolinite heterostructures
was systematically studied using tetracycline hydrochloride as a target
contaminant. Compared with other reported literatures [33,34], the
addition of much less amount of the prepared photocatalyst led to
effective degradation of TCH with higher concentration under visible
light illumination, manifesting its excellent degradation efficiency for
antibiotics with an apparent rate constant reaching to 0.0231 min− 1.
Based on the crystal phases, morphologies, surface chemical states, pore
structure parameters, and optical properties of the as-prepared ternary
composite photocatalyst, the possible mechanism for the enhanced
photocatalytic performance was also investigated. This study provides a
new strategy for developing efficient photocatalysts with natural clay as
support materials, which demonstrates great potential in the treatment
of antibiotic wastewater.
2. Experimental
2.1. Materials
Zinc acetate (Zn(Ac)2, 99.5%), thioacetamide (CH3CSNH2, TAA,
AR), indium (III) chloride tetrahydrate (InCl3⋅4H2O, 98%), stannic
chloride hydrated (SnCl4⋅5H2O, 99%), TCH, 1,4-Benzoquinone (BQ), L-
histidine, isopropyl alcohol (IPA), K2Cr2O7, NaHCO3 were provided by
Beijing Inncohem Technology Co., Ltd (Beijing, China). Kaolinite was
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Chemical Engineering Journal 429 (2022) 132105
purchased from Aladdin. All reagents were directly used without further
purification.
2.2. Preparation of ZnIn2S4 microspheres
As illustrated in Scheme 1, 1 mmol Zn(Ac)2 and 2 mmol InCl3‧4H2O
were dissolved in 30 mL deionized water to obtain solution A, followed
with magnetic stirring for 30 min. At the same time, 4 mmol TAA were
dissolved in 30 mL deionized water to get solution B and the solution
was stirred for 30 min. After that, solution A was added into solution B
dropwise with continuous stirring for 1 h. Then the mixed solution was
put into a 100 mL reaction kettle lined with polytetrafluoroethylene
(PTFE) and kept at 160 ◦ C for 12 h. After the end of reaction, the product
was cooled to room temperature and washed with deionized water and
anhydrous ethanol for three times, respectively. The obtained product
was centrifuged at 9000 rpm and dried in the oven at 70 ◦ C for 24 h.
2.3. Preparation of SnS2 nanoparticles and SnS2@ZnIn2S4@kaolinite
composites
The SnS2@ZnIn2S4@kaolinite composites were synthesized by hy­
drothermal method in Scheme 1. To obtain composites with different
ratios of SnS2 to ZnIn2S4, the mass of SnS2 was varied sequentially with
the weight of ZnIn2S4 and kaolinite kept the same under all experiments.
SnCl4⋅5H2O (0.2461 g, 0,4922 g, 0.7832 g and 0.9843 g) was stirred
with solution A respectively for 30 min to obtain solution C. TAA
(0.3875 g, 0.4744 g, 0.5614 g, 0.6484 g) and 1 g kaolinite were
dispersed in 30 mL deionized water respectively and stirred for 30 min
to obtain solution D. Then solution C was added into solution D dropwise
with continuous stirring for 1 h under same reaction conditions to
synthetize samples with different weight ratios of SnS2/ZnIn2S4 ranging
from 0.25:1, 0.50:1, 0.75:1 to1:1, which were labeled as SZK-0.25, SZK-
0.50, SZK-0.75, SZK-1.0. Under the above conditions, 1 mmol
SnCl4⋅5H2O and 2 mmol TAA were dissolved in 30 mL deionized water
to obtained pure SnS2.
2.4. Characterization
Crystal phases of all samples were tested by XRD (BRUKER D8
ADVANCE X-ray powder diffractometer). Morphologies and structures
were recorded with a Field emission scanning electron microscope
(FESEM, MAIA3 LMH, China) with acceleration voltage 200 V–30 kV.
The transmission electron microscopy (TEM) was conducted using a
Tecnai G2 F20 to show the morphologies and interface assembly of the
as-obtained composites. Infrared spectroscope (FTIR, PerkinElmer) was
employed to investigate the valence bonding and functional groups of
materials using a KBr pellet technique. The Brunauer-Emmett-Teller
(BET) surface area and Density Function Theory (DFT) pore size distri­
bution were measured using a Quantachrome Autosorb-iQ analyzer with
UHP-grade nitrogen (99.999 %) at 77 K. The X-ray photoelectron
spectroscopies (XPS, THERMO FISHER Co., Ltd, ESCALAB 250Xi) were
tested to measure the valence state and surface composition of all ions in
as-obtained photocatalyst compounds. The valence-band of pure SnS2
and ZnIn2S4 were detected by Ultraviolet Photoelectron Spectra (UPS,
ESCALAB 250Xi, THERMO FISHER Co., Ltd. USA). UV-Vis diffuse
reflectance spectra (UV-vis DRS) were recorded using a UV-Vis spec­
trophotometer (Shimadzu UV2600, Corporation of Japan) equipped
with an integrating sphere attachment and BaSO4 as background.
Electrochemical impedance spectroscopy (EIS) and photocurrent stud­
ied were conducted with an electrochemical workstation (CHI650E,
Shanghai Chenhua Instrument Co., Ltd) with 0.2 M Na2SO4 as electro­
lytes and 300 W xenon lamp (CEL-HXF300, Beijing Zhongjiao Aulight
Technology Co., Ltd.) as light source. A TOC analyzer (Elementer, vario
TOC) was used to analyze the total organic carbon (TOC). The analysis of
intermediates was performed by high-performance liquid chromato­
graph (HPLC, Agilent, 1290) with a tandem mass spectrometer (MS,
Y. Li et al.
Scheme 1. Schematic illustration of the synthesis strategy of SnS2, ZnIn2S4 and SnS2@ ZnIn2S4@kaolinite.
Agilent, QTOF 6550).
2.5. Photocatalytic activity measurement
The photocatalytic activities of as-prepared SnS2@ZnIn2S4@Kao­
linite composites were measured by photodegradation of TCH using a
300 W xenon lamp (Perfect Light Technology Co., Ltd, China) with a
420 nm cut-off filter under the simulated solar light source, and the
distance between the liquid surface and the lamp was always maintained
at about 7 cm. When conducting the experiments, 20 mg photocatalyst
was dispersed in an aqueous solution of TCH (100 mL, 40 mg/L, pH =
6.0). Before irradiation, the systems were stirred in darkness for 30 min
to achieve adsorption-desorption equilibrium. After that, the systems
were exposed to visible light irradiation. The temperature of suspension
was maintained at 25 ◦ C in the circulating cooling water system during
photocatalytic tests. At given time intervals, about 3 mL solution was
sampled and filtered to remove the photocatalyst for the analysis of TCH
concentration by the dual-beam ultraviolet/visible spectrometer (Bei­
jing Purkinje general instrument Co. Ltd, TU-1900). Finally, the con­
centration of TCH were calculated by the follow equation (λmax = 356
nm):
Degradation efficiency = (C0 − C)/C0 × 100 %
where C and C0 represented the concentration of TCH after irradiation
and the initial TCH concentration, respectively.
For the recyclability experiments, SZK-0.75 was collected by
centrifugation after reaction and washed by deionized water and
ethanol for several times and dried in the oven at 60 ◦ C for 12 h. The
removal performance of recycled SZK-0.75 was studied to investigate
the reusability of catalyst.
2.6. Investigation of reactive species
In the quenching experiment, five different trapping agents (BQ, L-
histidine, IPA, K2Cr2O7, NaHCO3) were added into TCH solution to
detect the active species of photocatalytic reaction, respectively. BQ,
IPA, L-histidine, K2Cr2O7, NaHCO3 were used as trapping agents of su­
peroxide radical (•O2–), hydroxyl radical (•OH), singlet oxygen (1O2),
electron (e− ) and hole (h+) in the TCH degradation, respectively.
Chemical Engineering Journal 429 (2022) 132105
3. Result and discussion
3.1. XRD analysis
The XRD patterns in Fig. 1 show the results of structural character­
istics and crystallographic properties of kaolinite, SnS2, ZnIn2S4 and
SnS2/ZnIn2S4/kaolinite composites photocatalysts with different mass
ratios. For the pure SnS2 and ZnIn2S4, typical diffraction spectrums with
specific peaks were indexed with (PDF#23-0677) and (PDF#49-1562),
respectively. The typical peaks of SnS2 located at 15.03◦ , 28.20◦ , 32.12◦ ,
49.96◦ , 52.45◦ and 70.33◦ are well corresponding to (0 0 1), (1 0 0),
(1 0 1), (1 1 0), (1 1 1), and (1 1 3) crystal planes with lattice constants on
a = b = 3.649 Å, c = 5.899 Å. The appearance of no impurity peaks
indicates that pure SnS2 has been successfully synthetized. For the
pristine ZnIn2S4, the main diffraction peaks at 21.59◦ , 27.02◦ , 46.99◦ ,
52.26◦ and 55.77◦ can be indexed to (0 0 9), (0 1 2), (1 1 0), (1 1 9), and
(0 2 4) lattice planes. The SZK-0.25, SZK-0.50, SZK-0.75 and SZK-1.00
heterostructures exhibited the characteristic diffraction peaks of SnS2,
ZnIn2S4 and kaolinite, and no impurity peaks was observed, demon­
strating the successful formation of the heterostructures. Additionally,
the intensities of the (1 1 0) crystal plane of SnS2 gradually enhanced
(1)
Fig. 1. XRD patterns of kaolinite, SnS2, ZnIn2S4, SZK-0.25, SZK-0.50, SZK-0.75
and SZK-1.00.
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 Y. Li et al. Chemical Engineering Journal 429 (2022) 132105

with increasing its content, along with the decrease of intensities in the
(0 0 9) and (1 1 0) lattice planes of ZnIn2S4. Overall, the XRD character­
ization results preliminarily demonstrates that the SnS2@ZnIn2
S4@kaolinite heterostructures with good crystalline structures were
successfully obtained.
3.2. Morphology observation
The FESEM images of kaolinite, ZnIn2S4, SnS2 and SZK-0.75 were
displayed in Fig. 2(a–d). Kaolinite is a natural layered mineral with edge
and basal surfaces. As shown in Fig. 2(a), the pure kaolinite plates have a
smooth surface and were arranged in booklet agglomerates. The pre­
pared pure ZnIn2S4 displays nanosheet structure and some nanosheets
assembled into microsphere structures (Fig. 2(b)). As displayed in Fig. 2
(c), the average particle size of the obtained pure SnS2 is about 30 nm.
Pure SnS2 suffers from the problem of severe agglomeration, which may
lead to the reduction of catalytic surface area and restricted photo­
catalytic performance. Fig. 2(d) exhibits the irregular morphology of the
SZK-0.75 which consists of layered kaolinite, ZnIn2S4 nanosheets and
SnS2 particles. It can be observed that the SZK-0.75 has a large specific
surface with ZnIn2S4 nanosheets and SnS2 nanoparticles distributed on
the surface of the layered kaolinite. Besides, as exhibited in Fig. 2(e–g),
the EDS measurement illustrates the presence of kaolinite, SnS2 and
ZnIn2S4.
Although typical forms of SnS2 and ZnIn2S4 were found on kaolinite
in Fig. 2(d), the heterojunction between the components cannot be
clearly seen from the SEM images. Therefore, we further acquired TEM
and HRTEM images to prove the formation of heterojunction structures.
As shown in Fig. 3, SnS2 and ZnIn2S4 continuously covered the layered
surface of kaolinite, forming a stable ternary heterojunction structure.
HRTEM image (Fig. 3(c)) further shows that the two different lattice
fringe distances are 0.329 and 0.182 nm, corresponding to the (0 1 2)
crystal plane of ZnIn2S4 and the (1 1 0) crystal plane of SnS2, respec­
tively. These results further confirmed the successful synthesis of
SnS2@ZnIn2S4@kaolinite composites.
3.3. IR analysis
Moreover, the surface structure and internal molecular bonding of
the photocatalysts were investigated by Fourier transform infrared

Fig. 2. FESEM images of (a) kaolinite, (b) ZnIn2S4, (c) SnS2, (d) SZK-0.75; (f) EDS spectrum of the SZK-0.75; (e) and (g) SEM-EDS elemental mappings of SZK-0.75.

4
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Y. Li et al.
Fig. 3. TEM images (a, b) and HRTEM image of SZK-0.75.
spectroscopy (FTIR). Fig. 4 displays the FTIR spectra of the as-obtained
kaolinite, SnS2, ZnIn2S4 and their composites in the range of 4000–500
cm− 1. Apparently, the SZK samples exhibit the characteristic absorption
peaks of kaolinite, SnS2 and ZnIn2S4 in the FTIR spectra, which in
consistence with the results of XRD detection and FESEM observation,
once again proves the successful synthesis of SZK composites. The peaks
at about 3450 cm− 1 and 1627 cm− 1 were ascribed to the surface
adsorbed water molecules and hydroxyl groups [35], which may be due
to moisture-bearing air and the hydrothermal preparation process of the
samples. For the ZnIn2S4 and SZK composites, a new peak appeared at
1404 cm− 1, which corresponds to the characteristic peak of ZnIn2S4
[36]. The sharp absorbance peaks at 1095 cm− 1 can be assigned to Si-O
stretching modes, and the peaks at 980 cm− 1 and 819 cm− 1 can be
attributed to Al–Al–OH bonds. Additionally, Si–O out-of-plane bending
(666 cm− 1) and Si–O–Si in-plane bending (481 cm− 1) were clearly
observed for kaolinite [37–39] and SZK composites.
3.4. XPS analysis
To study the valence state distribution of SZK-0.75 photocatalysts,
XPS was carried out. The survey spectrum of SZK-0.75 is exhibited in
Fig. 5(a), and high resolution XPS spectra of O 1 s, Al 2p, Si 2p, Zn 2p, In
3d, Sn 3d and S 2p are shown in Fig. 5(b-h). It can be seen from Fig. 4
(b–d) that the O 1 s, Al 2p and Si 2p were detected, implying the exis­
tence of kaolinite in SZK-0.75. The binding energy of 532.45 eV is the
characteristic peak of O 1 s which could be taken as adsorbed H2O.
Furthermore, as for the Al 2p and Si 2p spectra, binding energy at
Fig. 4. FTIR spectra of kaolinite, SnS2, ZnIn2S4, SZK-0.25, SZK-0.50, SZK-0.75
and SZK-1.00.
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Chemical Engineering Journal 429 (2022) 132105
around 75.09 eV and 103.19 eV can be attributed to the AlO(OH) or
Al2O3 and SiO2 in the structure of kaolinite for SZK-0.75, respectively
[29]. Besides, as can be seen in Zn 2p spectrum (Fig. 5(e)), the two peaks
correspond to Zn 2p1/2 (1045.12 eV) and Zn 2p3/2 (1022.13 eV), indi­
cating the presence of Zn2+ [40]. The In 3d high resolution XPS spec­
trum (Fig. 4(f)) splits into 3d3/2 (452.50 eV) and 3d5/2 (444.96 eV)
peaks, which can be assigned to In3+. As shown in Fig. 5(g), two strong
characteristic peaks at 494.89 eV (Sn 3d3/2) and 486.48 eV (Sn 3d5/2),
which can be attributed to Sn4+. In addition, Fig. 5(h) shows two peaks
at 162.80 eV and 161.52 eV corresponding to the S 2p1/2 and S 2p3/2
binding energies respectively, which can be ascribed to S2− ions in SZK-
0.75. Overall, the valence states and elements were O 1 s, Al 2p, Si 2p, Zn
2p, In 3d, Sn 3d and S 2p in the SZK-0.75 heterostructures.
3.5. UV-vis DRS analysis
UV-vis DRS can be used to investigate the light absorption properties
of solid samples. The UV-vis DRS spectra of SnS2, ZnIn2S4, kaolinite and
their composites are shown in Fig. 6(a). For SZK composites, all samples
exhibit a red shift after loading SnS2, which indicating that the combi­
nation of SnS2 can improve the visible light absorption efficiency and
consequently generate e− /h+ pairs. The kaolinite has a broad absorption
edge at 382 nm, and the band gap of kaolinite was calculated to be 3.15
eV based on the Tauc function [41]:
(αhv)n = K(hv − Eg ) (2)
where α, hv, n, K, and Eg represented the absorption coefficient, photon
energy, the transition properties of semiconductors (indirect semi­
conductors: n = 1/2, direct semiconductors: n = 2), characteristic con­
stant of semiconductors and band gap, respectively. Herein, n = 1/2 due
to the as-prepared solid samples have indirect semiconductor properties
[25]. For the ZnIn2S4, it has a sharp absorption edge at around 585 nm,
corresponding to the 2.48 eV band gap. The pure SnS2 has a broad ab­
sorption edge at 787 nm and the band gap is calculated to be 1.54 eV. In
Fig. 6(b), for the SZK-0.25, SZK-0.50, SZK-0.75 and SZK-1.00 compos­
ites, their band gaps are in the between of the band gaps of SnS2, ZnIn2S4
and kaolinite. Therefore, the SZK photocatalysts can utilize visible light
more efficiently to promote the effective separation of photogenerated
charge carriers, and further improve the degradation efficiency of TCH
under visible light irradiation.
3.6. BET analysis and surface analysis
The N2 adsorption were carried out for the activated kaolinite, SZK-
0.25, SZK-0.50, SZK-0.75 and SZK-1.0 in order to evaluate the perma­
nent porosity. The surface area and pore volume of all samples were
calculated and shown in Table 1 using the Density Function Theory
(DFT) model. It reveals that the surface area of kaolinite was increased
after compounding of SnS2 and ZnIn2S4, which provided more surface-
active sites for the adsorption and photocatalytic degradation of
Y. Li et al. Chemical Engineering Journal 429 (2022) 132105

Fig. 5. XPS spectra of the SZK-0.75: (a) survey scan, (b) O 1 s, (c) Al 2p, (d) Si 2p, (e) Zn 2p, (f) In 3d, (g) Sn 3d, and (h) S 2p.

1/2
Fig. 6. (a) UV-vis absorbance spectra of kaolinite, SnS2, ZnIn2S4, SZK-0.25, SZK-0.50, SZK-0.75 and SZK-1.00.; (b) plot of (αhν) vs. hν.

within the scope of 1–80 nm.

Table 1
Surface area and pore volume of kaolinite, SZK-0.25, SZK-0.50, SZK-0.75 and
SZK-1.0. 3.7. Photocatalytic degradation of TCH
2 3
Sample SBET (m /g) Pore Volume (cm /g)
With TCH as a target pollutant, the degradation efficiencies of pure
kaolinite 10.354 0.037
kaolinite, SnS2, ZnIn2S4, and their composites with different mass ratios
SZK-0.25 26.628 0.088
SZK-0.50 19.643 0.066 were evaluated. Fig. 8(a) shows the time profile (0.0–60.0 min) of the
SZK-0.75 16.040 0.078 removal performance of kaolinite, SnS2, ZnIn2S4, SZK-0.25, SZK-0.50,
SZK-1.0 14.116 0.069 SZK-0.75 and SZK-1.0. For all the samples, the TCH solution was stirred
under darkness for 30 min firstly to make the photocatalysts reach
adsorption/desorption equilibrium. From Fig. 8(a), it can be observed
pollutants, and thus promoted the photocatalytic degradation efficiency.
that 1.52%, 12.94%, 27.38%, 17.83%, 28.11%, 45.08% and 41.17% of
In Fig. 7(a), all samples exhibited reversible type-IV isotherm with a H3
TCH were adsorbed for kaolinite, SnS2, ZnIn2S4, SZK-0.25, SZK-0.50,
hysteresis loop according to the classification rule of IUPAC [42], which
SZK-0.75 and SZK-1.0, respectively, indicating the different adsorption
is the main characteristics of mesoporous materials. The pore size dis­
abilities of the catalysts. Among all the prepared samples, SZK-0.75
tribution data of kaolinite, SZK-0.25, SZK-0.50, SZK-0.75 and SZK-1.0
exhibited a higher adsorption ability than other samples. As adsorp­
composites shown in Fig. 7(b) demonstrates that the pore size were
tion is related to many influence factors including surface area, pore

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Fig. 7. (a) The N2 adsorption-desorption isotherm of kaolinite, SZK-0.25, SZK-0.50, SZK-0.75 and SZK-1.0 composites; (b) DFT pore size distributions.

Fig. 8. (a) Photocatalytic activity curves of kaolinite, SnS2, ZnIn2S4 and SZK composites for the degradation of TCH aqueous solution under visible light irradiation;
(b) linear transform -ln(C/C0) of the kinetic curves of TCH degradation (R2: SZK-0.75: 0.841; SZK-1.0: 0.895; SZK-0.50: 0.953; ZnIn2S4: 0.901; SnS2,: 0.999; kaolinite:
1.000); (c) comparison of the apparent rate constants k (×10− 3/min) of the kaolinite, SnS2, ZnIn2S4 and SZK composites for the degradation of TCH; (d) successive
photocatalysis using SZK-0.75 as photocatalyst.

width as well as interaction sites, the superior adsorption performance of
SZK-0.75 may be attributed to the optimal combination of these aspects.
After 60 min under simulated solar light, for pure kaolinites, only 2.24%
of TCH was removed while the SZK-0.75 photocatalyst exhibited the
highest removal efficiency compared to all the other samples with a
removal rate of 88.23%, which confirms the enhanced adsorption-
photocatalytic degradation ability due to the synergistic effect of the
constructed heterostructure.
Based on the pseudo-first-order kinetic constants, the apparent re­
action rate constants (k) of the samples were calculated and exhibited in
Fig. 8(b, c). The insignificant degradation rate (0.14 × 10− 3 min− 1) of
kaolinite may attribute to the restriction of the visible light absorption
range. Owing to the severe aggregation and photo-corrosion, the SnS2
displayed a relatively low degradation rate (1.11 × 10− 3 min− 1). The
ZnIn2S4 degradation rate was calculated to be 9.99 × 10− 3 min− 1, which
was not satisfactory due to inherent recombination of photogenerated
electrons and holes. However, the composites of the three components
presented greatly enhanced photocatalytic degradation rate except SZK-
0.25. In particular, the SZK-0.75 sample displays the highest photo­
catalytic activity. Its reaction rate constant was calculated to be 23.1 ×

7
 Y. Li et al.
10− 3 min− 1, which exceeded that of kaolinite, SnS2 and ZnIn2S4 by a
factor of 165, 20.81 and 2.31, respectively. Further increase of SnS2
loading in the composites to SZK-1.0 led to a declined kinetic rate
constant (21.9 × 10− 3 min− 1), which may be ascribed to the decreased
surface area and shielded active sites of ZnIn2S4. Generally, with
increasing the amount of SnS2, the removal rate of TCH grew rapidly
first and then decreased slightly with the best weight ratio of 0.75:1.
The stability and reusability of the prepared SZK-0.75 for degrading
TCH were investigated by three consecutive cycles, as presented in Fig. 8
(d). In the repeated experiment operation of catalyst recovery, the
catalyst sedimentation performance is excellent and can precipitate
quickly in a short time, which indicates the feasibility of recycling and
recovery. The removal efficiency of the materials after three cycles is
comparable with that of newly prepared samples with only a decrease of
6.86%.
3.8. Confirmation of active species
The roles of main active species were investigated to reveal the
mechanism in photocatalytic degradation of TCH over SnS2@ZnIn2
S4@kaolinite photocatalysts. Herein, BQ, L-histidine, IPA, K2Cr2O7 and
NaHCO3 were adopted as •O2− , 1O2, •OH, e− and h+ scavengers,
respectively. As demonstrated in Fig. 9(a), the degradation of TCH was
obviously depressed upon the addition of BQ, L-histidine and K2Cr2O7,
among which the function of BQ was the weakest. The results indicated
•O2− and 1O2 were the pivotal active species and e− played a modest role
in the degradation of TCH. For IPA and NaHCO3, the suppressing effects
were not as prominent as those of BQ and K2Cr2O7, which indicated the
roles of •OH and h+ were insignificant in the photocatalytic degradation
process of TCH. As illustrated in Fig. 9(b), with the addition of BQ, L-
histidine, IPA, K2Cr2O7 and NaHCO3 into the TCH solution, the total
removal ratios were 67.04%, 72.50%, 88.54%, 78.64% and 88.52%
under 60 min visible light irradiation, respectively. To exclude adsorp­
tive removal of the materials, the TCH removal efficiencies only under
illumination were shown in Fig. S1. These results imply that •O2− ,1O2
and e− were the main active species in the process of photocatalytic
degradation of TCH visible light, and the order of dominant roles was
•O2− >1O2 > e− .
3.9. Photocurrent and EIS analysis
To compare the photo-generated charge separation efficiency of SZK
composites with different weight ratios, photocurrent-time (I-t) curves
and Electrochemical impedance spectroscopies (EIS) were measured. As
shown in Fig. 10(a), the SZK composites displayed photoelectric
Fig. 9. (a) Reactive species trapping experiments of SZK-0.75; (b) the degradation efficiency of SZK-0.75 sample in the present of different capture reagents under
visible light irradiation.
8
­
Chemical Engineering Journal 429 (2022) 132105
response to different extent. After modification with SnS2@ZnIn2S4, the
photocurrents of kaolinite were all improved, among which the SZK-
0.75 photocatalyst had the strongest photocurrent response. The
average photocurrent density of SZK-0.75 (913nA/cm2) is higher than
that of SZK-0.25 (489nA/cm2), SZK-0.50 (460nA/cm2), SZK-1.00
(839nA/cm2) and kaolinite (444nA/cm2), implying that the SZK-0.75
photocatalyst has the maximum separation of e− and h+. Fig. 10(b)
shows EIS Nyquist plots of kaolinite, SZK-0.25, SZK-0.50, SZK-0.75 and
SZK-1.0. The arc radius of the SZK-0.75 is the smallest among all the
samples, indicating faster surface reaction speed, lower inherent charge
recombination rate and improved migration of photoinduced charge
carriers of the SZK-0.75. These properties contribute to the excellent
performance of SZK-0.75 in the degradation of TCH.
3.10. Mineralization of TCH
To investigate the degree of mineralization of TCH by SZK-0.75
photocatalyst, the TOC contents of reaction solutions were measured
(Fig. 11). SZK-0.75 obtains a TOC removal efficiency of 55.86 % after 60
min illumination, which was lower than the adsorption-degradation
efficiency (88.23%, Fig. 8(a)), indicating the incomplete mineraliza­
tion of TCH by the SZK-0.75 photocatalyst within 60 min and the
presence of intermediate products.
3.11. Degradation intermediates and pathways
HPLC-MS was employed to monitor the degradation process and
detect the intermediates (Table S1). According to the main detected
intermediates, two possible transformation mechanisms for TCH pho­
todegradation were proposed (Scheme 2). In pathway I, products with
m/z of 509 (P1), 496 (P2), 432 (P3), 383 (P4) and 362 (P5) were
assigned as the dealkylation and deamination products of TCH due to
the oxidization by •O2− [43]. In pathway II, Compound P6 (m/z = 427)
was formed through the dehydroxylation of TCH (m/z = 445). Com­
pound P7 (m/z = 383), compound P8 (m/z = 361) and compound P9
(m/z = 272) were formed through the dealkylation reaction and N-
demethylation owing to the low energy of N-C bond of compound P6
(m/z = 427) [44,45]. The P10 (m/z = 278) was then transformed to the
compound P9 (m/z = 272) via the dehydroxylation. The P11 (m/z =
222) and P12 (m/z = 116) were formed through the further oxidation of
products P10 (m/z = 278) and P9 (m/z = 272) [44]. These ring-opening
products (P11, P12) were finally oxidized into CO2 and H2O with the
extension of irradiation time.
Y. Li et al. Chemical Engineering Journal 429 (2022) 132105

Fig. 10. (a) Transient photocurrent; (b) electrochemical impedance spectra of kaolinite and SZK composites.

3.12. Photocatalytic mechanism of SnS2@ZnIn2S4@kaolinite

In Fig. 12, the ionization potentials of SnS2 and ZnIn2S4, which are
equal to the valence band energy (EVB), were determined by Ultraviolet
Photoelectron Spectra (UPS). According to the formula [46]:
EVB (vs. vacuum) = hν + EFermi − ECutoff (3)

EVB(RHE) = EVB (vs. vacuum) − 4.44 (4)

where hν is 21.22 eV (the excitation energy of the He I Source Gun)

Fig. 11. The TOC removal curves of TCH on SZK-0.75 sample.
[47,48], the EVB of SnS2 and ZnIn2S4 can be obtained. As shown in
Fig. 12(a), the EFermi is 5.87 eV and the ECutoff is 21.54 eV, giving 1.11 eV
as the EVB of SnS2. Combined with the Eg of SnS2 (1.54 eV) obtained from
the UV-vis diffuse reflectance spectra, the ECB of SnS2 was calculated to
be − 0.43 eV. The EVB of ZnIn2S4 was obtained by a similar procedure
from Fig. 12(b) to be 2.07 eV, and thereby the ECB of ZnIn2S4 was esti­
mated to be − 0.06 eV.
According to the above results, a direct Z-scheme heterojunction
model can well depict the TCH degradation process in the
SnS2@ZnIn2S4@kaolinite system under visible light irradiation. As
shown in Scheme 3, upon visible light illumination, the photogenerated
e− in ZnIn2S4 CB will recombine with the photogenerated h+ in SnS2 VB,
leaving h+ in ZnIn2S4 VB and e− in SnS2 CB separated. The potential of

Scheme 2. The proposed transformation pathways of TCH degradation.

9
Y. Li et al.
Fig. 12. UPS spectrum of (a) SnS2 and (b) ZnIn2S4.
Scheme 3. Possible photocatalytic degradation mechanism of the SnS2@ ZnIn2S4@kaolinite under visible light.
the e− in SnS2 CB is − 0.43 eV (vs. NHE), which can generate •O2− as it is
more negative compared to the standard of oxygen reduction reaction
O2/•O2− (− 0.33 eV vs. NHE) [42]. The •O2− can directly react with TCH
to further oxidize it. Some e− can direct attack TCH under visible light
excitation. The h+ in ZnIn2S4 VB have a potential of 2.07 eV, which can
oxidize O2 to generate 1O2 because its more positive redox potential than
O2/1O2 oxidation reaction (1.88 eV vs. NHE) [49]. Meanwhile, the 1O2
can further oxidize TCH to form intermediates and even to CO2 and H2O.
The proposed hypothesis of the SnS2@ZnIn2S4@kaolinite system based
on direct Z-scheme heterostructure model is consistent with the exper­
imental results.
4. Conclusions
In summary, a novel direct Z-scheme SnS2@ZnIn2S4@kaolinite het­
erostructure photocatalyst has been successfully synthetized by hydro­
thermal method. The crystal phase, morphologies, functional groups,
chemical states, band gap and pore structures were analyzed by XRD,
SEM, FTIR, XPS, UV-vis DRS and BET, which confirmed the formation of
a novel ternary heterojunction structure and deeply studied the possible
mechanism. Under visible light irradiation, compared to the bare
kaolinite, SnS2 and ZnIn2S4, the as-obtained heterostructure displayed
an excellently improved photocatalytic performance for the degradation
of TCH with an apparent reaction rate of 0.0231 min− 1, which is 20.81
10
Chemical Engineering Journal 429 (2022) 132105
times and 2.31 times higher than that of SnS2 and ZnIn2S4, respectively.
In trapping experiments, active radicals, •O2− ,1O2 and e− , were
generated in the process of photodegradation. The •O2− and 1O2 were
proven to play dominant roles, while the e− was also involved in the
degradation process. Based on the intermediates identified by HPLC-MS
analysis, two possible degradation pathways of TCH were proposed. A
direct Z-scheme mechanism was proposed to depict the enhanced pho­
tocatalytic activity of the SnS2@ZnIn2S4@kaolinite heterostructure. The
direct Z-scheme SnS2@ZnIn2S4@kaolinite heterostructure photo­
catalysis system has broad application prospects in the use of solar en­
ergy to remove antibiotic contaminated wastewater.
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.
Acknowledgments
This work is supported by the National Natural Science Foundation
of China (21905303), the Natural Science Foundation of Jiangsu Prov­
ince (BK20180635), National Key Research and Development Program-
Technology integration and engineering demonstration of contaminated
Y. Li et al.
site remediation in Cluster district of coal industry (2020YFC1806505).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.132105.
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