硫族化物基S型异质结光催化剂

doi:10.1016/S1872-2067(24)60072-0

催化学报 ›› 2024, Vol. 63: 81-108.DOI: 10.1016/S1872-2067(24)60072-0

硫族化物基S型异质结光催化剂

陈春光^a^,¹, 张金锋^b^,¹, 褚海亮^a^,^*(), 孙立贤^a^,^*(), Graham Dawson^c, 代凯^b^,^c^,^*()

^a桂林电子科技大学, 广西电子信息材料构效关系重点实验室, 广西桂林 541004
^b淮北师范大学物理与电子信息学院, 绿色和精准合成化学及应用教育部重点实验室, 安徽淮北 235000
^c西交利物浦大学化学系, 江苏苏州 215123

收稿日期:2024-04-07 接受日期:2024-05-28 出版日期:2024-08-18 发布日期:2024-08-19
通讯作者: *电子信箱: daikai940@chnu.edu.cn (代凯),sunlx@guet.edu.cn (孙立贤),chuhailiang@guet.edu.cn (褚海亮).
作者简介:
¹共同第一作者.
基金资助:
国家自然科学基金(22278169);国家自然科学基金(22179026);国家自然科学基金(U20A20237);国家自然科学基金(52371218);安徽省高校优秀科研创新团队(2022AH010028);安徽省教育厅重大项目(2022AH040068);安徽省质量工程项目(2022sx134);桂林市创新平台与人才计划项目(20210102-4);桂林市漓江学者基金和广西八桂学者基金

Chalcogenide-based S-scheme heterojunction photocatalysts

Chunguang Chen^a^,¹, Jinfeng Zhang^b^,¹, Hailiang Chu^a^,^*(), Lixian Sun^a^,^*(), Graham Dawson^c, Kai Dai^b^,^c^,^*()

^aGuangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, Guangxi, China
^bLaboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000, Anhui, China
^cDepartment of Chemistry, Xi’an Jiaotong Liverpool University, Suzhou 215123, Jiangsu, China

Received:2024-04-07 Accepted:2024-05-28 Online:2024-08-18 Published:2024-08-19
Contact: *E-mail: daikai940@chnu.edu.cn (K. Dai), sunlx@guet.edu.cn (L. Sun), chuhailiang@guet.edu.cn (H. Chu).
About author:Hailiang Chu (School of Materials Science and Engineering, Guilin University of Electronic Technology) received his Ph.D. degree from Dalian Institute of Chemical Physics, Chinese Academy of Sciences in 2008. His research interests focus on the synthesis and application of high-performance electrode materials for secondary batteries and supercapacitors and high-capacity hydrogen storage materials, including alloys, metal borohydrides, metal-N-H materials, ammonia borane, and their derivatives.
Lixian Sun (School of Materials Science and Engineering, Guilin University of Electronic Technology). He graduated from Hunan University with a Ph.D. degree in 1994. He is currently focusing on research in energy storage, especially hydrogen storage materials, biofuel cells, thermochemistry, and sensors.
Kai Dai (Huaibei Normal University) was invited as a member of the Youth Editorial Board of Chinese Journal of Catalysis, Renewable and Sustainable Energy, Chinese Journal of Structural Chemistry and Acta Physico-Chimica Sinica. Prof. Kai Dai received his B.A. degree from Anhui University (China) in 2002, and Ph.D. degree from Shanghai University (China) in 2007. He worked in Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences in 2007, and then in Huaibei Normal University in 2010. He is Distinguished Young Scholars Recipients of Natural Science Foundation of Anhui Province (2018) and serves as the head of Anhui Provincial Excellent research and innovation team in universities (2022) and Anhui Provincial Teaching Team (2019). He has also been invited by Xi’an Jiaotong Liverpool University to be a visiting Professor and PhD co-supervisor since 2022. His research interests mainly focus on semiconductor nanomaterials for solar energy conversion. He has published more than 150 peer-reviewed papers, including 11 hot paper of ESI and 24 highly cited papers of ESI.
¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22278169);National Natural Science Foundation of China(22179026);National Natural Science Foundation of China(U20A20237);National Natural Science Foundation of China(52371218);Excellent scientific research and innovation team of Education Department of Anhui Province(2022AH010028);Major projects of Education Department of Anhui Province(2022AH040068);Anhui Provincial Quality Engineering Project(2022sx134);Innovation Platform and Talent Program Project of Guilin(20210102-4);Guilin Lijiang Scholar Foundation and the Guangxi Bagui Scholar Foundation

摘要/Abstract

摘要：

硫族化物因具有较宽的光吸收范围和较好的光还原能力, 在光催化领域备受关注. 目前已经开发的硫族化物光催化剂种类较多, 但是单组分光催化剂始终面对着一个难以解决的矛盾--难以同时满足宽的光吸收范围和强的氧化还原能力. 构建半导体异质结成为解决上述矛盾的有效办法. 近年来, S型异质结因其独特的光催化机理为研发新型高效光催化剂提供了重要途径. 因此, 通过合理的选择硫族化物与其他半导体构建S型异质结光催化剂, 可以充分发挥硫族化物和S型异质结的优势, 改善载流子快速复合情况, 提高光能转换效率, 从而展现出硫族化物基S型异质结光催化剂在光催化领域的巨大发展潜力.

本文综述了硫族化物基S型异质结光催化剂的作用机理、合成方法、在光催化领域的应用以及对应的先进表征技术. 首先, 系统总结了光催化的基本原理, 并介绍了异质结光催化剂的工作机制, 重点阐述了S型异质结的能带结构及其对硫族化物基S型异质结光催化剂光催化活性和稳定性的提升机制. 其次, 概述了几种常见的制备硫族化物基S型异质结光催化剂的方法, 并讨论了每种方法的各自特点, 为设计异质结光催化剂提供了思路. 此外, 深入探讨了硫族化物基S型异质结光催化剂在光催化领域的应用, 表明其在能源储备和环境保护等方面的发展潜力和优势. 同时, 本文还讨论了用于验证S型异质结机理的一系列稳态和瞬态的先进表征和模拟技术, 包括原位表征技术和密度泛函理论等. 最后, 提出了硫族化物基S型异质结光催化剂面临的问题和挑战以及相对应的建议, 并且对其在光催化领域的发展趋势进行了展望.

综上, 本文详细综述了硫族化物基S型异质结光催化剂的研究进展, 为硫族化物基S型异质结光催化剂在光催化领域的进一步应用提供参考.

关键词: 光催化, 硫族化物, S型异质结, 电荷分离, 应用

Abstract:

The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts. By carefully selecting semiconductors for S-scheme heterojunction photocatalysts, it is possible to reduce the rate of photogenerated carrier recombination and increase the conversion efficiency of light into energy. Chalcogenides are a group of compounds that include sulfides and selenides (e.g., CdS, ZnS, Bi₂S₃, MoS₂, ZnSe, CdSe, and CuSe). Chalcogenides have attracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap, wide light absorption range, and excellent photoreduction properties. This paper presents a thorough analysis of S-scheme heterojunction photocatalysts based on chalcogenides. Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocatalysts, various chalcogenide-based S-scheme heterojunction photocatalyst synthesis techniques are summarized. These photocatalysts are used in numerous significant photocatalytic reactions, including the reduction of carbon dioxide, synthesis of hydrogen peroxide, conversion of organic matter, generation of hydrogen from water, nitrogen fixation, degradation of organic pollutants, and sterilization. In addition, cutting-edge characterization techniques, including in situ characterization techniques, are discussed to validate the steady and transient states of photocatalysts with an S-scheme heterojunction. Finally, the design and challenges of chalcogenide-based S-scheme heterojunction photocatalysts are explored and recommended in light of state-of-the-art research.

Key words: Photocatalysis, Chalcogenide, S-scheme heterojunction, Charge separation, Application

陈春光, 张金锋, 褚海亮, 孙立贤, Graham Dawson, 代凯. 硫族化物基S型异质结光催化剂[J]. 催化学报, 2024, 63: 81-108.

Chunguang Chen, Jinfeng Zhang, Hailiang Chu, Lixian Sun, Graham Dawson, Kai Dai. Chalcogenide-based S-scheme heterojunction photocatalysts[J]. Chinese Journal of Catalysis, 2024, 63: 81-108.

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图/表 29

Fig. 1. Advantages of chalcogenides in photocatalytic applications.

Fig. 2. Schematic overview of the chalcogenide-based S-scheme heterojunctions.

Fig. 3. Band structure and charge transfer direction of type-II heterojunction (a), conventional Z-scheme heterojunction (b), all-solid Z-scheme heterojunction (c), and direct Z-scheme heterojunction (d).

Fig. 4. Photocatalytic reaction mechanism of S-scheme heterojunction photocatalyst.

Fig. 5. (a) Fabrication process of Ti3C2-ZnIn2S4-NiSe2 composites. (b) Schematic of interfacial electron transfer, Ef equilibrium, and migration of photogenerated carriers in MX-modified ZIS-NiSe2 S-scheme heterojunction under illumination [43]. Copyright 2022, Elsevier.

Fig. 6. (a) SEM images of ZZS-20 nanofibers. (b) TEM images of ZZS-20. (c) HRTEM images of ZZS-20. (d) Photocatalytic H2O2 evolution performance of different photocatalysts. (e) Stability cycle test of H2O2 production by ZZS-20. (f) XRD pattern before and after four cycles of ZZS-20 [47]. Copyright 2023, Elsevier.

Fig. 7. (a) The preparation process of core-shell MC nanocomposite. (b) SEM image and EDS result of MC-10. (c) TEM image of MC-10. (d) H2-evolution rates of all synthesized samples. (e) Stability test of H2 generation by MC-10 [49]. Copyright 2021, Springer Nature.

Fig. 8. TEM images of 10MCS (a) and 15MCS (b) samples. The location of the MoS2 nanosheets is shown in the inset images, highlighted in blue. (c) Time-based H2 evolution curves for different samples. (d) Cyclic photocatalytic H2 evolution performance of the 2.5MCS sample under visible-light illumination. (e) Schematic of the charge transfer and recombination processes in the MoS2-tipped CdS NRs and MoS2-coated CdS NRs for photocatalytic H2 evolution [50]. Copyright 2020, Elsevier.

Fig. 9. (a) Schematic of the experimental process for TiO2/CdS well-distributed hybrid nanofibers. FESEM images of TiO2 (b), CdS (c), and TC10 (d). (e) HRTEM image of TC10 [57]. Copyright 2019. John Wiley and Sons.

Fig. 10. Schematic of the application of chalcogenide-based S-scheme heterojunction photocatalysts in the field of photocatalysis.

Fig. 11. SEM images of ZnWO4-ZnIn2S4-40 at low (a) and high (b) magnification. Amount (c) and rate (d) of H2 evolution for different samples. (e,f) Cyclic stability of H2 evolution activity over ZnWO4-ZnIn2S4-40 [14]. Copyright 2022, Elsevier.

Fig. 13. Band positions of various photocatalysts relative to the redox potentials at pH = 7 of compounds involved in CO2 reduction.

Fig. 14. (a) Schematic of the preparation process of the MoO3-x@ZnIn2S4 composites. (b) CH4 production and (c) CO production as a function of the irradiation time under full-spectrum illumination over different samples. (d) Product yields, CH4 selectivity, and surface temperature of different samples under full-spectrum illumination. (e) Product yields and CH4 selectivity of the samples under different temperatures [97]. Copyright 2023, Royal Society of Chemistry.

Fig. 15. UV-DRS (a) and TPRL (b) spectra of different samples. (c) Photocatalytic performance of H2 evolution and benzyl alcohol oxidation for different samples. (d) EPR spectra of DMPO-?O2? for different samples under visible light irradiation. (e) Schematic depicting simultaneous photocatalytic H2 evolution and aromatic alcohol oxidation at CMZIS heterojunctions [100]. Copyright 2023, Elsevier.

Fig. 18. N2 adsorption-desorption isotherms (a) and UV-visible light absorption spectra (b) of different samples. (c) Photocatalytic ammonia production under different conditions, (d) the N2 fixation rate of different samples [122]. Copyright 2023, Elsevier.

Fig. 19. (a) Synergistic adsorption and photo-Fenton mechanisms of PLS-MBB composite sponge in the removal of fluoroquinolones. (b) Trapping experiment of active species during the photo-Fenton degradation of norfloxacin by PLS-MBB. (c) PL spectra of hydroxybenzoic acid are generated in different systems [132]. Copyright 2022, Elsevier.

Fig. 20. Antibacterial efficiency of the sample against Escherichia coli (a) and Staphylococcus aureus (b). Growth rate constants of Escherichia coli (c) and Staphylococcus aureus (d) at different concentrations of F101@MoS2/ZnO [143]. Copyright 2022, American Chemical Society.

Table 1 Overview of catalytic efficiency of chalcogenide-based S-scheme heterojunction photocatalysts.

Photocatalyst	Mechanism	Synthesis method	Light source	Application	Photocatalytic efficacy	Ref.
CdS/pyrene-alt-triphenylamine	S-scheme	in situ growth	350 W Xenon arc lamp with 420 nm cut off filter	H₂ evolution	9.28 mmol h^-1 g^-1	[79]
Co₉S₈/ZnSe	S-scheme	hydrothermal and solvothermal methods	300W Xe lamp (λ ≥ 420 nm)	H₂ evolution	967.8 μmol g^-1 h^-1	[25]
ZnWO₄-ZnIn₂S₄	S-scheme	low-temperature solvothermal method	300 W Xenon arc lamp (λ ≥ 420 nm)	H₂ evolution	4925.3 μmol g^-1 h^-1	[14]
MoO_3-_x@ZnIn₂S₄	S-scheme	low-temperature reflux method	300 W Xe lamp	reduce CO₂ to CH₄ and CO	28.3 and 4.65 μmol g^-1 h^-1	[97]
CoS₁₊_x cocatalyst modified MIL-88B (Fe)/ZnIn₂S₄	S-scheme	in situ photo-deposition method	300W Xe lamp (λ > 420 nm)	H₂ evolution and oxidate benzyl alcohol to benzaldehyde	3164.9 and 3417.8 μmol g^-1 h^-1	[100]
CdSe/KPN-HCP	S-scheme	two-step calcination method	300W Xe lamp with a 420 nm cutoff filter	H₂ evolution, H₂O₂ production, degradation of TC	1860.8 and 900.0 μmol g^-1 h^-1, 95.6% in 60 min (TC, 10 mg L^-1)	[115]
OV-TiO₂@Cu₇S₄	S-scheme	anion exchange and hydrothermal methods	350W Xe lamp with a 420 nm cutoff filter	NH₃ production	133.42 μmol cm^-2 h^-1	[122]
CuSe-Cu₃Se₂/ Ag-polyaniline	Dual S-scheme	co-precipitation method	30W LED lamp	degradation of methylene blue (MB)	100% in 45 min (MB, 20 mg L^-1)	[27]
Ta₃N₅/CdS	S-scheme	wet-chemical method	300W Xe lamp (λ ≥ 420 nm)	degradation of TC and Cr(VI)	88.5% in 50 min (TC, 20 mg L^-1), 96.1% in 40 min (Cr(VI), 10 mg L^-1)	[133]
MoS₂/SnO₂	S-scheme	hydrothermal method	300W halogen lamp with a 420 nm cutoff filter	degradation of ciprofloxacin (CIP) and Cr(VI) and antibacterial	97.6% in 100 min (CIP, 10 mg L^-1) and 92.5% in 60 min (Cr(VI), 10 mg L^-1) and 100% in 10 min (Escherichia coli, 30 mL)	[144]

Table 1 Overview of catalytic efficiency of chalcogenide-based S-scheme heterojunction photocatalysts.

Photocatalyst	Mechanism	Synthesis method	Light source	Application	Photocatalytic efficacy	Ref.
CdS/pyrene-alt-triphenylamine	S-scheme	in situ growth	350 W Xenon arc lamp with 420 nm cut off filter	H₂ evolution	9.28 mmol h^-1 g^-1	[79]
Co₉S₈/ZnSe	S-scheme	hydrothermal and solvothermal methods	300W Xe lamp (λ ≥ 420 nm)	H₂ evolution	967.8 μmol g^-1 h^-1	[25]
ZnWO₄-ZnIn₂S₄	S-scheme	low-temperature solvothermal method	300 W Xenon arc lamp (λ ≥ 420 nm)	H₂ evolution	4925.3 μmol g^-1 h^-1	[14]
MoO_3-_x@ZnIn₂S₄	S-scheme	low-temperature reflux method	300 W Xe lamp	reduce CO₂ to CH₄ and CO	28.3 and 4.65 μmol g^-1 h^-1	[97]
CoS₁₊_x cocatalyst modified MIL-88B (Fe)/ZnIn₂S₄	S-scheme	in situ photo-deposition method	300W Xe lamp (λ > 420 nm)	H₂ evolution and oxidate benzyl alcohol to benzaldehyde	3164.9 and 3417.8 μmol g^-1 h^-1	[100]
CdSe/KPN-HCP	S-scheme	two-step calcination method	300W Xe lamp with a 420 nm cutoff filter	H₂ evolution, H₂O₂ production, degradation of TC	1860.8 and 900.0 μmol g^-1 h^-1, 95.6% in 60 min (TC, 10 mg L^-1)	[115]
OV-TiO₂@Cu₇S₄	S-scheme	anion exchange and hydrothermal methods	350W Xe lamp with a 420 nm cutoff filter	NH₃ production	133.42 μmol cm^-2 h^-1	[122]
CuSe-Cu₃Se₂/ Ag-polyaniline	Dual S-scheme	co-precipitation method	30W LED lamp	degradation of methylene blue (MB)	100% in 45 min (MB, 20 mg L^-1)	[27]
Ta₃N₅/CdS	S-scheme	wet-chemical method	300W Xe lamp (λ ≥ 420 nm)	degradation of TC and Cr(VI)	88.5% in 50 min (TC, 20 mg L^-1), 96.1% in 40 min (Cr(VI), 10 mg L^-1)	[133]
MoS₂/SnO₂	S-scheme	hydrothermal method	300W halogen lamp with a 420 nm cutoff filter	degradation of ciprofloxacin (CIP) and Cr(VI) and antibacterial	97.6% in 100 min (CIP, 10 mg L^-1) and 92.5% in 60 min (Cr(VI), 10 mg L^-1) and 100% in 10 min (Escherichia coli, 30 mL)	[144]

Fig. 21. Ex situ and in situ irradiated XPS spectra of the RF, CdS and CdS/RF samples. High resolution spectra: C 1s (a), S 2p (b), and Cd 3d (c). (d) CPDs of RF and CdS. (e) Charge transfer mechanism of CdS/RF S-scheme heterojunction [153]. Copyright 2023, Elsevier.

Fig. 22. DMPO spin-trapping EPR signals for BIO, CdS, and the CdS-10/BIO hybrid: DMPO-?O2- (a) and DMPO-?OH (b). (c) Schematic of the S-scheme charge transfer mechanism of CdS-10/BIO photocatalyst [150]. Copyright 2023, Elsevier.

Fig. 23. CO2-TPD (a) and CO-TPD (b) profiles of Ta2O5, NiS, and 20NSTO. In situ DRIFTS measurements of Ta2O5 (c) and 20NSTO (d) under full spectrum light irradiation in pure CO2 [164]. Copyright 2023, Elsevier.

Fig. 26. Transient absorption spectra of pure TiO2 (a) and TC5 (b). (c) The corresponding transient absorption kinetic trajectories of TiO2 and TC5 at 645 nm within 100 ps [171]. Copyright 2022, American Chemical Society.

Fig. 27. AFM image of 7ZCS@DBTCN (a), and corresponding surface potential images of 7ZCS@DBTCN under dark (b) and light-irradiation (c) conditions; (d) The surface potential of the line scan from point A to point B [58]. Copyright 2023, Elsevier.

Fig. 28. Schematic of the band structures of HCN (a), ZIS (b), and HCN@ZIS (c). Planar average electron density difference Δρ(d), differential charge density plot (e) of HCN@ZIS. (f) Band positions and charge transfer maps of HCN and ZIS [179]. Copyright 2023, John Wiley and Sons.

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硫族化物基S型异质结光催化剂

Chalcogenide-based S-scheme heterojunction photocatalysts

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