Modified Synthesis and Photocatalytic Properties of Indium Zinc Sulfide

Hongfei Bi; Jinsong Liu; Zhengying Wu; He Suo; Xueliang Lv; Yunlong Fu

doi:10.7536/PC201111

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (12) : 2334-2347 DOI: 10.7536/PC201111

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Modified Synthesis and Photocatalytic Properties of Indium Zinc Sulfide

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Abstract

With rapid development of social economy, shortage of energy and destruction of ecology have gradually aroused people’s strong concern. In recent years, finding the suitable solution has become the focus of attention. As a green environmental protection technology, photocatalysis has become a research hotspot to deal with energy and environmental issues because of its high efficiency and low cost. In many photocatalytic materials, ternary sulfide Indium Zinc Sulfide (ZnIn₂S₄) has shown great potential due to visible-light-responding characteristics, simple preparation and excellent stability. However, high carrier recombination rate of the ZnIn₂S₄ limits its photocatalytic activity. In recent years, many studies on modifying ZnIn₂S₄ have been reported. Here, different modification researches are introduced in detail including synthesis of ZnIn₂S₄ monomer, construction of semiconductor compounds, noble metal deposition, carbon element modification, and ion doping. Then, their photocatalytic properties and corresponding mechanisms including hydrogen evolution, degradation of organic pollutants, reduction of hexavalent chromium and CO₂, and organic synthesis are systematically summarized. Finally, development direction and prospect of ZnIn₂S₄ are put forward for more extensive and in-depth research on photocatalytic properties and application in practical production as soon as possible.

Contents

1 Introduction

1.1 Photocatalytic technology

1.2 Preparation of indium zinc sulfide

2 Synthesis and modification of indium zinc sulfide

2.1 Synthesis of indium zinc sulfide monomer

2.2 Semiconductor compounds construction

2.3 Nobel metal deposition

2.4 Carbon element modification

2.5 Ion doping

3 Application of indium zinc sulfide in the field of photocatalysis

3.1 Photocatalytic hydrogen evolution

3.2 Photocatalytic degradation of organic pollutants

3.3 Application of indium zinc sulfide in other fields

3.4 Stability of indium zinc sulfide

4 Conclusion and outlook

Graphical abstract

Keywords

ZnIn₂S₄ / photocatalysis / hydrogen production / degradation

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Hongfei Bi, Jinsong Liu, Zhengying Wu, He Suo, Xueliang Lv, Yunlong Fu. Modified Synthesis and Photocatalytic Properties of Indium Zinc Sulfide. Progress in Chemistry, 2021, 33(12): 2334-2347 DOI:10.7536/PC201111

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1 Introduction

1.1 Brief Introduction of Photocatalytic Technology

With the rapid development of social economy, the problems of energy shortage and ecological environment destruction have aroused people's strong concern, and sustainable development has become the choice that contemporary society must face. Semiconductor photocatalysis, based on the utilization of solar energy, is a very promising technology to deal with this problem. In 1972, Honda and Fujishima first discovered the phenomenon of photolysis of water to produce hydrogen and oxygen on the TiO₂, which was an opportunity to start the study of photocatalysis^[1]. Later, Carey et al and Frank et al found that TiO₂ could remove a variety of refractory organics and cyanide in water by photocatalysis, which promoted the research and application of semiconductor photocatalytic technology in the field of wastewater treatment^[2,3]. With the in-depth study of nano-semiconductor materials, many semiconductor materials have been developed in the field of photocatalysis, including oxides, sulfides and nitrides^[4⇓~6].

The photocatalytic effect of semiconductor comes from the photocatalytic reaction on the surface. As shown in fig. 1A, when light with energy greater than the forbidden band width (E_g) irradiates the semiconductor, electrons in the valence band are excited to jump to the conduction band, and corresponding holes are generated in the valence band^[7]. The electron-hole pairs generated in the semiconductor move by diffusion under the action of the electric field, and redox reaction occurs with the substances adsorbed on the surface of the catalyst particles, that is, photocatalytic reaction.

1.2 Properties of Indium Zinc Sulfide

Due to the wide band gap, TiO₂ can only respond to ultraviolet or near ultraviolet light, which is difficult to meet the requirements of practical applications. Therefore, in order to make better use of solar energy, the development of visible light response photocatalysts has attracted much attention. Among many semiconductors, transition metal sulfides have narrow band gaps and can absorb more visible light in the process of photocatalytic reaction^[11,12]. Among them, ZnIn₂S₄, a ternary sulfide, is an n-type semiconductor, which has attracted wide attention because of its suitable energy band position, environmental protection and excellent chemical stability^{[13⇓⇓~16]}. Compared with traditional sulfide semiconductors (such as CdS), ZnIn₂S₄ are non-toxic, which is conducive to their wide application in the field of environmental protection^[17]. Compared with other ternary sulfides (such as CuGaS₂, AgInS₂, etc.), ZnIn₂S₄ has a more abundant source of elements, which is conducive to its wide application in industry^[18,19]. At present, ZnIn₂S₄ have shown great potential applications in the fields of photocatalysis, photoelectrocatalysis, solar cells, lithium ion batteries and photosensors^{[20⇓⇓⇓⇓~25]}.

As a layered semiconductor, ZnIn₂S₄ has two crystal structures, cubic and hexagonal, both of which have sulfur atoms as connecting atoms. The hexagonal ZnIn₂S₄ has a layered structure, and the atoms are arranged and stacked along the c-axis In a repeating sequence of S-Zn-S-In-S-In-S, wherein all the zinc atoms and half of the indium atoms are tetrahedrally coordinated to the sulfur atoms, and the other indium atoms are octahedrally coordinated (fig. 1b)^[8]. In the cubic ZnIn₂S₄, the zinc atom is tetrahedrally coordinated to the sulfur atom, and the indium atom is octahedrally coordinated to the sulfur atom (Fig. 1C)^[9]. The ZnIn₂S₄ of the two polymorphs can change from hexagonal phase to cubic phase under the pressure of about 4 MPa and the temperature of about 400 ℃, and the cubic phase will change into hexagonal phase when the temperature is higher than 500 ℃. ZnIn₂S₄ also exhibits excellent electronic and optical properties with a tunable band gap (2.06 ~ 2.85 eV)^[26,27]. According to the density functional theory (DFT) calculation, the ZnIn₂S₄ is a semiconductor with a direct band gap, and its conduction band and valence band are located at the G point of the Brillouin zone (Fig. 1 d, e)^[10]. The difference in structure leads to the difference in the properties of the two crystal forms of ZnIn₂S₄. According to the research of Chen et al., the light absorption edge of the hexagonal phase is blue-shifted compared with that of the cubic phase, which indicates that the hexagonal phase ZnIn₂S₄ has a narrower band gap and can absorb more visible light, which is conducive to the improvement of photocatalytic performance^[28]. In addition, they also show some differences in other aspects. The study shows that the hexagonal phase has obvious photoluminescence characteristics, while the cubic phase shows pyroelectricity. Because of the layered structure, both of them show anisotropic conductivity^[10]. Both of the two polymorphs can show considerable photocatalytic activity, in which the interlayer sulfur atoms of the hexagonal ZnIn₂S₄ are easy to expose, which can form vacancies and other defects to act as electron traps, thus reducing the recombination rate of carriers, which makes the hexagonal ZnIn₂S₄ more suitable for photocatalysis^[29]. Therefore, the current research in the field of photocatalysis is mainly based on the hexagonal ZnIn₂S₄, and the reports on the cubic ZnIn₂S₄ are relatively few.

Admittedly, ZnIn₂S₄ has shown great potential in the field of photocatalysis, but its high electron-hole recombination rate and poor charge transfer rate reduce the carrier lifetime and limit its performance. Therefore, it is particularly important to improve the photocatalytic performance of ZnIn₂S₄ and stimulate its potential by modified synthesis to improve its shortcomings.

2 Synthesis and Modification of Indium Zinc Sulfide

2.1 Synthesis of Indium Zinc Sulfide Monomer

The morphology of the photocatalyst has a great influence on its performance. Therefore, it is of great significance to explore the appropriate synthesis process for optimizing the performance of the photocatalyst. In the synthesis process of hexagonal ZnIn₂S₄, the crystal nucleus will be formed first, and then the crystal nucleus will grow anisotropically into the layered structure of ZnIn₂S₄. The layered structure will change differently under different reaction conditions. In this process, the solvent, temperature, sulfur source, surfactant and so on will affect the morphology of the ZnIn₂S₄.

In general, the pH value, dielectric constant, viscosity, surface tension or dipole moment of the solvent have important effects on the morphology of the products, so ZnIn₂S₄ (nanotubes, nanospheres, microclusters, etc.) With different morphologies can be synthesized in different solvents^[8]^[8]^[30]^[14]. For example, compared with water, ethylene glycol has a higher dielectric constant, which will inhibit the growth of nanocrystals. Therefore, Shen et al. Used ethylene glycol as a solvent to obtain ZnIn₂S₄ micro-clusters, and used water as a solvent to obtain ZnIn₂S₄ flower-like microspheres^[14]. Gou et al. Obtained nanotubes or nanoribbons of ZnIn₂S₄ with pyridine as solvent and ZnSO₄, InCl₃ and thioacetamide (TAA) as reaction reagents, but failed to obtain nanotubes or nanoribbons with water, ethanol, tetrahydrofuran and acetonitrile as solvents^[8]. Through further research, Gou et al. Found that the reaction temperature would affect the crystal growth during the generation of the product. In the process of preparing one-dimensional ZnIn₂S₄, higher reaction temperature (180 ℃) would promote the curling of layered ZnIn₂S₄, thus obtaining ZnIn₂S₄ nanotubes, while lower temperature (120 ~ 160 ℃) would produce ZnIn₂S₄ nanobelts (Figure 2a)^[8].

Different sulfur sources contain different groups and have different coordination ability with metal ions in the reaction process, which will affect the growth process of crystals^[31⇓~33]. For example, Pudkon et al. obtained stacked ZnIn₂S₄ nanosheets by using TAA as a sulfur source, and obtained microspherical ZnIn₂S₄ by using L-cysteine, because the -SH functional group of L-cysteine is easy to coordinate with metal ions to form a complex, and the speed of releasing S^2- ions from the complex is slow, which affects the growth of nanocrystals^[34]. Ding et al. Made full use of the coordination ability of glutathione (GSH) with metal ions to obtain ZnIn₂S₄ hollow spheres by one-step hydrothermal method. GSH contains — SH, — COOH and —NH₂ groups, and the metal ion complex M-GSH is formed during the reaction. With the increase of temperature, small ZnIn₂S₄ nanocrystals are formed, and CO₂ and NH₃ bubbles are released. Driven by the interfacial energy, the nanocrystals will aggregate at the gas/liquid interface of bubbles and water, and the subsequent growth forms ZnIn₂S₄ hollow spheres^[35].

Surfactants can be used as templates in the process of structure formation, and different surfactants have different effects on the morphology of products due to their different properties. For example, the spherical micelles formed by cetyltrimethylammonium bromide (CTAB) due to its hydrophilic head and hydrophobic alkyl chain can promote the formation of ZnIn₂S₄ microspheres, while the nucleation and crystal growth of ZnIn₂S₄ are restricted within the chain due to a large number of active oxygen atoms in the molecular chain of polyethylene glycol (PEG), leading to the formation of nanowires (Figure 2b)^[8]. The amount of active agent also affects the morphology of the product. For example, Chaudhari et al. Obtained ZnIn₂S₄ with flower-like microspheres, nanoplates, nanobelts and other morphologies by adjusting the amount of triethylamine (TEA). When 0.005 mol TEA was added, a twisted flower-like morphology composed of nanoplates was observed; When 0.01 mol TEA was added, the ZnIn₂S₄ were stacked nanoplates and nanobelts. When the amount of TEA was further increased to 0. 015 mol, the ZnIn₂S₄ transformed into a flower-like structure composed of nanobelts. This change in morphology may be caused by the coordination bonds and van der Waals forces between the surface atoms of ZnIn₂S₄ and TEA^[36].

2.2 Build compound semiconductor

Limited by the high carrier recombination rate, the performance of ZnIn₂S₄ monomer is limited. The construction of compound semiconductor can improve the performance by making up for the insufficiency of single semiconductor and improve the charge separation efficiency of photocatalytic system, which is one of the most commonly used modification methods. At present, there are many reports about ZnIn₂S₄-based composite structures.Including ZnIn₂S₄ and oxides (TiO₂, WO₃, In₂O₃, BiVO₄,Bi₂WO₆, Bi₂MoO₆, CeO₂, MoO₃, Ag₂O, etc.),Sulfides (MoS₂, NiS, CdS, U WS₂ UN Bi₂S₃Co₉S₈ 、UAgIn₅S₈ UNCuInS₂ tS、UNKSnS₂Graphite phase carbon nitride (g-C₃N₄), metal organic frameworks (thiol-UiO66, MIL-88a (Fe), MIL-101, U NH₂-MIL-125(Ti, etc.), conductive polymers (PANI) and other metal compounds (NiP, UN Cu₃P NK MoSe₂ composite^{[16,25,37⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~49]}^{[29,34,50⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~68]}^{[69⇓⇓~72]}^{[73⇓⇓~76]}^[77]^[78⇓~80].

The construction method of the composite structure is very flexible, and the semiconductor can be contacted in different forms by adjusting the process conditions. For example, Zhu et al. First synthesized In₂O₃ nanocubes.Two different morphologies of In₂O₃/ZnIn₂S₄ composites, In₂O₃ nanocubic /ZnIn₂S₄ nanoparticles (160 ° C) and In₂O₃ nanocubic /ZnIn₂S₄ nanosheets (80 ° C), were obtained by solvothermal reaction at different reaction temperatures (Fig. 3A, B)^[37]. The intimate contact between semiconductors can enhance the transfer and separation of carriers, so the 2D/2D structure of face-to-face contact has attracted the attention of researchers^[55,66,81]. For example, Yang et al. prepared g-C₃N₄ and ZnIn₂S₄ sheets respectively, and then combined them by electrostatic self-assembly method. In addition to having a large contact area, the sheet structure also shortens the charge transfer distance, which is conducive to the improvement of performance^[82]. In addition to increasing the contact area of the heterostructure, the formation of the hollow structure of the composite is also conducive to improving the photocatalytic performance. Compared with the solid structure, the hollow structure can not only provide a larger specific surface area and active sites, but also enhance the light absorption through light scattering/reflection (Fig. 4A)^[35,64,83]. In general, the hollow structure is obtained by a template method. For example, Li et al. And Jiang et al. First synthesized TiO₂ hollow spheres using SiO₂ and carbon spheres as templates, respectively, and then further hydrothermally grew ZnIn₂S₄ on the surface of the TiO₂ (Fig. 4 B, C)^[84,85]. Wang et al. Used In-MIL-68 as a template to obtain a hexagonal tubular In₂O₃, and then grew the ZnIn₂S₄ on the inner and outer surfaces of the In₂O₃ by a low-temperature hydrothermal method. Different from the usual hollow composites, the growth of the ZnIn₂S₄ on the inner surface is conducive to further improving the catalytic performance^[43]. In order to simplify the preparation process of the composites, some semiconductors with similar structure or chemical composition to ZnIn₂S₄ can be directly obtained by one-step synthesis. For example, MoS₂ and ZnIn₂S₄ are both layered sulfides, and Zhang et al. And Swain et al. Synthesized MoS₂/ZnIn₂S₄ by one-step hydrothermal method^[86,87]. Similarly, Wang et al. complexed Ir₂S₃ with ZnIn₂S₄ by a one-step solvothermal process^[88]. The elemental composition of CdIn₂S₄ is much closer to that of ZnIn₂S₄, and Sun et al. Obtained ZnIn₂S₄/CdIn₂S₄ composite by one-step chemical co-precipitation method^[89].

2.3 Precious metal deposition

Noble metals (Ag, Au, Pt, etc.) Have excellent conductivity and can quickly attract electrons to suppress the recombination rate of carriers, so they are excellent promoters^[90,91]. At the same time, noble metals have the ability to absorb a large amount of visible light due to the surface plasmon resonance (SPR) effect, which can improve the light absorption capacity of the catalyst system^[92⇓~94]. Noble metals such as Au, Pt and Pd can be deposited on ZnIn₂S₄ by photoreduction or chemical reduction. For example, Zhu et al. and Mandal et al. deposited Au on ZnIn₂S₄ by photoreduction and citrate-reduction of HAuCl₄, respectively^[95,96]. Swain et al. deposited Au nanodots on MoS₂/ZnIn₂S₄ using L-cysteine as a linker and ascorbic acid as a reducing agent^[87]. Yang et al. and Wang et al. deposited Pt and Pd particles on ZnIn₂S₄ by photoreduction of H₂PtCl₆·6H₂O and Pd(CH₃CN)₂Cl₂, respectively^[80,97]. Feng et al. reduced HAuCl₄ and Au-Pd/ZnIn₂S₄ simultaneously to obtain Au-Pd/ZnIn₂S₄ modified by bimetallic nanoparticles simultaneously (fig. 5A)^[98].

2.4 Carbon simple substance modification

Precious metal deposition is a good modification method, but its scarcity and high cost limit its wide application. Low-cost carbon dots can replace noble metals to modify ZnIn₂S₄, and its research has also been paid attention to. For example, Lei et al. First prepared carbon nanodots from starch by hydrothermal method, and then prepared CDs/ZnIn₂S₄ by one-pot hydrothermal method, hydrothermal deposition method and stirring method, among which the one-pot hydrothermal method can load more carbon nanodots^[99]. Xu and Shi et al. Also prepared carbon nanodot modified ZnIn₂S₄ by hydrothermal method on pre-synthesized carbon nanodots (fig. 5B)^[100,101].

As a new type of carbon nanomaterial, graphene has many advantages, such as high electron mobility, high transparency, large theoretical surface area and so on. The composite of ZnIn₂S₄ and graphene has attracted the attention of researchers. For example, Yuan et al. First synthesized graphene oxide (GO) by Hummers method, and then prepared RGO/ZnIn₂S₄ composite by one-pot reflow wet chemistry method^[102]. Kale et al., Tian et al., and Ye et al. directly synthesized ZnIn₂S₄/ graphene nanoheterostructures by hydrothermal or solvothermal methods in the presence of GO^[24,103,104]. Zhang et al. supported MoS₂ on ZnIn₂S₄@RGO to form a ternary complex of MoS₂QDs@ZnIn₂S₄@RGO^[105].

2.5 Ion Doping

Ion doping can introduce new charges, form defects or change the lattice type in the semiconductor lattice, thus affecting the movement and distribution of photogenerated carriers, and ultimately leading to the change of photocatalytic performance of semiconductors. According to the different doping ions, it can be divided into metal ion doping and non-metal ion doping. At present, the research on the doping modification of ZnIn₂S₄ is mainly based on metal ion doping. The doping method of the metal ions is relatively simple and convenient, and the corresponding doping elements can be added during the hydrothermal/solvothermal preparation of the ZnIn₂S₄. For example, Tan et al. Added Sm(NO₃)₃·6H₂O in the process of hydrothermal synthesis of ZnIn₂S₄, and obtained Sm doped ZnIn₂S₄ photocatalyst^[106]. Researchers have prepared ZnIn₂S₄ doped with Mg, Sr, Ba, Ca, Mo, Cu and Ni by similar methods^{[107⇓⇓⇓~111]}. For the study of ZnIn₂S₄ doped with nonmetal ions, Yang et al. Added polyvinylpyrrolidone to the synthesis of ZnIn₂S₄ to dope oxygen into the ZnIn₂S₄^[112].

Table 1 shows the hydrogen production performance of different ZnIn₂S₄ based photocatalysts under specific illumination conditions.

3 Application of Indium Zinc Sulfide in Photocatalysis

3.1 Photocatalytic hydrogen production

(1) The ZnIn₂S₄ of ultrathin sheet structure can provide a large contact surface area, and the photogenerated carriers can migrate to the surface in a short distance, which is conducive to reducing the recombination of carriers. In addition, the ultrathin sheet structure of ZnIn₂S₄ often exposes more (110) active surface, which is of great significance to the improvement of hydrogen production performance^[16]. For example, the ZnIn₂S₄ ultrathin nanosheet synthesized by Du et al. Has a hydrogen production rate of 1.723 mmol/G/H under visible light, which is much higher than the ZnIn₂S₄(0.799 mmol/g/h) of ordinary sheet structure. In order to further improve the hydrogen production activity, Du et al. Introduced sulfur vacancies, which can be used as electron capture centers to inhibit the recombination of carriers, and the hydrogen production rate was increased to 13. 478 mmol/G/H^[15].

(2) It is an effective way to improve the photocatalytic activity to construct heterostructures by closely contacting two or more semiconductors on the nanoscale, and the formation of heterojunctions can promote the transfer and separation of carriers between semiconductors. Studies have shown that,The ZnIn₂S₄ may be mixed with MoS₂, WS₂, NiS, TiO₂, Co₉S₈,Heterostructures are formed in a variety of semiconductors, such as g-C₃N₄, AgIn₅S₈, CuInS₂, and metal-organic frameworks^{[34,57,64,65,69,75,84,86]}. Taking the MoS₂/ZnIn₂S₄ as an example, as shown in fig. 6a, the conduction band energy level of the MoS₂ is more positive than that of the ZnIn₂S₄, and electrons from the ZnIn₂S₄ can be accepted.At the same time, the holes on the valence band of the MoS₂ can be transferred to the valence band of the ZnIn₂S₄, and the close contact between the MoS₂ with a layered structure and the ZnIn₂S₄ can effectively reduce the energy barrier of carrier transfer and accelerate the separation of electrons and holes^[54]. For example, the hydrogen production rate of the MoS₂/ZnIn₂S₄ heterojunction prepared by Liu et al. Reaches 2512.5 μmol/G/H, which is 8.7 times faster than that of the pure ZnIn₂S₄ and even higher than that of the Pt/ZnIn₂S₄ (Fig. 6B)^[53]. The obvious hydrogen production performance is improved in the WS₂/ZnIn₂S₄, the NiS/ZnIn₂S₄, the AgIn₅S₈/ZnIn₂S₄,g-C₃N₄/ZnIn₂S₄, Au/thiol-UiO66/ZnIn₂S₄, ZnIn₂S₄/NH₂-MIL-125(Ti) and other heterojunctions are also reflected^{[34,56,65,69,73,76]}. TiO₂/ZnIn₂S₄ and Co₉S₈@ZnIn₂S₄ prepared by Wang et al and Li et al benefited from the larger specific surface area and more active sites provided by the hollow structure, and the hydrogen production rates reached 1129.5 μmol/G/H and 6250 μmol/G/H, respectively^[64,84].

The closer contact between semiconductors is also beneficial to the transfer and separation of carriers in the heterostructure. For example, Huang et al. And Guan et al. Synthesized MoS₂/ZnIn₂S₄ and CuInS₂/ZnIn₂S₄ heterojunctions with 2D/2D structures, respectively. This structure provides a larger contact area, which is beneficial to the improvement of photocatalytic performance (Figure 6 C)^[55,66]. Wang et al. synthesized MoS₂/CQDs/ZnIn₂S₄ and NiS/CQDs/ZnIn₂S₄ by introducing CQDs on the basis of the original binary complex. Conductive CQDs act as electron mediators to promote the electron transfer from ZnIn₂S₄ to MoS₂(NiS), which is an important reason for the improvement of its performance (Figure 6d)^[113,114].

(3) Different from the heterojunction, as shown in Fig. 7A, the Z-scheme structure can not only spatially isolate the photogenerated electrons and holes, but also retain the strong reducibility and strong oxidizability of carriers^[41]. The WO₃/ZnIn₂S₄ and Cu₃P/ZnIn₂S₄ constructed by Tan et al. And Yang et al. Respectively showed a Z-scheme structure, and the hydrogen production rates reached 2 202. 9 μmol/G/H and 2 561. 1 μmol/G/H, respectively^[42,80]. Ding et al. introduced PtS and MnO₂ as co-catalysts instead of sacrificial agents in the photocatalytic hydrogen production experiment on WO₃/ZnIn₂S₄, and 50 mg of the catalyst produced 5. 94 μmol of hydrogen and 2. 24 μmol of oxygen within 8 H^[41]. Zhu et al. introduced RGO into the ZnIn₂S₄/BiVO₄Z-schemestructure, and used Pt and RuO₂ as hydrogen production and degradation cocatalysts to produce 10 120 μmol/G hydrogen in 5 mol/L formaldehyde solution (pH = 13) for 6 H under visible light. The RGO acts as a bridge for electron transfer from the BiVO₄ conduction band to the ZnIn₂S₄ valence band in the photocatalytic system^[115].

(5) Graphene is an excellent cocatalyst for photocatalytic hydrogen production due to its high specific surface area, conductivity, stability, and adjustable surface properties. For example, the RGO/ZnIn₂S₄ synthesized by Ye et al. Produced 817 μmol/G/H hydrogen under visible light^[104]. The hydrogen production rate of RGO/ZnIn₂S₄ synthesized by Tian et al. With Pt as the cocatalyst was 1210 μmol/G/H under visible light, which was 26.3 times of that of pure ZnIn₂S₄. This obvious improvement benefited from the good conductivity of RGO, which could be used as the acceptor of electrons generated by ZnIn₂S₄ and realized the rapid separation of photogenerated carriers. Meanwhile, the carbon defects in RGO could be used as active sites for hydrogen production, which was conducive to the hydrogen production reaction^[103].

(6) Ion doping can introduce ions into the semiconductor lattice structure, thus introducing new charges, forming defects or changing the lattice type, which will affect the movement of photogenerated electrons and holes, adjust their distribution or change their energy band structure, thus affecting the photocatalytic activity of the semiconductor. At the same time, doping induces surface defects, which act as charge trapping centers, effectively improving charge separation. For example, Shen et al. Found that the doping of Ca can greatly improve the hydrogen production activity of ZnIn₂S₄^[107]. Yang et al. Doped oxygen into ZnIn₂S₄ ultrathin nanosheets and found that the average lifetime of photogenerated electrons increased by 1.53 times. As shown in Fig. 7 B, the hydrogen production rate of oxygen-doped ZnIn₂S₄ nanosheets reached 2120 μmol/G/H under visible light, and the activity hardly decreased after 12 cycles^[112].

The structure of ZnIn₂S₄ affects its hydrogen production performance, which makes the modification method closely related to the structure. For example, in the morphology control of monomers, the layered structure of hexagonal ZnIn₂S₄ makes the advantages of ultra-thin nanosheets reflected, and its performance is improved^[16]. However, it is difficult for a single semiconductor to inhibit the recombination of carriers, so further modification (introducing vacancies, building composite structures, etc.) Can be carried out on the basis of morphology control. The construction of composite structure is an effective method to reduce the recombination rate of charge carriers. Heterojunction is one of the most commonly used methods, which can effectively improve the performance of ZnIn₂S₄. Similarly, the recombination with graphene can also inhibit the recombination of charge carriers. Compared with the heterojunction, the Z-scheme structure can not only separate the carriers, but also retain its high redox ability, but it requires a higher degree of band matching between the two semiconductors. The construction of the composite structure is also influenced by the structure. The semiconductor recombination of similar structures helps to reduce the carrier transport resistance at the interface. Therefore, the recombination of ZnIn₂S₄ with layered structural materials such as g-C₃N₄, MoS₂, and BiVO₄ has attracted much attention. Ion doping can improve the performance by changing the internal lattice of the semiconductor, and its synthesis method is relatively simple, but only appropriate ion doping can improve the performance, and some ions may reduce its performance^[107].

3.2 Photocatalytic degradation of organic pollutants

Photocatalytic degradation is an effective method to treat organic pollutants which are stable and exist in the water environment for a long time. It has the advantages of low cost, no secondary pollution and high efficiency. Different from the hydrogen production reaction relying on photogenerated electrons, the degradation of organic matter mainly depends on strong oxidizing substances such as h⁺, · OH and ·

O 2 -

produced under light. These radicals are generally produced by further reactions of photogenerated electrons and holes with water molecules, hydroxyl ions and oxygen molecules in water.

ZnIn₂S₄ has been widely studied in the field of photocatalytic degradation of organic pollutants. ZnIn₂S₄ and its complexes have obvious degradation effects on various organic pollutants such as rhodamine B (RhB), methyl orange (MO), tetracycline (TC), methylene blue (MB), phenol, levofloxacin (LEV), fluvastatin and metronidazole (MTZ). The studies on degradation of pollutants by ZnIn₂S₄ complexes in recent years are listed in Table 2. Under visible light, ZnIn₂S₄ monomer showed a certain ability to degrade RhB, MO and fluvastatin, but the degradation activity needs to be further improved^[116⇓~118]. Construction of heterojunction or Z-scheme structure, introduction of carbon dots, noble metal modification, doping and dye sensitization can effectively improve the degradation activity of ZnIn₂S₄.

(1) Heterojunction construction is a common method to improve the photocatalytic degradation activity, and its enhancement mechanism is similar to that of hydrogen production. Through the rapid transfer of carriers between semiconductors, photogenerated electrons and holes are separated, so that more carriers participate in the degradation reaction. Studies have shown that,C₃N₄ 、TiO₂ 、MoS₂ 、In₂O₃ 、BiPO₄ 、And the heterostructure formed by compounding the CdIn₂S₄ and the ZnIn₂S₄ can improve the performance of photocatalytic degradation of organic pollutants. For example, the ZnIn₂S₄/g-C₃N₄ heterojunction prepared by Liu et al. Can degrade 95. 3% of MO in 120 min, which is significantly higher than that of pure ZnIn₂S₄(72.6%) and g-C₃N₄(5.7%)^[70]. This obvious improvement was also shown in the degradation of organic pollutants such as phenol, TC, MB, RhB, carbamazepine, 2,4-dichlorophenol and sulfamethoxazole (SMZ) by ZnIn₂S₄-based heterojunctions^{[37,38,49,51,70,71,74,89,119,120]}. In order to further improve the performance, Jiang et al. prepared hollow TiO₂/ZnIn₂S₄. Benefiting from the unique advantages of the hollow structure, they increased the absorption of light through multiple reflection, and showed considerable degradation ability for LEV, TC and RhB under visible light^[85]. Guo et al and Yang et al showed enhanced photocatalytic activity for the degradation of phenol and TC by forming a 2D/2D BiOCl/ZnIn₂S₄ and g-C₃N₄/ZnIn₂S₄ to increase the contact area between the two semiconductors^[81,82]. Jiang et al. introduced CQDs on the BiOCl/ZnIn₂S₄, and the excellent conductivity of the carbon dots could further accelerate the charge transport (Fig. 8A)^[121]. Guo et al. Decorated Ag₃PO₄ nanoparticles on the g-C₃N₄/ZnIn₂S₄, which further accelerated the transfer and separation of carriers, and degraded 83% of tetracycline in 60 min under visible light^[122].

(2) As mentioned above, the Z-scheme structure can separate electrons and holes and retain its strong reducing and oxidizing properties, which is particularly important in the photocatalytic degradation of organic pollutants. Higher reduction and oxidation potentials are conducive to the production of ·

O 2 -

and · OH, which can accelerate the degradation of organic pollutants. Our research group has studied the degradation of pollutants by Z-scheme structural materials for many years^[124⇓~126].

In the research of ZnIn₂S₄-based composite catalyst with Z-scheme structure, the WO₃/ZnIn₂S₄ synthesized by Tang et al. Has a degradation rate of 74.1% for acetylenopyran within 40 min. The

O 2 -

plays an important role in the photocatalytic reaction, so it is analyzed that the WO₃/ZnIn₂S₄ is of Z-scheme structure (Fig. 8 B, C)^[127]. The WO_2.72/ZnIn₂S₄ synthesized by Chen et al. Also showed a Z-scheme structure and could degrade 97. 3% TC in 60 min^[123]. In addition, the Z-scheme structure formed by ZnIn₂S₄ with Bi₂S₃, Bi₂WO₆, MoO₃, BiVO₄, etc. Also showed improved photocatalytic performance in the degradation of MO, MB, RhB, and MTZ^{[44,45,48,63]}.

(3) Carbon is a low-cost conductor with excellent performance, and the modification of ZnIn₂S₄ with carbon dots can promote the transfer of electrons, thereby inhibiting the recombination of electrons and holes. For example, Xu and Shi et al. prepared CQDs/ZnIn₂S₄ composites, which can rapidly degrade TC and MO, as shown in Fig. 8d. CQDs receive electrons generated by ZnIn₂S₄, reduce the recombination rate of carriers, and improve the photocatalytic performance^[100,101].

(4) The introduction of noble metals on the surface of the catalyst can enhance the absorption of light through the SPR effect, so as to produce more electrons to participate in the reaction. For example, Swain et al. introduced Au nanoparticles on the basis of MoS₂/ZnIn₂S₄ heterojunction, as shown in Figure 9a. Under visible light irradiation, Au will excite hot electrons, which will be transferred to the conduction band of ZnIn₂S₄ to further participate in the photocatalytic reaction^[87].

(5) Doping is also one of the effective methods to improve the photocatalytic degradation performance of ZnIn₂S₄. Dye sensitization enhances the photocatalytic activity through the strong light absorption ability of organic dyes. For example, Tan et al. doped Sm into the ZnIn₂S₄ to degrade RhB, as shown in fig. 9b, the doping of Sm can cause the defect level to capture electrons to inhibit the recombination of photogenerated carriers, RhB can be excited by visible light due to dye sensitization and transfer electrons to the conduction band of the ZnIn₂S₄, and the generated oxidation species can degrade RhB^[106].

In terms of degradation, the modification of ZnIn₂S₄ has commonality with hydrogen production. In the construction of composite structures, the recombination of ZnIn₂S₄ with layered materials (g-C₃N₄, MoS₂, Bi₂WO₆, etc.) Has been widely studied, which can accelerate the transmission of carriers to improve performance. It is worth noting that the advantage of Z-scheme structure is more important in the degradation of organic matter, and the stronger redox ability is conducive to the generation of active free radicals, which directly determines the degradation ability of the catalyst. Noble metal loading improves the performance of ZnIn₂S₄ through excellent conductivity and SPR effect, but the high cost is not conducive to its large-scale application, and carbon dot modification is a low-cost alternative modification scheme. Dye sensitization can also enhance the photocatalytic degradation ability of ZnIn₂S₄, but only for specific dye sensitized pollutants. It can be seen that different modification methods have different characteristics, and appropriate methods can be selected according to actual needs. Furthermore, different methods can also be combined to give full play to the advantages of different modification methods.

3.3 Other applications of indium zinc sulfides

Chromium is a typical heavy metal pollutant in water pollution. Hexavalent chromium (Cr (Ⅵ)) is a serious threat to the ecological environment and human health due to its high solubility, high toxicity and carcinogenicity. Photocatalytic reduction of Cr (Ⅵ) has been developed. For example, the ZnIn₂S₄/SnS₂ heterojunction prepared by Pan et al. Has a Cr (Ⅵ) reduction rate of 80. 2% within 120 min^[68]. The TiO₂/ZnIn₂S₄ and ZnIn₂S₄/CdS prepared by Li et al. And Zhang et al. Completely reduced Cr (Ⅵ) within 50 min and 30 min, respectively (Fig. 10a)^[39,59]. ZnIn₂S₄ can also be used to treat polluted gases in the air. For example, the Bi₂MoO₆/ZnIn₂S₄ prepared by Wan et al. Can be used to oxidize NO to produce N

O 3 -

, and the removal rate of NO reaches 84. 94% in 80 min^[46].

In addition to hydrogen production, ZnIn₂S₄ can also deal with energy problems by carbon sequestration, and CO₂ can be reduced to CO, CH₄, CH₃OH and other substances. For example, ZnIn₂S₄/TiO₂ prepared by Yang et al. Can reduce CO₂ to CH₄ with a yield of 1.135 μmol/G/H^[40]. Zhou and Wang et al. Found that g-C₃N₄/ZnIn₂S₄ and ZnIn₂S₄/In₂O₃ could reduce CO₂ to CO, with CO formation rates of 33.2, 892, and 3075 μmol/G/H, respectively^[43,72]. CeO₂/ZnIn₂S₄ synthesized by Yang et al. Can reduce CO₂ to produce CH₃OH,CH₃OH with a maximum production rate of 0.542 μmol/G/H (Fig. 10B)^[47].

The ZnIn₂S₄ can also be used in the field of organic synthesis. For example, the MoS₂/ZnIn₂S₄ composite prepared by Hao et al. Can photocatalyze the semi-dehydrogenation of 1,2,3,4-tetrahydroisoquinoline to 3,4-dihydroisoquinoline with a conversion of 94%^[50]. The conversion rate of Au-Pd/ZnIn₂S₄ synthesized by Feng et al for photocatalytic oxidation of benzyl alcohol to benzaldehyde is 55.4%, which is much higher than that of ZnIn₂S₄ and ZnIn₂ modified by monometallic nanoparticles

S 4 [98]

. CdS@ZnIn₂S₄ and P-C₃N₄/ZnIn₂S₄ prepare by Chen et al. Can be used to reduce 4-nitroaniline (4-NA) to 4-phenylenediamine (4-PDA)^[58,128]. The PtS/ZnIn₂S₄ prepared by Xu et al. Can photocatalytically crack thiols to disulfide and hydrogen, and benzyl thiol can be completely converted to dibenzyl disulfide and hydrogen within 6 H^[67].

3.4 Stability of Indium Zinc Sulfide

The stability of photocatalyst is an important indicator for its industrial application, and an excellent photocatalyst should have excellent cycle stability. As the ZnIn₂S₄ of sulfide semiconductor, the existence of photoetching reduces its stability^[12]. As shown in Formula 1, in the photocatalytic reaction process, the holes generated by the semiconductor can oxidize the sulfur ions in the sulfide into elemental sulfur, so that the ZnIn₂S₄ is gradually corroded and the performance is reduced^[129]. Therefore, improving its stability has been one of the research priorities of researchers.

(1)

Z n I n 2 S 4 + 10 h + → Z n 4 + + 2 I n 3 + + 4 S

In the previous paper, we summarized the modification methods to improve the performance of ZnIn₂S₄, such as morphology control, construction of composite structures, noble metal deposition, carbon modification, ion doping and so on, some of which also have obvious effects on improving the stability. In the process of photocatalysis, photocorrosion is caused by photogenerated holes, so by accelerating the transport of carriers, they can quickly participate in the photocatalytic reaction and inhibit the generation of photocorrosion. By construct that compound semiconductor, the recombination of carriers can be inhibit, the transmission of the carriers can be accelerated, and the stability of the ZnIn₂S₄ can be improved. For example, the ZnIn₂S₄-based composite structures synthesized by Hao et al., Swain et al., Li et al, Xiong et al. and Yang et al. respectively showed considerable hydrogen generation cycle stability, and the performance did not show a significant decrease after 3 to 5 cycles (Fig. 11A)^{[50,62,78,80,87]}. The same situation is also reflected in the degradation of organic pollutants, as shown in Figure 11b, after 7 cycles, the performance of ZnIn₂S₄ degradation of TC is significantly reduced, while WO_2.72/ZnIn₂S₄ maintains good stability, which indicates that the stability of the catalyst can be enhanced by accelerating the transport of carriers through the composite structure^{[70,82,85,122]}^[123]. By introducing noble metals, RGO and carbon dots, their excellent conductivity can be used to accelerate the transport of carriers to improve the stability. For example, Wang et al., Feng et al., Tian et al. Yuan et al. Xu et al. and Shi et al. have obtained photocatalysts with good stability by using the above methods^{[97,98,100⇓⇓~103]}. Doping can form defects to inhibit the recombination of electrons and holes, which can also play a role in improving the stability. For example, the oxygen-doped ZnIn₂S₄ prepared by Yang et al. Still maintained a high hydrogen production activity after 12 cycles (Fig. 7B)^[112].

4 Conclusion and prospect

As the potential of ZnIn₂S₄ in the field of photocatalysis has attracted wide attention, the synthesis methods, photocatalytic properties and mechanism of ZnIn₂S₄ and their complexes containing oxygen and sulfur compounds are summarized in this paper. It is found that the formation of heterojunction and Z-scheme structure improves the photocatalytic performance of ZnIn₂S₄ in hydrogen production, degradation, carbon fixation and other aspects, which provides a reference for ZnIn₂S₄ photocatalysts in dealing with energy crisis and environmental pollution. With the increasing attention to environmental issues and the increasing demand for new energy sources, higher requirements are put forward for the photocatalytic performance of ZnIn₂S₄.

In view of the current research status and shortcomings of ZnIn₂S₄, the following valuable development directions are put forward: the mechanism of hydrogen production and degradation of organic pollutants in :(1)ZnIn₂S₄ is interlinked.Hydrogen production often requires the addition of sacrificial agents, and the synergy of hydrogen production and degradation is a good development direction, which has been reported in a small amount, but needs more extensive and in-depth research and discussion^[105,115]. (2) The research on the modification of ZnIn₂S₄ by doping mainly focuses on metal ions, and there is a lack of research reports on non-metal ions. In addition, doping two or more ions at the same time is also a noteworthy research direction. (3) The combination of different modification methods deserves further study, such as the combination of doping and building composite structures, which may further improve the performance of ZnIn₂S₄; (4) There are many kinds of pollutants in the wastewater discharged from the chemical industry. At present, the research on the degradation of organic pollutants by ZnIn₂S₄ is relatively single, and the degradation of complex mixed organic substances is lacking. More theoretical and experimental support is needed for the wide application of ZnIn₂S₄ to degrade organic pollutants. (5) Recycle and reuse is an important factor affecting the industrial application of photocatalyst, and catalyst thin film is one of the good development directions. At present, the research on the preparation of thin film by ZnIn₂S₄still depends on the well-developed Ti

O 2 [22,120,130]

, and further research is needed for the preparation of its own thin film. Although (6)ZnIn₂S₄ has been reported in the field of organic synthesis, its redox selectivity needs to be further studied in order to apply to practical production. (7) The novel coronavirus pneumonia virus has brought a huge impact to the world. As a photosensitive material, ZnIn₂S₄ can be used as a photoelectric sensor to detect prostate-specific antigen and other substances. If it can be further studied and developed, it is believed that it can play an important role in the detection of bacteria and viruses^[25].

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Funding

Open Fund of Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies (No. EEST2020-1)、the Science and Technology Development Project of Suzhou(SYG201818)

Jiangsu Collaborative Innovation Center of Technology and Material for Water Treatment(XTCXSZ2020-1)