Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in-situ characterization

doi:10.1016/S1872-2067(23)64444-4

Chinese Journal of Catalysis ›› 2023, Vol. 49: 42-67.DOI: 10.1016/S1872-2067(23)64444-4

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Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in-situ characterization

Haibo Zhang^a^,^b, Zhongliao Wang^b^,^*(), Jinfeng Zhang^b^,^*(), Kai Dai^a^,^b^,^*()

^aKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal University, Huaibei 235000, Anhui, China
^bAnhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000, Anhui, China

Received:2023-03-12 Accepted:2023-04-18 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: daikai940@chnu.edu.cn (K. Dai), wangzl@chnu.edu.cn (Z. Wang), jfzhang@chnu.edu.cn (J. Zhang).
About author:Zhongliao Wang received his B.A. degree from Huaibei Normal University (China) in 2015, Master degree under the supervision of Prof. Kai Dai from Huaibei Normal University in 2018, and Ph.D. degree under the supervision of Prof. Jiaguo Yu from State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology (China) in 2021. His research interests mainly focus on the controllable synthesis of photocatalysts, CO₂ photoreduction, overall utilization of photogenerated charge, photocatalytic mechanism research, and DFT calculation.
Jinfeng Zhang (Huaibei Normal University) received his M.S. degree from Ningxia University (China) in 2007, and Ph.D. degree from Wuhan University of Technology (China) in 2016. He carried out postdoctoral research in Wuhan University of Technology from 2016 to 2018. Since the end of 2007, he has been working in Huaibei Normal University. His research interests mainly focus on semiconductor photocatalysis. As the first author or corresponding author, he has published more than 50 SCI papers, including 3 hot paper of ESI and 12 highly cited papers of ESI. He has mainly undertaken more than 6 research projects, including the National Natural Science Foundation of China, China Postdoctoral Science Foundation and Anhui Provincial Department of Education.
Kai Dai (Huaibei Normal University) 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 at 2007, and then in Huaibei Normal University at 2010. He is a recipient of National Science Foundation for Distinguished Young Scholars of Anhui Province (2018) and 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 140 peer-reviewed papers, including 9 hot paper of ESI and 22 highly cited papers of ESI. He was invited as a member of the 5^th and 6^th editorial board of Acta Phys.-Chim. Sin.
Supported by:
National Natural Science Foundation of China(22278169);National Natural Science Foundation of China(51973078);Excellent Scientific Research and Innovation Team of Education Department of Anhui Province(2022AH010028);Major Projects of Education Department of Anhui Province(2022AH040068);Key Foundation of Educational Commission of Anhui Province(2022AH050396)

Abstract

Abstract:

Semiconductor photocatalysis is a new sustainable development technology that has demonstrated remarkable potential in the fields of energy-production and environmental-protection. However, a single photocatalyst usually does not possess both strong redox and fast charge-separation properties, greatly limiting photocatalysis efficiency. Heterojunction photocatalysts can perfectly solve this problem by providing multiple reactive sites and fast charge separation and migration, elevating photocatalytic efficiency to a new higher level. Metal sulfides are a family of compounds composed of metals and sulfur (e.g., CdS, CuS, MoS₂, In₂S₃, ZnIn₂S₄, and Zn_xCd_1-_xS) that are preferred choices for heterojunction photocatalysts due to their narrow bandgaps, broad visible-light absorption ranges, and convenient preparation methods. This review article introduces the characteristics of metal sulfides, summarizes methods for their synthesis, and discusses various types of metal-sulfide-based heterojunctions. The use of such photocatalysts in energy and environmental-remediation applications is subsequently discussed. In addition, the roles of charge separation and transfer in heterojunction photocatalysts are demonstrated using in-situ characterization techniques. Finally, we discuss some application prospects and challenges concerning metal-sulfide-based heterojunction photocatalysts.

Key words: Photocatalysis, Metal sulfide, Heterojunction, Charge separation, Application

Haibo Zhang, Zhongliao Wang, Jinfeng Zhang, Kai Dai. Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in-situ characterization[J]. Chinese Journal of Catalysis, 2023, 49: 42-67.

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Figures/Tables 27

Fig. 1. Band positions of some typical oxides and metal sulfides.

Fig. 2. Advantages of metal sulfides in photocatalysis applications.

Fig. 3. Basic steps involved in a photocatalytic reaction.

Fig. 4. (a) Schematic depicting the synthesis of a ZnIn2S4-CdS composite; (b) Process for preparing the Cu2?xS-MoX2 (X = S or Se) heterostructure. (c) Procedure for preparing a ternary CdIn2S4/CNFs/Co4S3 composite. (d) Schematic depicting the syntheses of 1D Cd1?xZnxS@O-MoS2 and Cd1?xZnxS@O-MoS2/NiOx nanohybrids. (a) Reprinted with permission from Ref. [62]. Copyright 2020, Springer Nature. (b) Reprinted with permission from Ref. [63]. Copyright 2017, American Chemical Society. (c) Reprinted with permission from Ref. [66]. Copyright 2021, Elsevier. (d) Reprinted with permission from Ref. [67]. Copyright 2019, John Wiley and Sons.

Fig. 5. Architectural designs of conventional heterojunction photocatalysts with various junctions. (a) Schottky junction; (b) type II; (c) direct Z-scheme; (d) S-scheme heterojunctions. Φ: Work function. Ef: Fermi level. RP: Reduction photocatalyst. OP: Oxidation photocatalyst.

Fig. 6. Contact potential differences (a) and work functions (b) for ZCS, ZCS/Pt, and Pt. (c) Schematic showing Schottky-junction formation in ZCS/Pt and the charge-transfer mechanism. Reprinted with permission from Ref. [70]. Copyright 2021, John Wiley and Sons.

Fig. 7. (a) Photocatalytic H2-evolution and AQE data for 4 mol% Ni0.1Co0.9P-Zn0.5Cd0.5S. (b) Fermi levels and work functions of Ni2P, CoP, and Ni0.1Co0.9P. (c) Diagram showing band-edge positions before and after contact between Zn0.5Cd0.5S and Ni0.1Co0.9P. Reprinted with permission from Ref. [71]. Copyright 2019, Elsevier.

Fig. 8. (a) Time-yield plots for ZnIn2S4, MNZIS-X, MNs, and a MNs+ZnIn2S4 physical mixture. (b) Cyclic H2-evolution experiments with MNZIS-4. Calculated average potential profile along the Z axis of MNs (c) and ZnIn2S4 (d). (e) Schematic showing the band structure of MNZIS-4. Reprinted with permission from Ref. [72]. Copyright 2020, John Wiley and Sons.

Fig. 9. (a) Schematic showing of the fabrication of PBA/CdS (CP) and an active hybrid photocatalyst composed of NiS and CdS (CN). Photocatalytic H2 evolution amount from (b) CdS, CP-1, CP-2, CP-3, CdS/NiS, and Ni-Co PBA in the 0.35 mol L?1 Na2S and 0.25 mol L?1 Na2SO3 and (c) CdS, CP-2, CN-2 and CdS/NiS in the non-sulfur 10 vol % LA solution. (d) Proposed photocatalytic mechanisms over CP-2 and CN-2. Reprinted with permission from Ref [74]. Copyright 2022, American Chemical Society.

Fig. 10. (a) Photocatalytic H2-evolution over a CdS hexagonal pyramid, CdS nanorod, and CdS nanoparticles. (b) H2-production photostability of a CdS hexagonal pyramid under visible light over 100 h. (c) SEM image of the facet-selective photodeposition of Pt particles on the CdS hexagonal pyramid and a schematic diagram showing the proposed charge-carrier transfer and H2-evolution mechanism on the CdS hexagonal pyramid. Reprinted with permission from Ref. [76]. Copyright 2021, Elsevier.

Fig. 11. Femtosecond TA traces for ZnIn2S4 (a) and WO3?x/ZnIn2S4 (b). (c) Photocatalytic H2-evolution over WO3?x/ZnIn2S4 when irradiated with light; (d) DFT-calculated GH* values and adsorption configurations for the ZnIn2S4, WO3?x, and WO3?x/ZnIn2S4 systems. Reprinted with permission from Ref. [80]. Copyright 2021, Royal Society of Chemistry.

Fig. 12. Pseudocolor plots and transient absorption spectra recorded at indicated delay times when excited at 350 nm: TiO2 (a,c) and TiO2/Ce2S3 (TC5) (b,d). (e) Corresponding transient absorption kinetic traces for TiO2 and TC5 at 645 nm over 100 ps. (f) Schematic showing the photocatalytic mechanism over TiO2/Ce2S3. Reprinted with permission from Ref. [87]. Copyright 2021, American Chemical Society.

Fig. 13. (a) Photocatalytic H2-evolution activities of catalysts. PL spectra (b) and time-resolved PL spectra (c) of SCN, NMS and 19.3%-NMS/SCN. Electrostatic potentials of the SCN (001) (d) and NMS (002) (e) surfaces. (f) Schematic showing the photocatalytic mechanism over NMS/SCN. Reprinted with permission from Ref. [89]. Copyright 2021, Elsevier.

Fig. 14. Applications of metal-sulfide-based heterojunction photocatalysts.

Table 1 Comparing typical metal-sulfide-based heterojunction systems.

Mechanism	Photocatalyst	Synthesis	Morphology	Light source	Application	Production rate	Ref.
Type II	TiO₂/CdIn₂S₄	simple precipitation method	microspheres	sunlight	H₂ evolution	7.86 mmol h⁻¹ g⁻¹	[75]
Type II	α-S/CdS	facile solvent-evapora- tion-deposition-precipitation method	α-S nanoparticles load on the surfaces of CdS nanorods	visible light, λ > 420 nm	H₂ evolution	10.01 mmol h⁻¹ g⁻¹ after 3 h of irradiation	[100]
Type II	CdS/ TpPa-1-COF	ion adsorption	microspheres	300 W Xe lamp, λ ≥ 420 nm	NH₃ production	241 mmol g⁻¹ h⁻¹	[101]
Type II	CdS/ZnIn₂S₄	hydrothermal synthesis	rod-covered layer nanosheets	300 W Xe lamp, λ = 420 nm	H₂ evolution	113 μmol h⁻¹	[102]
Type II	CdS/NiS	ion exchange	hollow cubes	100 mW cm⁻² LED, 420 nm	H₂ evolution	66.3 mmol g⁻¹ h⁻¹	[74]
Type II	Pt-CdS/ g-C₃N₄-MnO_x	mixing heating	nanorods	300 W Xe lamp with a 400 nm cutoff filter	H₂ evolution	9.244 μmol h⁻¹	[103]
Type II	ZnIn₂S₄/BiPO₄	hydrothermal synthesis	dandelion-like flowers	300 W Xe lamp	degradation of tetracycline	degraded 84% tetracycline (TC, 40 mg L⁻¹) in 90 min	[104]
Z-scheme	Sv-ZnIn₂S₄/ MoSe₂	assisted hydrothermal method	flower-like microspheres	300 W Xe Lamp with a 420 nm cut-off filter	H₂ evolution	63.21 mmol g⁻¹ h⁻¹	[32]
Z-scheme	ZnIn₂S₄@MoO₃	in-site growth	nanowires grown on nanosheets	300 W Xe Lamp with a λ > 420 nm cut-off filter	degradation of TC-HCl	94.5% in 90 min (TC-HCl 100 mL, 30 mg L⁻¹)	[84]
Z-scheme	AgVO₃/ZnIn₂S₄	two-step hydrothermal process.	nanosheets grown on flower-like microspheres	250 W Xe lamp with a λ > 420 nm cut of filter	degradation of Cr(VI) to Cr(III)	100% in 25 min (K₂Cr₂O₇, 20 mg L⁻¹))	[105]
Z-scheme	Mo₂C/ MoS₂/In₂S₃	one-pot solvothermal synthesis	porous flower-like microspheres	350 W Xe Lamp with a 420 nm cut-off filter	degradation of Cr(VI) to Cr(III)	K₂Cr₂O₇, 40 mg L⁻¹	[106]
Z-scheme	WO_3‒_x/ZnIn₂S₄	oil bath heating	ultrathin nanosheets	300W Xe lamp with a 400 nm cutoff filter	H₂ evolution	20.957 mmol g⁻¹ h⁻¹	[80]
Z-scheme	Sn-In₂O₃/ In₂S₃	in-situ gas-phase vulcanization	nanowire structures	300 W Xe lamp with a 420 nm cutoff filter	reduction of CO₂ to CH₄ and CO	0.41 and 1.03 μmol cm⁻² h⁻¹	[83]
Z-scheme	CdS/MOF-5	hydrothermal method	nanoparticles grows on the surfaces of rods	300 W Xe lamp with a 420 nm cutoff filter	H₂ evolution	11.62 mmol h⁻¹ g⁻¹	[107]
S-scheme	CdS/pyrene-alt-triphenylamine (CP)	electrostatic interaction	nanosheets	350 W Xe arc lamp with 420 nm cut off filter	H₂ evolution	9.28 mmol h⁻¹ g⁻¹	[93]
S-scheme	S-doped g-C₃N₄/ N-doped MoS₂	high temperature calcination	willow-leaf-like nanobelts	300 W Xe lamp	H₂ evolution	658.5 μmol g⁻¹ h⁻¹	[89]
S-scheme	COF/CdS	precipitation method	block-like cubes	300 W Xe lamp with a 420 nm cut off filter	H₂ evolution	8670 μmol g⁻¹ h⁻¹	[108]
S-scheme	MoS₂/CoAl LDH	simple Hydrothermal method	3D carnation-like structure	300 W Xe lamp	H₂ evolution	17.1 μmol g⁻¹ h⁻¹	[109]
S-scheme	CdS/Bi₂WO₆	in-situ hydrothermal method	microspheres grown on monolayer nanosheets	300 W Xe lamp	degradation of C₂H₄	100% in 15 min, 100 ppm C₂H₄	[24]
S-scheme	MoS_x/MnWO₄	solvothermal method	nanorods dispersed on amorphous	300 W Xe lamp (λ > 420 nm)	O₂ evolution	267.8 μmol g⁻¹	[110]
Schottky junction	Mn_0.2Cd_0.8S/Ti₃C₂	in-situ solvothermal method	nanorods	300 W Xe lamp (λ > 420 nm)	H₂ evolution	15.73 mmol g⁻¹h⁻¹	[111]
Schottky junction	Ni-P/ZnS	in-situ photo- deposition	nanospheres	300 W Xe lamp with a 420 nm cut-off filter	H₂ evolution	69.92 μmol g⁻¹ h⁻¹	[112]
Schottky junction	CdS/Nb₂CT_x	electrostatically driven self-assembly	1D nanorods grown on nanosheets	300 W Xe lamp (λ ≥ 420 nm)	H₂ evolution	5.3 mmol g⁻¹ h⁻¹	[113]

Table 1 Comparing typical metal-sulfide-based heterojunction systems.

Mechanism	Photocatalyst	Synthesis	Morphology	Light source	Application	Production rate	Ref.
Type II	TiO₂/CdIn₂S₄	simple precipitation method	microspheres	sunlight	H₂ evolution	7.86 mmol h⁻¹ g⁻¹	[75]
Type II	α-S/CdS	facile solvent-evapora- tion-deposition-precipitation method	α-S nanoparticles load on the surfaces of CdS nanorods	visible light, λ > 420 nm	H₂ evolution	10.01 mmol h⁻¹ g⁻¹ after 3 h of irradiation	[100]
Type II	CdS/ TpPa-1-COF	ion adsorption	microspheres	300 W Xe lamp, λ ≥ 420 nm	NH₃ production	241 mmol g⁻¹ h⁻¹	[101]
Type II	CdS/ZnIn₂S₄	hydrothermal synthesis	rod-covered layer nanosheets	300 W Xe lamp, λ = 420 nm	H₂ evolution	113 μmol h⁻¹	[102]
Type II	CdS/NiS	ion exchange	hollow cubes	100 mW cm⁻² LED, 420 nm	H₂ evolution	66.3 mmol g⁻¹ h⁻¹	[74]
Type II	Pt-CdS/ g-C₃N₄-MnO_x	mixing heating	nanorods	300 W Xe lamp with a 400 nm cutoff filter	H₂ evolution	9.244 μmol h⁻¹	[103]
Type II	ZnIn₂S₄/BiPO₄	hydrothermal synthesis	dandelion-like flowers	300 W Xe lamp	degradation of tetracycline	degraded 84% tetracycline (TC, 40 mg L⁻¹) in 90 min	[104]
Z-scheme	Sv-ZnIn₂S₄/ MoSe₂	assisted hydrothermal method	flower-like microspheres	300 W Xe Lamp with a 420 nm cut-off filter	H₂ evolution	63.21 mmol g⁻¹ h⁻¹	[32]
Z-scheme	ZnIn₂S₄@MoO₃	in-site growth	nanowires grown on nanosheets	300 W Xe Lamp with a λ > 420 nm cut-off filter	degradation of TC-HCl	94.5% in 90 min (TC-HCl 100 mL, 30 mg L⁻¹)	[84]
Z-scheme	AgVO₃/ZnIn₂S₄	two-step hydrothermal process.	nanosheets grown on flower-like microspheres	250 W Xe lamp with a λ > 420 nm cut of filter	degradation of Cr(VI) to Cr(III)	100% in 25 min (K₂Cr₂O₇, 20 mg L⁻¹))	[105]
Z-scheme	Mo₂C/ MoS₂/In₂S₃	one-pot solvothermal synthesis	porous flower-like microspheres	350 W Xe Lamp with a 420 nm cut-off filter	degradation of Cr(VI) to Cr(III)	K₂Cr₂O₇, 40 mg L⁻¹	[106]
Z-scheme	WO_3‒_x/ZnIn₂S₄	oil bath heating	ultrathin nanosheets	300W Xe lamp with a 400 nm cutoff filter	H₂ evolution	20.957 mmol g⁻¹ h⁻¹	[80]
Z-scheme	Sn-In₂O₃/ In₂S₃	in-situ gas-phase vulcanization	nanowire structures	300 W Xe lamp with a 420 nm cutoff filter	reduction of CO₂ to CH₄ and CO	0.41 and 1.03 μmol cm⁻² h⁻¹	[83]
Z-scheme	CdS/MOF-5	hydrothermal method	nanoparticles grows on the surfaces of rods	300 W Xe lamp with a 420 nm cutoff filter	H₂ evolution	11.62 mmol h⁻¹ g⁻¹	[107]
S-scheme	CdS/pyrene-alt-triphenylamine (CP)	electrostatic interaction	nanosheets	350 W Xe arc lamp with 420 nm cut off filter	H₂ evolution	9.28 mmol h⁻¹ g⁻¹	[93]
S-scheme	S-doped g-C₃N₄/ N-doped MoS₂	high temperature calcination	willow-leaf-like nanobelts	300 W Xe lamp	H₂ evolution	658.5 μmol g⁻¹ h⁻¹	[89]
S-scheme	COF/CdS	precipitation method	block-like cubes	300 W Xe lamp with a 420 nm cut off filter	H₂ evolution	8670 μmol g⁻¹ h⁻¹	[108]
S-scheme	MoS₂/CoAl LDH	simple Hydrothermal method	3D carnation-like structure	300 W Xe lamp	H₂ evolution	17.1 μmol g⁻¹ h⁻¹	[109]
S-scheme	CdS/Bi₂WO₆	in-situ hydrothermal method	microspheres grown on monolayer nanosheets	300 W Xe lamp	degradation of C₂H₄	100% in 15 min, 100 ppm C₂H₄	[24]
S-scheme	MoS_x/MnWO₄	solvothermal method	nanorods dispersed on amorphous	300 W Xe lamp (λ > 420 nm)	O₂ evolution	267.8 μmol g⁻¹	[110]
Schottky junction	Mn_0.2Cd_0.8S/Ti₃C₂	in-situ solvothermal method	nanorods	300 W Xe lamp (λ > 420 nm)	H₂ evolution	15.73 mmol g⁻¹h⁻¹	[111]
Schottky junction	Ni-P/ZnS	in-situ photo- deposition	nanospheres	300 W Xe lamp with a 420 nm cut-off filter	H₂ evolution	69.92 μmol g⁻¹ h⁻¹	[112]
Schottky junction	CdS/Nb₂CT_x	electrostatically driven self-assembly	1D nanorods grown on nanosheets	300 W Xe lamp (λ ≥ 420 nm)	H₂ evolution	5.3 mmol g⁻¹ h⁻¹	[113]

Fig. 15. (a) Comparing photocatalytic H2-generation performance of SNO, CdS-D, X%SNO/CdS-D, 1%NiP-10%SNO/CdS-D, and 1%Pt- 10%SNO/CdS-D. (b) Photocatalytic H2-generation recyclabilities of SNO, CdS-D, 10%SNO/CdS-D, 1%NiP-10%SNO/CdS-D, and 1%Pt-10%SNO/ CdS-D. (c) Photocatalytic mechanism of Ni2P-SNO/CdS-D. Reprinted with permission from Ref. [126]. Copyright 2021, Elsevier.

Fig. 16. (a) H2-evolution rates of various catalysts. (b) Wavelength-dependent apparent quantum yield (AQY) of Sv-ZIS/5.0MoSe2; (c) SPV spectra of Sv-ZIS, MoSe2, and Sv-ZIS/MoSe2. (d) EPR spectra of DMPO-?O2? for Sv-ZIS/MoSe2 in methanol. Reprinted with permission from Ref. [32]. Copyright 2021, Springer Nature.

Fig. 17. (a) Depicting the formation of CdS/TiO2 HS. (b) Photocatalytic CO2-reduction activity testing with catalysts irradiated with full-spectrum light. (c) CdS/TiO2 HS 1:1 stability testing. In-situ DRIFTS spectra of surface-adsorbed carbonate species (d) and intermediates (e) in the photocatalytic CO2-reduction over CdS/TiO2 HS (0-60 min in the dark and 60-120 min under full-spectrum light). Reprinted with permission from Ref. [97]. Copyright 2020, Elsevier.

Fig. 18. (a) Photocatalytic CO2-reduction activities of ZnS, ZIS, ZnS/ZIS-X, and Phys. Mix. (b) Acetaldehyde formation rate (inset: shows stability data for ZnS/ZIS-3). (c) Schematic illustrating lattice mismatch and the strain effect between the cubic ZnS and hexagonal ZIS phases in ZnS/ZIS-3. (d) Direct Z-scheme for the ZnS/ZIS (n-n+) heterojunction in ZnS/ZIS-3. Reprinted with permission from Ref. [147]. Copyright 2022, Elsevier.

Fig. 19. (a) Photocatalytic degradation performance of WO3, N-WO3, and N-WO3/Ce2S3. (b) Cycling performance of N-WO3/Ce2S3 NBs during the photocatalytic degradation of phenol; ESR spectra of DMPO-?O2? (c) and DMPO-?OH (d) acquired for N-WO3/Ce2S3 NBs. Reprinted with permission from Ref. [164]. Copyright 2019, John Wiley and Sons.

Fig. 20. (a,b) FDTD electric-field distributions at a Ru/CoSx nanoparticle; (c) NH3-production rates for CN and Vs-CoS/Ru-Vs-CoS/CN. (d) AQEs (blue dots) for N2 fixation over Ru-Vs-CoS/CN. (e) N2RR pathway at the Ru (001)/CoSx(101) interface (optimized atomic structures are shown). Reprinted with permission from Ref. [171]. Copyright 2020, John Wiley and Sons.

Fig. 21. BH4+ (a) and NO3? (b) photocatalytic yields over WO3, CdS, and WO3/CdS. (c,d) EPR radical-trapping spectra for hydroxyl radicals (?OH) and superoxide radicals (?O2?). (e) Diagram showing photoelectron transfer from WO3 to CdS and the subsequent simultaneous oxidation and reduction of N2. Reprinted with permission from Ref. [172]. Copyright 2022, John Wiley and Sons.

Fig. 22. Escherichia coli (a) and Bacillus subtilis (b) regrowth curves in LB broth at 37 °C determined by the standard plate-counting method after treatment with various samples. (c) Scavenging experiments during photocatalytic disinfection with the CuS/Cu9S5 photocatalyst. (d) Photocatalytic bacterial inactivation mechanism under NIR light. Reprinted with permission from Ref. [26]. Copyright 2022, Elsevier.

Fig. 23. High-resolution Ti 2p (a) and Cd 3d (b) XPS profiles for TiO2/CdS in the dark or when irradiated with a 365-nm LED (UV-TiO2/CdS). (c) Schematic showing the charge-carrier migration mechanism. Reprinted with permission from Ref. [182]. Copyright 2018, John Wiley and Sons.

Fig. 24. EPR spectra of DMPO-?O2? in methanol (a) and DMPO-?OH in deionized H2O (b). KPFM surface potential images in the dark (c) and when irradiated (d). Reprinted with permission from Ref. [184]. Copyright 2022, Royal Society of Chemistry.

Fig. 25. (a,b) Photocatalytic H2- and PhCHO-production rates. (c) Photocatalytic H2-evolution activities of NP/ZIS-O using PhCH2OH, TEOA, Na2SO3/Na2S, and pure H2O. (d,e) In-situ EPR spectra of TEMPO in the presence of photogenerated holes and electrons and various additives over NP/ZIS-O. (f) EPR detection of the ?CH(OH)Ph radical by spin-trapping. Reprinted with permission from Ref. [186]. Copyright 2021, John Wiley and Sons.

Fig. 26. (a) Photocatalytic CO-production over α-MnS, X%α-MnS/Bi2MoO6 (X%M/BMO), and Bi2MoO4. (b) GC-MS 12CO and 13CO traces. (c) In-situ FT-IR spectra for the absorption and activation of CO2 on the Bi-5%M/BMO photocatalyst. (d) FT-IR spectra of γ-MnS and α-MnS. Reprinted with permission from Ref. [187]. Copyright 2021, Elsevier.

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Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in-situ characterization

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