Chalcogenide-based S-scheme heterojunction photocatalysts

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

Chinese Journal of Catalysis ›› 2024, Vol. 63: 81-108.DOI: 10.1016/S1872-2067(24)60072-0

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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

Abstract

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

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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Figures/Tables 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]

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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Chalcogenide-based S-scheme heterojunction photocatalysts

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