Environmental Research 225 (2023) 115585

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Heterostructured 2D/2D ZnIn2S4/g-C3N4 nanohybrids for photocatalytic

degradation of antibiotic sulfamethoxazole and
photoelectrochemical properties
Ch Venkata Reddy a, Raghava Reddy Kakarla b, ****, Bai Cheolho a, ***, Jaesool Shim a, **,
Tejraj M. Aminabhavi c, d, *
a
School of Mechanical Engineering, Yeungnam University, 280 Daehak-ro, Gyoungsan-si, Gyeongsangbuk-do, 38541, Republic of Korea
b
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2006, Australia
c
Center for Energy and Environment, School of Advanced Sciences, KLE Technological University, Hubballi, 580 031, Karnataka, India
d
University Center for Research & Development (UCRO), Chandigarh University, Gharuan, Mohali, 140413, Punjab, 140 413, India

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

Keywords: In recent years, antibiotic drugs have been extensively used owing to increased industrial growth, and this has
ZnIn2S4 nanostructures created issues related to drinking water and a green environment. Different techniques have been used to resolve
Graphitic carbon nitride these issues, among which heterogeneous photocatalysis has been widely explored for the elimination of toxic
Heterostructured hybrids
compounds from wastewater resources. In this study, ZnIn2S4, g-C3N4, and ZnIn2S4/g-C3N4 hybrid hetero­
Photocatalysis
Sulfamethoxazole
structured composites are synthesized via hydrothermal method and used these (i) for the removal of antibiotic
Photoelectrochemical property sulfamethoxazole pollutant and (ii) photoelectrochemical water oxidation. The nanomaterials were character­
Water treatment ized using X-ray diffraction, Scanning electron microscopy, transmission electron microscopy, and UV–vis
Environmental remediation spectroscopy. The developed hybrid heterostructured composites were able to degrade sulfamethoxazole pol­
lutants as well as offer improved photoelectrochemical properties compared to pristine samples. The catalytic
performance of the materials developed under visible light irradiation was greatly improved for the degradation
of the antibiotic drug up to 89.4% in 2 h. Moreover, the hybrid heterostructured photoelectrode showed a better
photocurrent density (8.68 mA/cm2) and exhibited ~19.2 and 29.9 times greater photocurrent density than the
pristine photoelectrodes. Such a considerably increased catalytic activity was attributed to the active separation
of charge carriers and transmission. The study offers an innovative approach to develop effective catalysts, and
for the degradation of sulfamethoxazole as well as the PEC properties for hydrogen production.

1. Introduction widely used synthetic antibiotic drug in human/veterinary healthcare

and food preservatives for animals (Luo et al., 2019), which has been
Due to the rapid growth of pharmaceutical industries and wide use of identified in surface water. Its removal requires the development of
antibiotics in the healthcare sector, contamination of natural water re­ effective and ecological techniques to improve water quality.
sources has resulted in health issues and environmental pollution Innumerable methods have been developed in efforts to remove
(Zhang et al., 2022; Shwetharani et al., 2020; Kainth et al., 2023; Reddy pharmaceutical contaminants from water resources (Kamyab et al.,
et al., 2023; Bharagav et al., 2023). Frequent uses of antibiotic polluted 2022), but some of these methods have not been highly successful
water pose severe risks to human organisms even if they are present in because of their low concentration of effluents in water bodies. Many
low concentrations (Wang et al., 2022; Cui et al., 2021; Shetti et al., methods are expensive, sluggish, and cannot achieve complete miner­
2019; Bukkitgar et al., 2019; Jyothi et al., 2019). Sulfamethoxazole is a alization for less persistent impurities. Advanced heterogeneous

* Corresponding authors. Center for Energy and Environment, School of Advanced Sciences, KLE Technological University, Hubballi, 580 031, Karnataka, India.
** Corresponding author.
*** Corresponding authors.
**** Corresponding author.
E-mail addresses: [email protected] (R.R. Kakarla), [email protected] (B. Cheolho), [email protected] (J. Shim), [email protected] (T.M. Aminabhavi).

https://doi.org/10.1016/j.envres.2023.115585
Received 30 December 2022; Received in revised form 12 February 2023; Accepted 25 February 2023
Available online 26 February 2023
0013-9351/© 2023 Elsevier Inc. All rights reserved.
C.V. Reddy et al. Environmental Research 225 (2023) 115585

photocatalysis (semiconductor-based photodegradation) is recognized catalytic activity of 2D/2D ZnIn2S4/g-C3N4 hybrid heterostructures for
as a useful approach to remove emerging contaminants from wastewater the removal of antibiotic sulfamethoxazole, which is one of the most
since methods are eco-friendly, cost-effective, and efficient (Balaraman widely used pharmaceuticals, under visible light irradiation, and PEC
et al., 2022; Liu et al., 2022; Reddy et al., 2021; Koutavarapu et al., water oxidation properties for H2 generation. Herein a simple, eco-
2020; Reddy et al., 2023; Kumar et al., 2022). Photocatalysis has been friendly, and inexpensive facile hydrothermal synthesis technique is
attractive for the reduction of NOx and Sox gases and hydrogen pro­ proposed to synthesize ZnIn2S4, g-C3N4, and ZnIn2S4/g-C3N4 hybrid
duction via water splitting (Li et al., 2019; Lakshmana Reddy et al., heterostructured composites. Using the ZnIn2S4/g-C3N4 hybrid com­
2018; Singla et al., 2020). posite, a possible mechanism for its photocatalytic activity for antibiotic
Hitherto, different semiconductor materials have been examined for sulfamethoxazole degradation is suggested based on the experimental
photocatalytic performance (Mesbah et al., 2020) and photo­ analysis. Also, ZnIn2S4/g-C3N4 hybrid heterostructured composites dis­
electrochemical (PEC) water oxidation properties (Zhang et al., 2020; played superior PEC water oxidation properties compared to pristine
Zhang et al., 2020; Reddy et al., 2022). Among these, two-dimensional samples. Moreover, these are suitable for improving the energetic sites
(2D) ZnIn2S4 has been considered effective owing to its stable physico­ for the redox response and charge separation transfer properties to offer
chemical properties, non-noxiousness, and appropriate optical band gap an improved catalytic activity for drug degradation and PEC properties.
(2.4–2.8 eV) (Qin et al., 2020). Moreover, positively charged sulfur The proposed method and the materials developed offer a new
vacancies can be created on ZnIn2S4 surface due to the displacement of perspective for inexpensive, multiplicative, and effective catalyst sys­
sulfur ions in the matrix (Feng et al., 2023); this can boost the ability to tems useful for the degradation of pharmaceuticals and PEC water
absorb visible light. Such promising properties make ZnIn2S4 a favorable oxidation for the production of H2, and the materials developed here can
catalyst for PEC water oxidation, but sluggish rate of charge carrier also be useful in other photocatalytic environmental applications.
movement, high recombination rate of charge carrier efficacy, and large
diffusion distance path length limit its catalytic activity. This has led to 2. Materials and methods
the development of new methods for overcoming the limitations such as
doping (Huang et al., 2019), functionalization with inorganic metals 2.1. Materials
(Wang et al., 2021), construction of heterojunctions (Li et al., 2020), and
increasing the catalytic performance. The formation of heterojunctions Zinc sulfate (ZnSO4.7H2O; ≥99.95%), indium chloride tetrahydrate
with other suitable semiconductors has been a suitable approach (InCl3.4H2O; ≥97%), thioacetamide (TAA), melamine, ethylene glycol
because it can adjust the energy levels to quicken the charge carrier (EG), and sulfamethoxazole were bought from Sigma-Aldrich and Dae­
separation, transfer of charge, and tuning of the band gap (Yang et al., jung Co., Ltd., South Korea. Deionized water and ethanol were used in
2019). all the experiments. All compounds were used without further
Recently, 2D g-C3N4 has been extensively used in dye degradation, purification.
hydrogen production, and other progressive photo-oxidation responses
owing to its higher surface area, appropriate band locations, outstanding 2.2. Synthesis procedure
thermal and chemical constancy, easy synthesis, and eco-friendly nature
(Yang et al., 2019). The g-C3N4 facilitates the heterojunction composite Melamine powder was used to produce g-C3N4 powder through
to achieve greater separation efficacy and movement of the photoin­ thermal polymerization. After grinding about 10 g of melamine powder
duced charge carriers in the heterojunction composite. Moreover, for 30 min, the powder was placed in alumina crucibles at 550 ◦ C for 2 h,
2D/2D heterojunctions exhibit better benefits than the 0D/2D com­ resulting in pale yellow-colored bulk g-C3N4 powder. A mixture of 25
posites, while 2D/2D heterojunctions have close interfacial interactions mmol of zinc sulfate heptahydrate (ZnSO4.7H2O), 50 mmol of indium
and greater interaction areas to offer abundant charge transmission (III) chloride tetrahydrate (InCl3.4H2O), and 100 mmol of TAA were
networks and smaller transfer distance for photoinduced charge carriers added to 50 mL of deionized water (DI), and magnetically stirred for 30
(Liu et al., 2023). min. Subsequently, 100 mg of g-C3N4 powder was added to above so­
Therefore, these features contribute to outstanding constancy, lution and stirred for 15 min. The solution was then transferred to an
improved charge separation, rapid charge transfer, and effective cata­ autoclave and maintained at 150 ◦ C for 12 h. After cooling it to room
lytic performance. Hao et al., (2022) prepared a hierarchical temperature, the sample was collected via centrifugation and washed
g-C3N4/ZnIn2S4 core/shell heterostructure catalyst via a low tempera­ with distilled water and ethanol several times. The obtained powder was
ture solvothermal route and examined its catalytic activity for tetracy­ desiccated at 60 ◦ C for 12 h under a vacuum. A similar procedure was
cline. Khan et al. (2020) prepared Z-scheme ZnIn2S4/MoO3 used to synthesize a pure ZnIn2S4 sample without the addition of g-C3N4
heterojunction to test for the photodegradation of pollutants. Jin et al., powder.
(2021) reported a ZnIn2S4@PCN-224 composite for tetracycline photo­
degradation. Yang et al. (2019) developed ZnIn2S4/protonated g-C3N4 2.3. Characterizations
composites used in H2 production and tetracycline degradation. How­
ever, as per the reported literature, there are few reports on Different characterization techniques were used to examine the
g-C3N4/ZnIn2S4 2D/2D heterojunction for visible light induced photo­ synthesized samples. A PANalytical X’Pert PRO instrument was used to
degradation of pharmaceutical pollutants. Particularly, no reports on study the crystal phases. Field-emission scanning electron microscopy
the photodegradation of sulfamethoxazole using ZnIn2S4/g-C3N4 hybrid (FE-SEM, S-4800-Hitachi) and high-resolution transmission electron
heterostructures under visible-light illumination were investigated. microscopy (HR-TEM, Tecnai G2F20 S-Twin) were used to examine the
Therefore, the relationship between its physicochemical activity and morphology and microstructure. A Cary 5000 spectrophotometer (UV-
photodegradation efficiency is worth investigating. Furthermore, the VIS-NIR Spectrophotometer) was used to analyze optical absorption. A
2D/2D heterojunctions development in the catalytic domain is still in Thermo Scientific instrument (K-Alpha) was used for X-ray photoelec­
the emergent phase. Although several researchers have reported metal tron spectroscopy (XPS) examination. Fourier transform infrared spec­
sulphide-based nanostructures, they mostly followed complicated troscopy (FTIR) was used to study functional groups using Thermo
preparation methods (Jing et al., 2021). Therefore, a simple facile sol­ Nicolet 6700 instrument.
vothermal method is used in the current research to prepare 2D nano­
structures and inspect their photodegradation efficiency and PEC 2.4. Photocatalytic studies
properties.
The objective of this study is to provide structure performance Sulfamethoxazole was used to examine the catalytic properties of the

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synthesized g-C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4 hybrid hetero­ doped into the ZnIn2S4 host (Gunjal et al., 2020). Hence, the XRD
structured materials under visible light illumination. In a typical cata­ analysis confirmed the coupling of both samples during the synthesis
lytic experiment, 20 mg of photocatalyst was evenly dispersed in 100 mL procedure. The formation of heterojunction is later established by the
of aqueous antibiotic solution (15 mg/L). The mixed solution was XPS and TEM analyses. XRD analysis confirmed the crystal purity and
initially stirred using a magnetic stirrer in the absence of light for 30 min heterojunction formation between g-C3N4 and ZnIn2S4.
until adsorption/desorption conditions were attained. The solution was
then exposed to visible light (solar simulation AM 1.5 G, intensity 100 3.2. Surface morphology
mW/cm− 2). During the catalytic experiment, 3 mL of the solution was
removed at regular intervals, and the catalyst was collected by centri­ SEM, TEM, and HR-TEM studies were performed to obtain the sur­
fugation. The change in antibiotic concentration was measured using a face morphologies and microstructural properties of the synthesized
UV–Vis spectrophotometer (Cary 5000 spectrophotometer, USA). samples. Fig. 2 illustrates the distinctive SEM images of the pristine g-
C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4 hybrid heterostructures. As dis­
2.5. PEC studies played in Fig. 2a, pristine g-C3N4 has a nanosheet-like smooth surface
morphology, which can be exfoliated into tiny sheet-like structures
PEC studies were conducted using a three-electrode electrochemical using ultrasonication (Fig. 2b). The SEM images of pristine ZnIn2S4
system (Biologic, Sp-200), in which Ag/AgCl (reference electrode), Pt displayed a regular spherical (marigold)-like surface morphology with
(counter electrode), and the fabricated samples (working electrode) 2–4 μm diameter composed of several uniform nanosheets as shown in
were used in aqueous Na2SO4 (2 mol/L) electrolyte solution. The pho­ the inset of Fig. 2a. Similarly, Fig. 2 (b) illustrates SEM images of
tocurrent–voltage curves were recorded using the linear sweep vol­ ZnIn2S4/g-C3N4 hybrids.
tammetry (LP) at a scan rate of 5 mV/s (vs. Ag/AgCl) under light on/off From the images, a clear attachment of g-C3N4 nanosheets on the
conditions. Electrochemical impedance spectroscopy (EIS) curves were microspheres of ZnIn2S4 can be observed. In addition, ZnIn2S4 spherical
recorded for 2 M Na2SO4 solution in the frequency range of 0.01 Hz–100 surface covered a high density of g-C3N4 nanosheets, and such a
kHz with a 0.1 V applied potential. distinctive classified heterostructure displays considerably greater spe­
cific surface area than the pristine samples, thereby offering extra active
3. Results and discussion sites for the catalytic performance. Furthermore, the linkage between
ZnIn2S4 and g-C3N4 nanosheets has increased the light-harvesting per­
3.1. X-ray diffraction analysis formance via multi-replication procedures for the occurrence of elec­
tromagnetic waves (Chen et al., 2019). The SEM analysis exhibits that
The structural phases of synthesized materials were examined using g-C3N4 and ZnIn2S4 are closely bound together, which may enhance the
X-ray diffraction (XRD), and the XRD patterns are shown in Fig. 1. charge carrier separation and improve the photodegradation efficiency
As can be seen from Figure, g-C3N4 nanosheets exhibit two distinct and PEC properties.
XRD peaks at 12.9◦ and 27.4◦ associated with (100) and (002) phases, TEM image of ZnIn2S4/g-C3N4 hybrid is illustrated in Fig. 3a, which
which signify the in-plane tri-s-triazine rings and the stacking of inter­ further confirms that the surface of the ZnIn2S4 nanosheet is covered
layer aromatic ring packing units, respectively (VanNguyen et al., 2022) with g-C3N4 nanosheets. Fig. 3b and c displays HR-TEM and selected
(Qin et al., 2020). In the case of ZnIn2S4, distinctive diffraction peaks area electron diffraction (SAED) patterns of ZnIn2S4/g-C3N4. As pre­
observed at 21.5◦ , 27.6◦ , 47.1◦ , 50.8◦ , and 55.5◦ are associated with sented in Fig. 3b, the identified lattice fringe of 0.32 nm is associated
(006), (101), (110), (115), and (022) lattice phases, respectively that are with (101) lattice plane of the hexagonal ZnIn2S4, which is in good
well-matched with the hexagonal phase of ZnIn2S4 (JCPDS No. agreement with the XRD analysis.
65–2023). The binary sulfide (ZnS and In2S3)-related contamination The SAED pattern confirmed the crystalline nature of the hybrid
patterns were not observed, which confirmed the structural purity of the composite. Fig. 3 d–i display scanning transmission electron microscopy
synthesized material. For ZnIn2S4/g-C3N4, the diffraction peaks of both (STEM) elemental mapping, which reveals the occurrence of C, N, Zn, I,
the materials were observed, and the characteristic patterns of ZnIn2S4 and S with distinct colors and successful synthesis of the hybrid com­
and g-C3N4 at 27.6◦ and 27.4◦ were very close and overlapped with each posite. Consequently, the close contact between ZnIn2S4 and g-C3N4
other (Yang et al., 2019), which may be due to the c-axis orientation of nanosheets may be advantageous for interfacial photo-excited electron-
ZnIn2S4 nanosheets (Fan et al., 2023). Furthermore, no substantial peak hole transmission from g-C3N4 to ZnIn2S4. Moreover, clear contact be­
shift was observed in the hybrid sample, indicating that g-C3N4 was not tween g-C3N4 to ZnIn2S4 could be advantageous for the photo-excited
charge transmission through the heterojunction (Khan et al., 2020).

3.3. Optical analysis

UV–vis reflectance spectroscopy was used to investigate the optical

properties of the synthesized photocatalysts, and the results are shown
in Fig. 4.
As can be observed from Fig. 4a, all the synthesized samples
exhibited a wide optical absorption range in the UV and visible regions.
The individual g-C3N4 and ZnIn2S4 samples showed absorption edges at
454 nm and 500 nm, respectively. After the addition of g-C3N4 to
ZnIn2S4, the ZnIn2S4/g-C3N4 hybrid sample showed noticeably
enhanced light absorption intensity in the visible region and a red-
shifted absorption edge (530 nm). The strong absorption capability in
the visible light region is chiefly attributed to a synergistic effect be­
tween g-C3N4 and ZnIn2S4 (Wu et al., 2019), (Liu et al., 2022). In
addition, a broader and stronger absorption of visible light produced
more photoinduced charge to contribute to the photocatalytic activity,
leading to enhanced photocatalytic performance for the removal of
Fig. 1. X-ray diffraction patterns of the synthesized samples. pollutants.

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Fig. 2. (a) Pristine g-C3N4, (b) ZnIn2S4/g-C3N4 hybrid heterostructure composites (Inset: pristine SEM image of ZnIn2S4).

Fig. 3. (a) TEM, (b) HR-TEM, (c) SAED, and (d–i) EDX mapping of Zn, In, S, C, and N of the ZnIn2S4/g-C3N4 hybrid heterostructure composites.

The optical band gaps of the samples were evaluated using Tauc plots 3.4. XPS analysis
of optical absorption as illustrated in Fig. 4b. The estimated band gap
values of g-C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4 hybrids were 2.68, 2.39, XPS was used to study the electronic states and chemical structure of
and 2.26 eV, respectively. The reduced band gap of ZnIn2S4/g-C3N4 ZnIn2S4/g-C3N4 as illustrated in Fig. 5.
signifies that the presence of g-C3N4 can efficiently improve the ab­ The survey XPS spectrum confirms that ZnIn2S4/g-C3N4 exhibits the
sorption ability of visible light and absorption edge, which is a signifi­ presence of all distinctive peaks of Zn (2p), S (2p), In (3 d), C (1s), and N
cant factor in increasing photocatalytic pollutant removal efficiency (1s) as displayed in Fig. 5a). The deconvoluted Zn 2p spectrum is shown
under the visible light illumination (Qin et al., 2020). in Fig. 5b. The XPS peaks of Zn 2p3/2 and Zn 2p1/2 were observed at the

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Fig. 4. (a) UV–vis DRS spectra, and (b) band gaps of synthesized samples.

Fig. 5. XPS spectra (a) survey, (b) Zn, (c) In, (d) S, (e) N, and (f) C of ZnIn2S4/g-C3N4 hybrid heterostructure composites.

binding energies (BE) of 1021.3 eV, and 1044.5 eV (Wang et al., 2023; Li also conclude that the synergic contact between g-C3N4 and ZnIn2S4
et al., 2023). Similarly, 3 d deconvoluted spectrum (Fig. 5c) showed two shows modification in the ZnIn2S4 electronic band structure and gen­
distinctive signals of In 3d5/2 and In 3d3/2 at BE of 444.3 and 451.8 eV erates energy levels between conduction and valence bands (Gunjal
(Gunjal et al., 2020). The XPS signals of S 2p3/2 and 2p1/2 were noticed et al., 2020).
at BE of 161.1 eV and 162.6 eV (Du et al., 2019; Tateishi et al., 2019) as FTIR technique was used to examine the chemical structures of g-
displayed in Fig. 5d, which are related to S2− in ZnIn2S4 (Li et al., 2019). C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4 as shown in Fig. 6. The distinctive
The deconvoluted N 1s XPS spectrum (Fig. 5e), which exhibited peaks stretching vibration of g-C3N4 is observed between 1200 and 1650 cm− 1,
related to C–N– – C, N–(C)3 and C–N–H at BE of 398.0 eV, 399.7 eV, and which is attributed to the stretching vibration of CN units (Zhou and Qiu,
400.6 eV, respectively (Tian et al., 2022). As noticed in Fig. 5f, three XPS 2019). The peaks between 3000 and 3600 cm− 1 were initiated in the NH
signals are observed at BE of 284.2 eV, 286.1 eV, and 287.5 eV, which and O–H stretching vibration modes. The peak at 807 cm− 1 can be
are associated with C–C bonds, C– – NH2, and N–C = N, respectively (Li attributed to s-triazine ring vibration mode (Wang et al., 2019). These
et al., 2022), (Chamanehpour et al., 2023). XPS analysis confirmed the consequences are also found in ZnIn2S4/g-C3N4, further showing the
chemical state of ZnIn2S4/g-C3N4. In comparison with reported pristine g-C3N4 presence in ZnIn2S4/g-C3N4 hybrid composites.
ZnIn2S4 BE, there is a shift in the BE of ZnIn2S4/g-C3N4, signifying a In addition, peaks identified between 1385 and 1630 cm− 1 are
strong interface between ZnIn2S4 and g-C3N4. This close interfacial related to surface-absorbed water molecules, and hydroxyl groups were
interaction assists electron transmission between g-C3N4 and ZnIn2S4 to observed in pure ZnIn2S4, which further occurred in ZnIn2S4/g-C3N4
attain an equivalent position of the Fermi level. The optical properties (Kumar et al., 2023). These results indicate that ZnIn2S4 was successfully

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Table 1
Photocurrent achieved from C–V and I–V for all the synthesized photoelectrodes.
Sample C–V I–V
Name
Photocurrents ΔJ (mA/ Photocurrents ΔJ (mA/
(mA/cm2) cm2) (mA/cm2) cm2)

Dark Light Dark Light

state state state state
g-C3N4 5.46 5.93 0.47 7.59 7.88 0.29
ZnIn2S4 11.02 12.20 1.18 20.99 21.44 0.45
ZnIn2S4/g- 14.32 19.47 5.15 26.12 34.80 8.68
C3N4

photocurrent density data are presented in Table 1. The hybrid hetero­

structure photoelectrode exhibited enhanced PEC activity compared to
that of pure photoelectrodes and the hybrid photoelectrode exhibited an
enhanced photocurrent density of 8.68 mA/cm2 compared to those of
pristine g-C3N4 (0.29 mA/cm2) and ZnIn2S4 (0.45 mA/cm2) photo­
electrodes, and ~19.2 and 29.9 folds higher photocurrent density than
Fig. 6. FTIR spectra of g-C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4 hybrid hetero­
the pure ZnIn2S4 and g-C3N4 photoelectrodes, respectively; the onset
structure composites.
potential also reduced with the formation of heterojunctions.
The enhanced photocurrent density attained in the hybrid composite
combined with g-C3N4. Moreover, after the addition of g-C3N4 with
photoelectrode might be due to reduced resistance of charge trans­
ZnIn2S4, the intensity of absorption band decreased. Hence, the out­
mission, greatly reduced recombination rate of the photoinduced
comes confirm that ZnIn2S4 is successfully integrated with g-C3N4 dur­
charge, and quick transfer of the charge carriers. Moreover, the ZnIn2S4/
ing the synthesis procedure.
g-C3N4 photoelectrode displays the lowest onset potential compared to
individual samples, further illuminating its best PEC activity.
3.5. PEC studies EIS was used to evaluate the surface charge transmission capability,
charge transmission resistance, and photoinduced charge separation
PEC studies were performed on the prepared ZnIn2S4, g-C3N4, and efficacy of the fabricated photoelectrodes (Khosya et al., 2023). Fig. 8a
ZnIn2S4/g-C3N4 photoelectrodes in 2 M Na2SO4 electrolyte solution. shows the Nyquist curves of the prepared photoelectrodes in 2 M Na2SO4
Fig. 7a shows cyclic voltammetry (C–V) curves of the prepared photo­ electrolyte solution. Generally, the diameter of the Nyquist curves in­
electrodes under dark/light illumination conditions. The ZnIn2S4/g- dicates the charge-transfer resistance at the electrode interface. A larger
C3N4 photoelectrode exhibited an improved photocurrent compared to diameter indicates greater resistance to charge transmission, while a
pristine photoelectrodes. smaller diameter indicates lower resistance to charge transmission
The observed photocurrent densities are presented in Table 1. Notice (Pudkon et al., 2019).
that the hybrid heterostructure photoelectrode displayed an enhanced As shown in Nyquist plots, the ZnIn2S4/g-C3N4 photoelectrode
photocurrent density of 5.15 mA/cm2 compared to pure g-C3N4 (0.47 diameter is smaller than that of the pristine electrodes. ZnIn2S4/g-C3N4
mA/cm2) and ZnIn2S4 (1.18 mA/cm2) photoelectrodes, respectively, hybrid photoelectrode showed the lowest diameter, representing a
while the hybrid heterostructure photoelectrode displayed ~4.3 and lower charge transmission resistance. Likewise, the larger diameter of
10.9 folds higher photocurrent density than the pristine ZnIn2S4 and g- the pristine electrodes suggests a greater charge transmission resistance
C3N4 photoelectrodes, respectively. in comparison to the composite photoelectrode. Therefore, the addition
Similarly, LP (I–V) curves were obtained for the prepared photo­ of g-C3N4 to ZnIn2S4 to form a heterojunction could efficiently enhance
electrodes under the same conditions as shown in Fig. 7b. It is observed the transmission and separation capability of the photoexcited charge
from the cures that photocurrent starts at 0.51 and 0.27 V (vs. Ag/AgCl) carriers. EIS analysis results are in good agreement with the photocur­
for pure g-C3N4 and ZnIn2S4, while it initiates at ~0.19 V (vs. Ag/AgCl) rent characteristics.
for hybrid photoelectrode under light irradiation. The observed

Fig. 7. (a) Cyclic voltammetry curves, and (b) linear sweep voltammetry curves of prepared photoelectrodes.

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Fig. 8. (a) Nyquist plots, and (b) Transient photocurrent (I-t) curves of prepared photoelectrodes.

The stability of photoelectrodes was evaluated using transient performance than the pristine photoelectrodes.
photocurrent (I-t) response as a function of time (Fig. 8b). The curves
show small photocurrent intensity in pristine photoelectrodes, while in 3.6. Photocatalytic studies
contrast, hybrid photoelectrode exhibited enhanced photocurrent den­
sity (Lv et al., 2023). This enhancement in light-excited photocurrent is Photodegradation activities of g-C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4
due to its appropriate band gap, improved separation and transportation catalysts were examined for sulfamethoxazole (SMX) antibiotic under
efficacy of the photoinduced electron-hole pairs in the hybrid photo­ the visible light irradiation and results are presented in Fig. 9.
electrode. The hybrid composite photoelectrode displayed better ab­ SMX photolysis in the absence of a catalyst revealed no significant
sorption of visible light than the individual photoelectrodes, and thus, degradation, while absorption–desorption equilibrium was attained
ZnIn2S4/g-C3N4 photoelectrode showed a better PEC water oxidation between the catalyst and the SMX in 45 min in the dark. After the

Fig. 9. (a) Photocatalytic degradation of SMX, (b) Pseudo-first-order kinetics, (c) Degradation rate constants, and (d) Repeatability tests.

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C.V. Reddy et al. Environmental Research 225 (2023) 115585

addition of SMX, a significant photodegradation was achieved under the performance of ZnIn2S4/g-C3N4 for SMX.
light irradiation (Fig. 9a). As can be observed, ZnIn2S4/g-C3N4 exhibited From the Figure, it is clear that higher removal efficiency of SMX was
enhanced photodegradation (89.4%) under 2 h of light illumination observed at pH 6, and a removal efficiency of 57% was observed at pH 7.
compared to the individual catalysts, while pristine catalysts exhibited However, the drug removal efficiency of ZMX was still higher at pH 5.
relatively lower photodegradation (g-C3N4: 31.4% and ZnIn2S4: 49.6%) This may be due to: (i) H+ content in solution reduced with increasing
due to its high photoexcited charge carrier recombination rate. Likewise, pH, leading to a lower intake of O•−2 radicals by H (Song et al., 2017) ;
+

ZnIn2S4/g-C3N4 showed considerably superior photodegradation per­ hence, extra O•−

2 radicals might contribute to catalytic activity; (ii) at pH
formance owing to synergetic effect and interface development after the >5.60, electron providing NH– group strength on the pollutant would be
addition of g-C3N4 to ZnIn2S4. In addition, g-C3N4 hybridization improved owing to the effect of deprotonation (Song et al., 2018).
considerably affected the degradation of the hybrid composite. There­
fore, the hybrid catalyst showed an uppermost catalytic performance
3.7. Catalytic reaction mechanism
(89.4%), which is around ~ 2.8 and 1.8 times greater than the indi­
vidual g-C3N4, and ZnIn2S4 catalysts, respectively.
To investigate catalytic performance mechanism and quenching
The photodegradation rate constants of SMX were evaluated using
species contributing to photodegradation, scavenger tests were carried
pseudo-first-order kinetic equation (Wang et al., 2023) to analyze the
out under similar conditions of catalytic activity under visible light
experimental data as shown in Fig. 9b. The slope of the plot, ln (C/C0)
illumination. Isopropyl alcohol (IPA), 1,4-benzoquinone (BQ), and
was used to determine the kinetics of catalytic reaction. The determined
ammonium oxalate (AO) were used as the quenchers to trap OH•, O•− 2
catalytic reaction rate kinetics were 0.00183 min− 1, 0.00547 min− 1, and
radicals, and h+, respectively, as shown in Fig. 10b. As a result of the
0.0587 min− 1 (Fig. 9c) for g-C3N4, ZnIn2S4, and ZnIn2S4/g-C3N4 hybrids,
addition of BQ and IPA quenchers, SMX photodegradation was signifi­
respectively, and hybrid catalysts showed improved degradation rate
cantly reduced, indicating that O•− 2 and OH active species played the
•
constants compared to individual catalysts. The results indicate that
leading roles in catalytic activity; in contrast, with the addition of AO, no
hybrid catalyst displays greater photodegradation of SMX than the
considerable degradation was observed, signifying that the hole is not
pristine catalysts, which may be attributed to synergistic interface in the
the chief reactive species for the organic pollutants degradation.
composite catalysts. Moreover, after the addition of g-C3N4 to ZnIn2S4,
Therefore, O•−2 and OH radicals contributed significantly to the drug
•
the composite exhibited considerably improved degradation activity
removal under visible-light irradiation.
with a removal rate of 89.4%. Such an enhanced degradation perfor­
Based on the above results, a possible photodegradation type–II
mance of the hybrid occurred because g-C3N4 acted as an electron
heterojunction mechanism for ZnIn2S4/g-C3N4 is schematically pre­
mediator, and surface properties can significantly prevent the charge
sented in Fig. 12. As shown in Fig. 11, ZnIn2S4 and g-C3N4 valence band
carrier’s recombination rate (Du et al., 2020). Furthermore, the signif­
(VB) potentials were evaluated as 1.08 and 1.55 eV (vs NHE) (Ma et al.,
icantly improved catalytic activity of the hybrid catalyst can be due to
2022). The conduction band (CB) potentials were evaluated using: ECB
the greater lifespan of the photoexcited electron-hole pairs, better use of
= EVB – Eg, where the evaluated potentials are − 1.31 and − 1.13 eV (vs
light, greater surface area, and appropriate band gap position (Li et al.,
NHE) for ZnIn2S4 and g-C3N4, respectively.
2023).
Under light illumination, photoinduced electron holes are produced
Repeated degradation tests were also performed to examine the
by both ZnIn2S4 and g-C3N4 in the CB and VB. Likewise, ZnIn2S4 CB
photo-constancy and reusability of ZnIn2S4/g-C3N4 for practical appli­
electrons are transferred to g-C3N4 CB, and g-C3N4 VB holes are trans­
cations. The hybrid catalyst showed outstanding photostability during
ferred to ZnIn2S4 VB owing to CB and VB potentials of ZnIn2S4 and g-
the degradation under visible light irradiation, and ZMX degradation
C3N4. The electrons in CB of g-C3N4 can respond with the adsorbed O2 to
efficacy was 80% after four successive reuses of the catalytic procedure.
produce O•−2 species due to the more negative CB edge than the standard
In particular, catalytic performance was marginally reduced with
reduction potential (O2/O•− 2 , − 0.33 eV vs NHE) (Saravanakumar et al.,
cycling repeatability as shown in Fig. 9d, which can be attributed to a
2023).
loss of the catalyst during the collection and deactivation of some cat­
Likewise, g-C3N4 VB had enough energy to create •OH radicals from
alytic sites on the material (Zhou et al., 2020).
OH− (Saravanakumar and Park 2021). Hence, the photoinduced holes
The solution pH is important for photodegradation because the dis­
cannot produce hydroxyl radicals. Instead, the photoinduced holes
charged organic impurities have dissimilar pH values. The initial pH
directly degraded the drug as confirmed by the scavenger tests, and the
values of SMX were adjusted using 0.1 M NaOH solution to reach the
hybrid catalyst degraded the drug into harmless products. In summary,
preferred pH values. Fig. 10a shows the influence of pH on the catalytic
strong interface contact increased the charge carrier mechanism and

Fig. 10. (a) pH effect, and (b) radical trapping experiments on ZnIn2S4/g-C3N4 catalyst.

8
C.V. Reddy et al. Environmental Research 225 (2023) 115585

Fig. 11. Valance band XPS of (a) ZnIn2S4, and (b) g-C3N4 catalysts.

scope of new catalysts to offer strong practical support for wastewater

treatment and PEC applications such as water splitting for hydrogen
production towards practical applications.

Credit author statement

The authors listed in the manuscript have contributed in this

research work, and agreed to submit the manuscript to this journal.

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.

Data availability
Fig. 12. Schematic illustration mechanism of SMX pollutant using ZnIn2S4/g-
C3N4 catalyst. No data was used for the research described in the article.

inhibited the recombination rate of the photoinduced charge carriers, Acknowledgments

leading to improved catalytic efficacy of ZnIn2S4/g-C3N4.
This work was supported by National Research Foundation (NRF) of
4. Conclusions Korea (2020R1A4A1019227 and 2020R1A2C1012439).

In summary, we have successfully developed a unique 2D/2D het­ References

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