Properties and modulation strategies of ZnIn₂S₄ for photoelectrochemical water splitting: opportunities and prospects

Abstract

The global energy crisis has driven significant research into renewable energy sources, and photoelectrochemical (PEC) water splitting stands out as one of the most promising solutions for hydrogen production. Among the various materials developed for PEC water splitting, ternary metal sulfides, particularly ZnIn₂S₄, have garnered considerable attention due to their unique combination of electronic, optical, and chemical properties. This paper presents a comprehensive analysis of the structure and properties of ZnIn₂S₄, explores modification strategies for ZnIn₂S₄-based photoanodes, and discusses their application in PEC water splitting. Furthermore, we address the challenges and limitations of ZnIn₂S₄-based photoanodes and highlight prospects for their future development.

Keywords

ZnIn₂S₄ / photoanode / photoelectrochemical water splitting / hydrogen production

References

[1] Roda D,Łapiński M.The new method of ZnIn₂S₄ synthesis on the titania nanotubes substrate with enhanced stability and photoelectrochemical performance.Sci Rep2023;13:21263 PMCID:PMC10692104

[2] Zhang G,Chen D.A mini-review on ZnIn₂S₄-based photocatalysts for energy and environmental application.Green Energy Environ2022;7:176-204

[3] Song Y,Dong X.A review and recent developments in full-spectrum photocatalysis using ZnIn₂S₄-based photocatalysts.Energy Tech2021;9:2100033

[4] Feng C,Huang KW,Zhang H.Surface modification of 2D photocatalysts for solar energy conversion.Adv Mater2022;34:2200180

[5] Yang L,Xiang Q.Advances and challenges in the modification of photoelectrode materials for photoelectrocatalytic water splitting.Mater Horiz2024;11:1638-57

[6] Gong Y,Shao B,Lu T.Stable metal-organic frameworks for PEC water splitting.FlatChem2021;27:100240

[7] Xu XT,Zhang X,Zou JJ.Rational design and construction of cocatalysts for semiconductor-based photo-electrochemical oxygen evolution: a comprehensive review.Adv Sci2019;6:1801505

[8] Sun J,Zhang X.Using VO₂ as a hole storage layer to improve PEC water splitting performance of BiVO₄ photoanode.Int J Hydrogen Energy2024;69:95-102

[9] Dong G,Bi Y.Advanced oxygen evolution reaction catalysts for solar-driven photoelectrochemical water splitting.J Mater Chem A2023;11:3888-903

[10] Song Y,Cheng H.Metal-organic framework glass catalysts from melting glass-forming cobalt-based zeolitic imidazolate framework for boosting photoelectrochemical water oxidation.Angew Chem Int Ed2023;62:e202306420

[11] Singh I,Mahajan A.Interfacial engineering of a TiO₂ photoanode via graphene nanoribbons for efficient quantum-dot-sensitized solar cells and photoelectrochemical water splitting.Energy Fuels2023;37:15054-66

[12] Feng Y,Li J.Fabrication of WO₃ photoanode on crystalline Si solar cell for water splitting.J Mater Sci Mater Electron2020;31:14137-44

[13] Krysiak OA,Conzuelo F.Importance of catalyst-photoabsorber interface design configuration on the performance of Mo-doped BiVO₄ water splitting photoanodes.J Solid State Electrochem2021;25:173-85

[14] Choi MJ,Choi KS.Controlled band offsets in ultrathin hematite for enhancing the photoelectrochemical water splitting performance of heterostructured photoanodes.ACS Appl Mater Interfaces2022;14:7788-95

[15] Zheng X,Liu Y.ZnIn₂S₄-based photocatalysts for photocatalytic hydrogen evolution via water splitting.Coord Chem Rev2023;475:214898

[16] Yan Y,Cheng X.Research progress of ZnIn₂S₄-based catalysts for photocatalytic overall water splitting.Catalysts2023;13:967

[17] Long C,Huang J.Latest progress on photocatalytic H₂ production by water splitting and H₂ production coupled with selective oxidation of organics over ZnIn₂S₄-based photocatalysts.Energy Fuels2023;37:136-58

[18] Ren Y,Zeng D.ZnIn₂S₄-based nanostructures in artificial photosynthesis: insights into photocatalytic reduction toward sustainable energy production.Small Struct2022;3:2200017

[19] Khosya M,Faraz M.Enhanced photoelectrochemical water splitting and photocatalytic degradation performance of visible light active ZnIn₂S₄/PANI nanocomposite.Int J Hydrogen Energy2023;48:2518-31

[20] Mahadik MA,Cho M.Metal oxide top layer as an interfacial promoter on a ZnIn₂S₄/TiO₂ heterostructure photoanode for enhanced photoelectrochemical performance.Appl Catal B Environ2016;184:337-46

[21] Pan F,Li Z.Substitutional Cd dopant as photohole transfer mediator boosting photoelectrochemical solar energy conversion of 2D Cd-ZnIn₂S₄ photoanode.Small2024;20:2304846

[22] Lin Y,Xv R.TiO₂ nanoparticles modified with ZnIn₂S₄ nanosheets and Co-Pi groups: type II heterojunction and cocatalysts coexisted photoanode for efficient photoelectrochemical water splitting.Int J Hydrogen Energy2022;47:33361-73

[23] Chen J,Cai X,Gu X.Sulfur vacancy-rich ZnIn₂S₄ nanosheet arrays for visible-light-driven water splitting.Mater Sci Semicond Process2022;143:106547

[24] Song Y,Yang Y.Heterojunction engineering of multinary metal sulfide-based photocatalysts for efficient photocatalytic hydrogen evolution.Adv Mater2024;36:2305835

[25] Bao Z,Zhang Z.Visible-light-responsive S-vacancy ZnIn₂S₄/N-doped TiO₂ nanoarray heterojunctions for high-performance photoelectrochemical water splitting.J Mater Chem A2024;12:15902-13

[26] Wang J,Zhou R.A review: synthesis, modification and photocatalytic applications of ZnIn₂S₄.J Mater Sci Technol2021;78:1-19

[27] Lee J,Lee T,Lee KH.Revisiting polytypism in hexagonal ternary sulfide ZnIn₂S₄ for photocatalytic hydrogen production within the Z-scheme.Chem Mater2019;31:9148-55

[28] Yang W,Fang T.Layered crystalline ZnIn₂S₄ nanosheets: CVD synthesis and photo-electrochemical properties.Nanoscale2016;8:18197-203

[29] Wang J,Zhou W.Cubic quantum dot/hexagonal microsphere ZnIn₂S₄ heterophase junctions for exceptional visible-light-driven photocatalytic H₂ evolution.J Mater Chem A2017;5:8451-60

[30] Luan Q,Li R.Boosting photocatalytic hydrogen evolution: orbital redistribution of ultrathin ZnIn₂S₄ nanosheets via atomic defects.Appl Catal B Environ2022;305:121007

[31] Chong W,Kong XY,Putri LK.Non-metal doping induced dual p-n charge properties in a single ZnIn₂S₄ crystal structure provoking charge transfer behaviors and boosting photocatalytic hydrogen generation.Appl Catal B Environ2023;325:122372

[32] Zhang W,Xing Y.Sandwich-like P-doped h-BN/ZnIn₂S₄ nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H₂ and H₂O₂ evolution.Chem Eng J2022;442:136151

[33] Dai M,Zhang P,Wang S.ZnWO₄-ZnIn₂S₄ S-scheme heterojunction for enhanced photocatalytic H₂ evolution.J Materi Sci Technol2022;122:231-42

[34] Hao C,Shi W,Guo F.Facile solvothermal synthesis of a Z-scheme 0D/3D CeO₂/ZnIn₂S₄ heterojunction with enhanced photocatalytic performance under visible light irradiation.Chem Eng J2021;409:128168

[35] Alshgari RA,Shah JH,Abid AG.Nanosphere-like ZnIn₂S₄ intercalated g-C₃N₄ for improved green oxygen production.J Korean Ceram Soc2024;61:1013-26

[36] Li H,Zhao L.Synthesis of TiO₂@ZnIn₂S₄ hollow nanospheres with enhanced photocatalytic hydrogen evolution.Rare Met2019;38:420-7

[37] Ye L.ZnIn₂S₄: a photocatalyst for the selective aerobic oxidation of amines to imines under visible light.ChemCatChem2014;6:2540-3

[38] Gou X,Shi Y.Shape-controlled synthesis of ternary chalcogenide ZnIn₂S₄ and CuIn(S,Se)₂ nano-/microstructures via facile solution route.J Am Chem Soc2006;128:7222-9

[39] Geng H,Li K,Gu X.Epitaxial In₂S₃/ZnIn₂S₄ heterojunction nanosheet arrays on FTO substrates for photoelectrochemical water splitting.Appl Surf Sci2021;563:150289

[40] Kale BB,Baeg JO.Template free architecture of hierarchical nanostructured ZnIn₂S₄ rose-like flowers for solar hydrogen production.J Nanosci Nanotechnol2017;17:1447-454

[41] Zhou MJ.Synthesis and photocatalytic properties of flower-like ZnIn₂S₄ microspheres by a solvothermal method.Adv Mater Res2013;881-3:1101-4

[42] Huang Y,Xu W.Converting Undesirable defects into activity sites enhances the photoelectrochemical performance of the ZnIn₂S₄ photoanode.Adv Energy Mater2024;14:2304376

[43] Cheng K.Preparation of Zn-In-S film electrodes using chemical bath deposition for photoelectrochemical applications.Sol Energy Mater Sol Cells2010;94:1137-45

[44] Sun Y,Chen L.Enhancement of interfacial charge transportation through construction of 2D-2D p-n heterojunctions in hierarchical 3D CNFs/MoS₂/ZnIn₂S ₄ composites to enable high-efficiency photocatalytic hydrogen evolution.Solar RRL2021;5:2000722

[45] Gao Y,Zhang D,Lu J.Microwave-assisted fabrication of CQDs/ZnIn₂S₄ nanocomposites for synergistic photocatalytic removal of Cr(VI) and rhodamine B.Inorg Nano-Metal Chem2021;51:451-7

[46] Chen Z,Xiao G,Xu Y.Microwave-assisted hydrothermal synthesis of marigold-like ZnIn₂S₄ microspheres and their visible light photocatalytic activity.J Solid State Chem2012;186:247-54

[47] Mahadik MA,Chae W,Cho M.Microwave-assisted rapid synthesis of Cu₂S:ZnIn₂S₄ marigold-like nanoflower heterojunctions and enhanced visible light photocatalytic hydrogen production via Pt sensitization.J Ind Eng Chem2022;108:203-14

[48] Chang YC,Pan KY.Microwave-assisted synthesis of SnO₂@ZnIn₂S₄ composites for highly efficient photocatalytic hydrogen evolution.Materials2024;17:2367 PMCID:PMC11123309

[49] Mishra M,Wang PH,Lee TR.Tuning the crystallinity and coverage of SiO₂-ZnIn₂S₄ core-shell nanoparticles for efficient hydrogen generation.ACS Appl Mater Interfaces2021;13:4043-50

[50] Sun M,Zeng Q.Facile synthesis of hierarchical ZnIn₂S₄/CdIn₂S₄ microspheres with enhanced visible light driven photocatalytic activity.Appl Surf Sci2017;407:328-36

[51] Bedala KK,Soleimani M.Facile synthesis of ZnIn₂S₄/Cu₂O hierarchical heterostructures for enhanced selectivity and sensitivity of NH₃ gas at room temperature.Appl Surf Sci2023;640:158315

[52] Xu Z,Shi Y.Carbon dots as solid-state electron mediator and electron acceptor in S-scheme heterojunction for boosted photocatalytic hydrogen evolution.Appl Surf Sci2022;595:153482

[53] Chen W,Zhu J,Chen Z.Highly efficient visible-light-driven photocatalytic hydrogen evolution by all-solid-state Z-scheme CdS/QDs/ZnIn₂S₄ architectures with MoS₂ quantum dots as solid-state electron mediator.Appl Surf Sci2020;504:144406

[54] Yang R,Fan Y.ZnIn₂S₄-based photocatalysts for energy and environmental applications.Small Methods2021;5:2100887

[55] Fang W,Zhang Y.Alkaline induced indium gradient distribution in Zn_mIn₂S_3+m/In(OH)₃ heterojunction for improved photocatalytic H₂ generation.Appl Surf Sci2020;530:147241

[56] Pan Y,Jiang L.Recent advances in synthesis, modification and photocatalytic applications of micro/nano-structured zinc indium sulfide.Chem Eng J2018;354:407-31

[57] Wang S,Zhang SL,Lou XWD.Supporting ultrathin ZnIn₂S₄ nanosheets on Co/N-doped graphitic carbon nanocages for efficient photocatalytic H₂ generation.Adv Mater2019;31:1903404

[58] Huang L,Huang X.Ultrathin 2D/2D ZnIn₂S₄/MoS₂ hybrids for boosted photocatalytic hydrogen evolution under visible light.J Alloys Compd2019;798:553-9

[59] Chen Y,Chen D.Exploring the different photocatalytic performance for dye degradations over hexagonal ZnIn₂S₄ microspheres and cubic ZnIn₂S₄ nanoparticles.ACS Appl Mater Interfaces2012;4:2273-9

[60] Uddin A,Guo Z,Chen H.Hydrothermal synthesis of 3D/2D heterojunctions of ZnIn₂S₄/oxygen doped g-C₃N₄ nanosheet for visible light driven photocatalysis of 2,4-dichlorophenoxyacetic acid degradation.J Alloys Compd2020;845:156206

[61] Xu L,Li Z.Photocatalytic splitting of thiols to produce disulfides and hydrogen over PtS/ZnIn₂S₄ nanocomposites under visible light.Appl Catal B Environ2018;234:50-5

[62] Li M,Yang X,Yang MQ.S-scheme homojunction of 0D cubic/2D hexagonal ZnIn₂S₄ for efficient photocatalytic reduction of nitroarenes.J Colloid Interface Sci2024;674:547-59

[63] Wang S,Lou XWD.Construction of ZnIn₂S₄-In₂O₃ hierarchical tubular heterostructures for efficient CO₂ photoreduction.J Am Chem Soc2018;140:5037-40

[64] Zuo G,Teo WL,Zhao Y.Direct Z-scheme TiO₂-ZnIn₂S₄ nanoflowers for cocatalyst-free photocatalytic water splitting.Appl Catal B Environ2021;291:120126

[65] Chen Y,He B,Wu Q.Facile design and fabrication of RP/ZnIn₂S₄ composite photocatalysts with efficient removal of antibiotics under visible-light irradiation.J Alloys Compd2023;968:171972

[66] Tu B,Wang F,Li J.New insights into the enhancement of TiO₂/ZnIn₂S₄ heterojunction via cerium doping.Appl Surf Sci2023;629:157451

[67] Zhou F,Wu J.Utilizing Er-doped ZnIn₂S₄ for efficient photocatalytic CO₂ conversion.Appl Catal B Environ2024;341:123347

[68] Khosya M,Khare N.Enhanced photoelectrochemical water splitting in ternary layered chalcogenide ZnIn₂S₄ coupled with MWCNT.Nano Trends2023;4:100018

[69] Zhou M,Song Q,Chen B.Hybrid 0D/2D edamame shaped ZnIn₂S₄ photoanode modified by Co-Pi and Pt for charge management towards efficient photoelectrochemical water splitting.Appl Catal B Environ2019;244:188-96

[70] Zhang S,Xiao H.Fast interfacial carrier dynamics modulated by bidirectional charge transport channels in ZnIn₂S₄-based composite photoanodes probed by scanning photoelectrochemical microscopy.Angew Chem Int Ed2024;63:e202315763

[71] Li J,Guo Z.Piezoelectric effect promoted photoelectrochemical water splitting ability of ZnIn₂S₄ photoanode with highly exposed active (110) facets.ChemCatChem2024;16:e202301318

[72] Li S,Tian W.Engineering interfacial band bending over ZnIn₂S₄/SnS₂ by interface chemical bond for efficient solar-driven photoelectrochemical water splitting.Adv Energy Mater2022;12:2200629

[73] Lv G,Wu X.Realizing highly efficient photoelectrochemical performance for vertically aligned 2D ZnIn₂S₄ array photoanode via controlled facet and phase modulation.Appl Surf Sci2023;609:155335

[74] Khosya M,Faraz M.Visible light active ZnIn₂S₄/g-C₃N₄ heterostructure nanocomposite photoelectrode for efficient photoelectrochemical water splitting activity.Adv Powder Technol2023;34:104051

[75] Hao Z,Zhang L.Sufficient energy band utilization profited from spatially discrete heterogeneous interfaces to induce efficient photoelectrochemical water splitting for ZnIn₂S₄ photoanode.Surf Interfaces2024;51:104667

[76] Wang L,Lai L.Immobilization of prussian blue nanoparticles onto Au-modified ZnIn₂S₄ photoanode for efficient photoelectrochemical water splitting.Eur J Inorg Chem2024;27:e202400007

[77] Fan B,Liu Q,Fang X.One-pot hydrothermal synthesis of Ni-doped ZnIn₂S₄ nanostructured film photoelectrodes with enhanced photoelectrochemical performance.Appl Surf Sci2016;370:252-9

[78] Qian H,Guo Z,Ma J.Hexagonal phase/cubic phase homogeneous ZnIn₂S₄ n-n junction photoanode for efficient photoelectrochemical water splitting.J Alloys Compd2020;830:154639

[79] Qian H,Ya J,Ma J.Construction homojunction and co-catalyst in ZnIn₂S₄ photoelectrode by Co ion doping for efficient photoelectrochemical water splitting.J Alloys Compd2021;867:159028

[80] Wu Y,Lv G.Construction of p-n junctions in single-unit-cell ZnIn₂S₄ nanosheet arrays toward promoted photoelectrochemical performance.J Catal2021;401:262-70

[81] Xu W,Meng L,Li L.Incorporation of sulfate anions and sulfur vacancies in ZnIn₂S₄ photoanode for enhanced photoelectrochemical water splitting.Adv Energy Mater2021;11:2101181

[82] Wu K,Wu P.Highly efficient hydrogen production performance of g-C₃N₄ quantum dot-sensitized WO₃/Ni-ZnIn₂S₄ nanosheets.Appl Phys A2022;128:6055

[83] Fan H,Liu K.One-step MOF-templated strategy to fabrication of Ce-doped ZnIn₂S₄ tetrakaidecahedron hollow nanocages as an efficient photocatalyst for hydrogen evolution.Adv Sci2022;9:2104579

[84] Zhou D,Wang X.Ni, In co-doped ZnIn₂S₄ for efficient hydrogen evolution: modulating charge flow and balancing H adsorption/desorption.Appl Catal B Environ2022;310:121337

[85] Dong W,Ma Y.N-doped C-coated MoO₂/ZnIn₂S₄ heterojunction for efficient photocatalytic hydrogen production.Rare Met2023;42:1195-204

[86] Shi X,Wang X.Facile construction TiO₂/ZnIn₂S₄/Zn_0.4Ca_0.6In₂S₄ ternary hetero-structure photo-anode with enhanced photo-electrochemical water-splitting performance.Surf Interfaces2021;26:101323

[87] Hu Z,Han C.Plasmon-induced hole-depletion layer on p-n heterojunction for highly efficient photoelectrochemical water splitting.J Colloid Interface Sci2022;628:946-54

[88] Zhao Y,Shu Y.Classification and catalytic mechanisms of heterojunction photocatalysts and the application of titanium dioxide (TiO₂)-based heterojunctions in environmental remediation.J Environ Chem Eng2022;10:108077

[89] Yue Y.Oxygen vacancy-suppression strengthened the internal electric field in ZnIn₂S₄/BiVO₄ S-scheme heterojunction to boost photocatalytic removal of aqueous pollutants.J Environ Chem Eng2024;12:113473

[90] Wang S,Pu X,Zhang D.Photothermal-enhanced S-scheme heterojunction of hollow core-shell FeNi₂S₄@ZnIn₂S₄ toward photocatalytic hydrogen evolution.Small2024;20:2311504

[91] Liu D,Chen D.Twin S-scheme g-C₃N₄/CuFe₂O₄/ZnIn₂S₄ heterojunction with a self-supporting three-phase system for photocatalytic CO₂ reduction: mechanism insight and DFT calculations.ACS Catal2024;14:5326-43

[92] Wang H,Tang Q.Ultrathin 2D/2D ZnIn₂S₄/La₂Ti₂O₇ nanosheets with a Z-scheme heterojunction for enhanced photocatalytic hydrogen evolution.Dalton Trans2024;53:13491-502

[93] Xu W,Meng L,Li L.Interfacial chemical bond-modulated Z-scheme charge transfer for efficient photoelectrochemical water splitting.Adv Energy Mater2021;11:2003500

[94] Li J,Li J,Zhao L.1D/2D TiO₂/ZnIn₂S₄ S-scheme heterojunction photocatalyst for efficient hydrogen evolution.Chin J Catal2022;43:339-49

[95] Yue Y.Boosting interfacial charge separation for ZnIn₂S₄ homojunction by lattice matching effect to enhance photocatalytic performance.J Alloys Compd2023;966:171659

[96] Wang H,You Z,Liu Y.An innovative Zn₃In₂S₆/ZnIn₂S₄ homojunction photocatalyst with enhanced interfacial charge transfer for the highly efficient degradation of tetracycline under visible radiation.J Environ Manage2024;365:121605

[97] Jiang Z,Cai X.Enhanced performance of FeOOH/ZnIn₂S₄/Au nanosheet arrays for visible light water splitting.J Mater Sci Mater Electron2022;33:6070-81

[98] Li C,Ding G.Interior and surface synergistic modifications modulate the SnNb₂O₆/Ni-doped ZnIn₂S₄ S-scheme heterojunction for efficient photocatalytic H₂ evolution.Inorg Chem2022;61:4681-9

[99] Wang G,Xia C,Dong B.Sulfur poisoning-resistant TiO₂/Cu-doped ZnIn₂S₄ photoanode for achieving efficient sulfur oxidation.Colloids Surf A Physicochem Eng Aspects2024;689:133656

[100] Peng Y,Xu S.Surface modulation of MoS₂/O-ZnIn₂S₄ to boost photocatalytic H₂ evolution.J Energy Chem2022;75:276-84

[101] Zhao H,Cai M.Synergistic selenium doping and colloidal quantum dots decoration over ZnIn₂S₄ enabling high-efficiency photoelectrochemical hydrogen peroxide production.Chem Eng J2024;491:151925

[102] Jeong YJ,Nam S.Rapid surface reconstruction of In₂S₃ photoanode via flame treatment for enhanced photoelectrochemical performance.Adv Mater2024;2403164

[103] Gao L,Sewell CD,Lin Z.Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction.Chem Soc Rev2021;50:8428-69

[104] Guo W,Yang F.Robust interfacial effect in multi-interface environment through hybrid reconstruction chemistry for enhanced energy storage.ACS Nano2023;17:25357-67