金属硫化物光催化析氢研究进展

doi:10.3969/j.issn.1000-1565.2026.01.007

摘要/Abstract

摘要： 过渡金属硫化物作为一种重要的半导体材料,因其在光吸收范围、电荷分离效率等方面的优异性能,近年来在可见光催化领域受到了广泛关注.特别是在能源转换领域,利用可见光驱动光催化反应将太阳能转化为化学能被认为是一种解决能源危机的有效途径.本文综述了金属硫化物在光催化析氢领域的研究进展,首先探讨了提升金属硫化物光催化性能的策略,随后回顾了金属硫化物在光催化水分解制氢的应用进展.最后,总结了金属硫化物光催化材料面临的挑战,并对未来研究方向和重点进行了展望.

关键词: 金属硫化物, 改性策略, 光催化析氢, 研究进展

Abstract: Transition metal sulfide, as an important semiconductor material, has attracted extensive attention in the field of visible light catalysis in recent years due to its excellent performance in light absorption range and charge separation efficiency.Especially in the field of energy conversion, the use of visible light to drive photocatalytic reactions to convert solar energy into chemical energy is considered to be an effective way to solve the energy crisis. In this paper, the research progress of metal sulfides in the field of photocatalytic hydrogen evolution is reviewed. Firstly, the strategies to improve the photocatalytic performance of metal sulfides are discussed,and then the application progress of metal sulfides in photocatalytic water decomposition to hydrogen production is reviewed. Finally, it summarizes the challenges faced by metal sulfide-based photocatalytic materials and provides an outlook on future research directions and areas.

Key words: metal sulfide, modification strategy, photocatalytic hydrogen evolution, research progress

中图分类号:

O643.36

刘洁,董逸琛,张斌,陶子晨,陈文鑫. 金属硫化物光催化析氢研究进展[J]. 河北大学学报(自然科学版), 2026, 46(1): 56-67.

LIU Jie,DONG Yichen,ZHANG Bin,TAO Zichen,CHEN Wenxin. Progress in the research of metal sulfide photocatalytic hydrogen evolution[J]. Journal of Hebei University(Natural Science Edition), 2026, 46(1): 56-67.

参考文献

[1] KUMARAVEL V, IMAM M D, BADRELDIN A, et al. Photocatalytic hydrogen production: role of sacrificial reagents on the activity of oxide, carbon, and sulfide catalysts [J]. Catalysts, 2019, 9(3):276. DOI: 10.3390/catal9030276.
[2] LOEB S K, ALVAREZ P J J, BRAME J A, et al. The technology horizon for photocatalytic water treatment: sunrise or sunset? [J]. Environ Sci Technol, 2019, 53(6): 2937-2947. DOI: 10.1021/acs.est.8b05041.
[3] JIN Z, ZENG S, CAO C, et al. Impacts of pollution abatement projects on happiness: An exploratory study in China [J]. J Clean Prod, 2020, 274:122869. DOI: 10.1016/j.jclepro.2020.122869.
[4] TAKATA T, JIANG J Z, SAKATA Y, et al. Photocatalytic water splitting with a quantum efficiency of almost unity [J].Nature, 2020, 581(7809): 411-414. DOI: 10.1038/s41586-020-2278-9.
[5] YU J X, CHANG S F, SHI L, et al. Single-crystalline Bi₂YO₄Cl with facet-aided photocarrier separation for robust solar water splitting [J]. ACS Catal, 2023, 13(6): 3854-3863. DOI: 10.1021/acscatal.2c05768.
[6] LEE D E, DANISH M, ALAM U, et al. Review on inorganic and polymeric materials-coordinated metal-organic-framework photocatalysts for green hydrogen evolution [J]. J Energy Chem, 2024, 92: 322-356. DOI: 10.1016/j.jechem.2023.12.029.
[7] BIE C B, WANG L X, YU J G. Challenges for photocatalytic overall water splitting [J]. Chem, 2022, 8(6): 1567-1574. DOI: 10.1016/j.chempr.2022.04.013.
[8] MORIKAWA T, SATO S, SEKIZAWA K, et al. Molecular catalysts immobilized on semiconductor photosensitizers for proton reduction toward visible-light-driven overall water splitting [J]. Chemsuschem, 2019, 12(9): 1807-1824. DOI: 10.1002/cssc.201900441.
[9] WANG L, XU H X. Two-dimensional conjugated polymer frameworks for solar fuel generation from water [J]. Prog Polym Sci, 2023, 145:101734. DOI: 10.1016/j.progpolymsci.2023.101734.
[10] WANG Z, LI C, DOMEN K. Recent developments in heterogeneous photocatalysts for solar-driven overall water splitting [J]. Chem Soc Rev, 2019, 48(7): 2109-2125. DOI: 10.1039/c8cs00542g.
[11] WEI Z S, MOGAN T R, WANG K L, et al. Morphology-governed performance of multi-dimensional photocatalysts for hydrogen generation [J]. Energies, 2021, 14(21):7223. DOI: 10.3390/en14217223.
[12] ACAR C, DINCER I, NATERER G F. Review of photocatalytic water-splitting methods for sustainable hydrogen production [J]. Int J Energy Res, 2016, 40(11): 1449-1473. DOI: 10.1002/er.3549.
[13] LU P, LIU K, LIU Y, et al. Heterostructure with tightly-bound interface between In₂O₃ hollow fiber and ZnIn₂S₄ nanosheet toward efficient visible light driven hydrogen evolution [J]. Appl Catal B-Environ, 2024, 345:123697. DOI: 10.1016/j.apcatb.2024.123697.
[14] TAHIR M, TASLEEM S, TAHIR B. Recent development in band engineering of binary semiconductor materials for solar driven photocatalytic hydrogen production [J]. Int J Hydrog Energy, 2020, 45(32): 15985-16038. DOI: 10.1016/j.ijhydene.2020.04.071.
[15] DENG F, PENG J L, LI X B, et al. Metal sulfide-based Z-scheme heterojunctions in photocatalytic removal of contaminants, H₂ evolution and CO₂ reduction: Current status and future perspectives [J]. J Clean Prod, 2023, 416:137957. DOI: 10.1016/j.jclepro.2023.137957.
[16] LIU Y, HUANG D L, CHENG M, et al. Metal sulfide/MOF-based composites as visible-light-driven photocatalysts for enhanced hydrogen production from water splitting [J]. Coord Chem Rev, 2020, 409:213220. DOI: 10.1016/j.ccr.2020.213220.
[17] LIN L, REN W, WANG C, et al. Crystalline carbon nitride semiconductors prepared at different temperatures for photocatalytic hydrogen production [J]. Appl Catal B-Environ, 2018, 231: 234-241. DOI: 10.1016/j.apcatb.2018.03.009.
[18] WANG S D, XIE Z P, ZHU D, et al. Efficient photocatalytic production of hydrogen peroxide using dispersible and photoactive porous polymers [J]. Nat Commun, 2023, 14(1):6891. DOI: 10.1038/s41467-023-42720-6.
[19] ZHAO C X, CHEN Z P, SHI R, et al. Recent advances in conjugated polymers for visible-light-driven water splitting [J]. Adv Mater, 2020, 32(28):1907296. DOI: 10.1002/adma.201907296.
[20] ZHANG J K, YU Z B, GAO Z, et al. Porous TiO₂ nanotubes with spatially separated platinum and CoOx cocatalysts produced by atomic layer deposition for photocatalytic hydrogen production [J]. Angew Chem Int Ed, 2017, 56(3): 816-820. DOI: 10.1002/anie.201611137.
[21] PAN J, DONG Z, WANG B, et al. The enhancement of photocatalytic hydrogen production via Ti³⁺self-doping black TiO₂/g-C₃N₄ hollow core-shell nano-heterojunction [J]. Appl Catal B-Eeviron, 2019, 242: 92-99. DOI: 10.1016/j.apcatb.2018.09.079.
[22] SINGH R, DUTTA S. A review on H₂ production through photocatalytic reactions using TiO₂/TiO₂-assisted catalysts [J]. Fuel, 2018, 220: 607-620. DOI: 10.1016/j.fuel.2018.02.068.
[23] YUAN Y-J, CHEN D Q, YU Z-T, et al. Cadmium sulfide-based nanomaterials for photocatalytic hydrogen production [J]. J Mater Chem A, 2018, 6(25): 11606-11630. DOI: 10.1039/c8ta00671g.
[24] BAI J X, CHEN W L, SHEN R C, et al. Regulating interfacial morphology and charge-carrier utilization of Ti₃C₂ modified all-sulfide CdS/ZnIn₂S₄ S-scheme heterojunctions for effective photocatalytic H₂ evolution [J]. J Mater Sci Technol, 2022, 112: 85-95. DOI: 10.1016/j.jmst.2021.11.003.
[25] LIU N, YU H, LIU Y B, et al. A novel hierarchical S-scheme heterojunction of 0D/3D Zn_0.5Cd_0.5S nanoparticles/hollow micro-flower MoS₂ for improved photocatalytic hydrogen evolution [J]. Appl Surf Sci, 2023, 632:157579. DOI: 10.1016/j.apsusc.2023.157579.
[26] XIAO Q, YANG T T, GUO X, et al. S-scheme heterojunction constructed by ZnCdS and CoWO₄ nano-ions promotes photocatalytic hydrogen production [J]. Surf Interfaces, 2023, 43:103577. DOI: 10.1016/j.surfin.2023.103577.
[27] LIU M M, LI H X, LIU S J, et al. Tailoring activation sites of metastable distorted IT'-phase MoS₂ by Ni doping for enhanced hydrogen evolution [J]. Nano Res, 2022, 15(7): 5946-5952. DOI:10.1007/s12274-022-4267-9.
[28] FAN X B, YU S, HOU B, et al. Quantum dots based photocatalytic hydrogen evolution [J]. Isr J Chem, 2019, 59(8): 762-773. DOI: 10.1002/ijch.201900029.
[29] HAO X Q, JIN Z L, YANG H, et al. Peculiar synergetic effect of MoS₂ quantum dots and graphene on metal-organic frameworks for photocatalytic hydrogen evolution [J]. Appl Catal B-Environ, 2017, 210: 45-56. DOI: 10.1016/j.apcatb.2017.03.057.
[30] ZHANG J J, ZHAO Y, QI K Z, et al. CuInS₂ quantum-dot-modified g-C₃N₄ S-scheme heterojunction photocatalyst for hydrogen production and tetracycline degradation [J]. J Mater Sci Technol, 2024, 172: 145-155. DOI: 10.1016/j.jmst.2023.06.042.
[31] HUANG Z Y, SUN P F, ZHANG H Z, et al. Solar-driven highly effective biomass-derived alcohols C-C coupling integrated with H₂ Production by CdS quantum dots modified Zn₂In₂S₅ nanosheets [J]. ACS Catal, 2024, 14(7): 4581-4592. DOI: 10.1021/acscatal.3c05826.
[32] BEN ALI M, JO W K, ELHOUICHET H, et al. Reduced graphene oxide as an efficient support for CdS-MoS₂ heterostructures for enhanced photocatalytic H₂ evolution [J]. Int J Hydrog Energy, 2017, 42(26): 16449-16458. DOI: 10.1016/j.ijhydene.2017.05.225.
[33] PAREEK A, KIM H G, PAIK P, et al. Nano-architecture based photoelectrochemical water oxidation efficiency enhancement by CdS photoanodes [J]. Mater Res Express, 2017, 4(2):026203. DOI:10.1088/2053-1591/aa5c93.
[34] WANG X T, LV R, WANG K. Synthesis of ZnO@ZnS-Bi₂S₃ core-shell nanorod grown on reduced graphene oxide sheets and its enhanced photocatalytic performance [J]. J Mater Chem A, 2014, 2(22): 8304-8313. DOI:10.1039/c4ta00696h.
[35] WANG J, SHI Y X, SUN H R, et al. Fabrication of Bi₄Ti₃O₁₂/ZnIn₂S₄ S-scheme heterojunction for achieving efficient photocatalytic hydrogen production [J]. J Alloy Compd, 2023, 930:167450. DOI: 10.1016/j.jallcom.2022.167450.
[36] BIE C B, FU J W, CHENG B, et al. Ultrathin CdS nanosheets with tunable thickness and efficient photocatalytic hydrogen generation [J]. Appl Surf Sci, 2018, 462: 606-614. DOI: 10.1016/j.apsusc.2018.08.130.
[37] XIE W J, LI X, ZHANG F J. Mo-vacancy induced high performance for photocatalytic hydrogen production over MoS₂ nanosheets cocatalyst [J]. Chem Phys Lett, 2020, 746:137276. DOI: 10.1016/j.cplett.2020.137276,
[38] FAN H T, JIN Y J, LIU K C, et al. One-step MOF-templated strategy to fabrication of Ce-doped ZnIn₂S₄ tetrakaidecahedron Hollow Nanocages as an efficient photocatalyst for hydrogen evolution [J]. Adv Sci, 2022, 9(9):2104579. DOI: 10.1002/advs.202104579.
[39] ZHANG P, YIN X, ZHANG D G, et al. MOF templated to construct hierarchical ZnIn₂S₄-In₂S₃ hollow nanotube for enhancing photocatalytic performance [J]. Chem Eng J, 2023, 458:141394. DOI: 10.1016/j.cej.2023.141394.
[40] SHEN R C, ZHANG L P, CHEN X Z, et al. Integrating 2D/2D CdS/α-Fe₂O₃ ultrathin bilayer Z-scheme heterojunction with metallic β-NiS nanosheet-based ohmic junction for efficient photocatalytic H₂ evolution [J]. Appl Catal B-Environ, 2020, 266:118619. DOI: 10.1016/j.apcatb.2020.118619.
[41] ZHANG W J, ZHAO S S, XING Y P, et al. Sandwich-like P-doped h-BN/ZnIn₂S₄ nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H₂ and H₂O₂ evolution [J]. Chem Eng J, 2022, 442:136151. DOI: 10.1016/j.cej.2022.136151.
[42] HU Y, HAO X Q, CUI Z W, et al. Enhanced photocarrier separation in conjugated polymer engineered CdS for direct Z-scheme photocatalytic hydrogen evolution [J]. Appl Catal B-Environ, 2020, 260:118131. DOI: 10.1016/j.apcatb.2019.118131.
[43] SHI Z, JIN W, SUN Y H, et al. Interface charge separation in Cu₂CoSnS₄/ZnIn₂S₄ heterojunction for boosting photocatalytic hydrogen production [J]. Chin J Struct Chem, 2023, 42(12):100201. DOI: 10.1016/j.cjsc.2023.100201.
[44] JIANG X, FAN D, YAO X T, et al. Highly efficient flower-like ZnIn₂S₄/CoFe₂O₄ photocatalyst with p-n type heterojunction for enhanced hydrogen evolution under visible light irradiation [J]. J Colloid Interf Sci, 2023, 641: 26-35. DOI: 10.1016/j.jcis.2023.03.055.
[45] WANG X P, JIN Z L, LI X. Monoclinic β-AgVO₃ coupled with CdS formed a 1D/1D p-n heterojunction for efficient photocatalytic hydrogen evolution [J]. Rare Met, 2023, 42(5): 1494-1507. DOI: 10.1007/s12598-022-02183-y.
[46] CHEN K Y, SHI Y X, SHU P, et al. Construction of core-shell FeS₂@ZnIn₂S₄ hollow hierarchical structure S-scheme heterojunction for boosted photothermal-assisted photocatalytic H₂ production [J]. Chem Eng J, 2023, 454:140053. DOI: 10.1016/j.cej.2022.140053.
[47] YANG W X, MA G Z, FU Y, et al. Rationally designed Ti₃C₂ MXene@TiO₂/CuInS₂ Schottky/S-scheme integrated heterojunction for enhanced photocatalytic hydrogen evolution [J]. Chem Eng J, 2022, 429:132381. DOI: 10.1016/j.cej.2021.132381.
[48] LI S S, WANG L, LI Y D, et al. Novel photocatalyst incorporating Ni-Co layered double hydroxides with P-doped CdS for enhancing photocatalytic activity towards hydrogen evolution [J]. Appl Catal B-Environ, 2019, 254: 145-155. DOI: 10.1016/j.apcatb.2019.05.001.
[49] CHAVA R K, SON N, KANG M. Controllable oxygen doping and sulfur vacancies in one dimensional CdS nanorods for boosted hydrogen evolution reaction [J]. J Alloy Compd, 2021, 873:159797. DOI: 10.1016/j.jallcom.2021.159797
[50] WANG Y J, CHEN J, LIU L M, et al. Novel metal doped carbon quantum dots/CdS composites for efficient photocatalytic hydrogen evolution [J]. Nanoscale, 2019, 11(4): 1618-1625. DOI: 10.1039/c8nr05807e.
[51] ZHOU D X, XUE X D, WANG X, et al. Ni, In co-doped ZnIn₂S₄ for efficient hydrogen evolution: Modulating charge flow and balancing H adsorption/desorption [J]. Appl Catal B-Environ, 2022, 310:121337. DOI: 10.1016/j.apcatb.2022.121337.
[52] SUN T, LI C X, BAO Y P, et al. S-scheme MnCo₂S₄/g-C₃N₄ heterojunction photocatalyst for H₂ production [J]. Acta Phys Chim Sin, 2023, 39(6):112121. DOI: 10.3866/PKU.WHXB202212009.
[53] RAN J R, ZHANG H P, FU S J, et al. NiPS₃ ultrathin nanosheets as versatile platform advancing highly active photocatalytic H₂ production [J]. Nat Commun, 2022, 13(1):4600. DOI: 10.1038/s41467-022-32256-6.
[54] XIN X, LI Y K, ZHANG Y Z, et al. Large electronegativity differences between adjacent atomic sites activate and stabilize ZnIn₂S₄ for efficient photocatalytic overall water splitting [J]. Nat Commun, 2024, 15(1):337. DOI: 10.1038/s41467-024-44725-1.
[55] XIONG Z, HOU Y D, YUAN R S, et al. Hollow NiC₂S₄ nanospheres as a cocatalyst to support ZnIn₂S₄ nanosheets for visible-light-driven hydrogen production [J]. Acta Phys Chim Sin, 2022, 38(7):2111021. DOI: 10.3866/PKU.WHXB202111021.
[56] ZHANG Y Z, ZHOU W, TANG Y, et al. Unravelling unsaturated edge S in amorphous NiSx for boosting photocatalytic H₂ evolution of metastable phase CdS confined inside hydrophilic beads [J]. Appl Catal B-Environ, 2022, 305:121055. DOI: 10.1016/j.apcatb.2021.121055.
[57] TAYYAB M, LIU Y J, MIN S X, et al. Simultaneous hydrogen production with the selective oxidation of benzyl alcohol to benzaldehyde by a noble-metal-free photocatalyst VC/CdS nanowires [J]. Chinese J Catal, 2022, 43(4): 1165-1175. DOI: 10.1016/S1872-2067(21)63997-9. (