Novel Z-Scheme ZnIn2S4-based photocatalysts for solar-driven environmental and energy applications: Progress and perspectives

doi:10.1016/j.jmst.2021.01.051

Abstract

Abstract:

Benefiting from strong redox ability, improved charge transport, and enhanced charge separation, Z-scheme heterostructures of ZnIn₂S₄ based photocatalysts have received considerable interest to tackle energy needs and environmental issues. The present review highlights the properties of ZnIn₂S_4, which make it a promising photocatalyst, and a suitable combination with oxidation photocatalyst to form Z-scheme, leading to improve their photocatalytic properties dramatically. As the central part of this review, various types of Z-scheme heterojunction developed recently based on ZnIn₂S₄ and their application in pollutant degradation, water splitting, CO₂ reduction, and toxic metals remediation. Some analytical techniques to detect or trap the active radical and study the charge separation and lifetime of charge carriers in these Z-schemes are highlighted. This review offers its readers a broad optical window for the structural architecture of ZnIn₂S₄-based Z-schemes, photocatalytic activity, stability, and their technological applications. Finally, we discuss the challenges and opportunities for further development on Z-Scheme ZnIn₂S₄-based photocatalysts toward energy and environmental applications based on the recent progress.

Key words: ZnIn₂S₄, Z-scheme photocatalyst, Charge transfer mechanism, Pollutant degradation, Environmental remediation

Yogesh Kumar, Rohit Kumar, Pankaj Raizada, Aftab Aslam Parwaz Khan, Quyet Van Le, Pardeep Singh, Van-Huy Nguyen. Novel Z-Scheme ZnIn₂S₄-based photocatalysts for solar-driven environmental and energy applications: Progress and perspectives[J]. J. Mater. Sci. Technol., 2021, 87: 234-257.

Figures/Tables 20

Fig. 1. (a) Basic mechanism of semiconductor photocatalysis (b) Bar graph depicting Scopus data from 2008 to Sept. 2020, using the keywords “ZnIn2S4+ photocatalysis”.

Fig. 2. Crystal structure of ZnIn2S4 polymorphs: (a) hexagonal; (b) cubic; (c) rhombohedral. Reprinted with permission from Elsevier (Licence No. 4,914,631,012,156) [53].

Fig. 3. (a) Growth mechanism of ZnIn2S4 in different morphologies with different templates; (b) Mechanism of MG adsorption on the surface of ZIS. Reproduced with permission from RSC (licence no. 1,065,197-1) [74].

Fig. 4. The density of states in ZnIn2S4 (a) hexagonal phase; (b) Cubic phase and the calculated band structure of ZnIn2S4 in (c) hexagonal phase (d) cubic phase. Reproduced with permission from RSC (Licence no. 1,065,200-1) [65].

Fig. 5. SEM image of ZnIn2S4 under different magnifications (a) low (b, c) high (d) Mechanism of microspheres of ZnIn2S4. Reprinted with permission from Ref. [76] Copyright 2008 American Chemical Society.

Fig. 6. SEM images of ZIS synthesised by microwave method at temperature (a) 100 °C (b) 120 °C (c) 140 °C (d) 160 °C (e) 180 °C (f) 195 °C. Reprinted with permission from Elsevier (Licence No. 4,914,681,325,601) [66].

Fig. 7. Schematic representation of charge transfers in conventional heterojunctions (a) Type-I (b) Type-II (c) Type-III (d) Reprinted with permission from Elsevier (Licence no. 4,923,610,251,257) [110].

Fig. 8. Schematic representation of charge transfers in (a) traditional Z-scheme (b) All solid-state Z-scheme (c) Direct Z-scheme. Reprinted with permission from Elsevier (Licence no. 4,923,610,251,257) [110].

Fig. 9. (a) Scheme for the fabrication of ZnIn2S4-Au-TiO2 by chemical deposition method; (b) Plot of hydrogen evolution with time for optimising ZnIn2S4 loading; (c) Rate of gases evolution with optimised photocatalyst; (d) Plot of H2 and O2 evolution with for optimising Au mass ratio; (e) Comparison of photocatalytic activity for optimised photocatalyst with various photocatalysts. Reprinted with permission from Elsevier (Licence No. 4,914,690,173,422) [130].

Fig. 10. (a) Photocatalytic activity for three cycles; (b) Proposed direct Z-scheme mechanism for water splitting over 0.5 %PtS-20 %ZIS/WO3-3.0 %MnO2 under visible light irradiation. Reprinted with permission from Elsevier (Licence No. 4,914,690,422,457) [119]; (c) Proposed direct Z-scheme mechanism for water splitting over ZIS/LaNiO3 under visible light irradiation. Reprinted with permission from Elsevier (Licence No. 4,914,701,316,108) [134].

Fig. 11. (a) Variation of PL intensity with irradiation time on dispersing ZnIn2S4/VS2 in terephthalic acid (b) Variation fluorescence intensity with time of bare ZnIn2S4 and ZnIn2S4/VS2 (c) Proposed direct Z-scheme mechanism for ZIS/VS2 under visible light irradiation. Reprinted with permission from John Wiley & Sons (Licence No. 4,914,741,383,204) [136]. (d) ESR spectra of DMPO adducts with TiO2, ZnIn2S4 and 5 ZTin (NH4)2C2O4 aqueous solution and standard ESR spectra of DMPO adducts with (·CO2-+ OH), O··H and ·CO2- in dotted line (e) Schematic illustration of the charge transfer pathway in ZT in two possible photocatalytic systems. Reprinted with permission from Elsevier (Licence No. 4,914,710,045,873) [137].

Fig. 12. (a) ESR spectra of DMPO-O·2- and (b) ESR spectra of DMPO-O·H adducts. (c) Schematic illustration of the charge transfer mechanism in WO3/ ZnIn2S4. Reprinted with permission from Elsevier (Licence No. 4,914,710,379,713) [138].

Fig. 13. (a) The effect of BQ, DMSO and AO on %DE of the photocatalyst (12.5 %wt-Bi2S3/ZnIn2S4; (b) Schematic of degradation mechanism of MB type-II and Z-scheme charge transfer. Reprinted with permission from Elsevier (Licence No. 4,914,710,607,793) [141].

Fig. 14. (a) The PL of bare WO3, ZIS and WO3/ZIS-0.7 (b)TRPL decay spectra of WO3, ZnIn2S4 and WO3/ ZnIn2S4-0.7 on excitation at 340 nm. Reprinted with permission from Elsevier (Licence No. 4,914,711,068,333) [143]. (c) Linear sweep voltammograms of the WO3, ZnIn2S4 and ZIS/WO3-3 modified by ITO in the dark and with 430 nm light. Reprinted with permission from Elsevier (Licence No. 4,914,711,384,918) [144]. (d) EIS Nyquist plot of the bare and composite photocatalysts. Reprinted with permission from Elsevier (Licence No. 4,914,720,550,185) [145].

Table 1 Summary of ZnIn2S4 based Z-Scheme photocatalysts for organic pollutant degradation.

Photocatalyst	Pollutant	Photocatalyst dose	Reaction conditions	Activity	Refs.
ZnIn₂S₄/RGO/BiVO₄	Formaldehyde	1.5 g L^-1	Visible light	22.2 mmol g^-1 h^-1	[26]
WO_2.72/ZnIn₂S₄	Tetracycline hydrochloride (30 mL of 50 mg L^-1)	30 mg	300W Xe lamp (λ > 400 nm); 60 min	97.3 %	[138]
Bi₂S₃/ ZnIn₂S₄	MB (100 mL of 40 ppm)	50 mg	30W Xe lamp; 300 min	95.4 %	[141]
ZnIn₂S₄-g-C₃N₄/BiVO₄	CR (500 mL of 10 mg L^-1)	100 mg	500W tungsten-halogen lamp		[164]
ZnIn₂S₄-g-C₃N₄/BiVO₄	MTZ (500 mL, 10 mg L^-1)	100 mg	500W tungsten-halogen lamp		[164]
BiVO₄/ ZnIn₂S₄	MO (15 mg L^-1)	0.2 g L^-1	LED visible light	86 % (0.00997 min^-1)	[165]
ZnIn₂S₄/Bi₂WO₆	Metronidazole	100 mg	500W tungsten-halogen lamp	56 % 0.00760 min^-1	[166]
ZnIn₂S₄/Bi₂WO₆	(500 mL, 10 mg L^-1)	100 mg	500W tungsten-halogen lamp	56 % 0.00760 min^-1	[166]
TiO₂/ ZnIn₂S₄	Metronidazole	10 mg	350W Xe lamp (λ > 400 nm)	min^-1	[167]
TiO₂/ ZnIn₂S₄	(50 mL, 50 mg L^-1)	10 mg	350W Xe lamp (λ > 400 nm)	min^-1	[167]
ZnIn₂S₄ /TiO₂	MO (50 mL of 20 mg L^-1)	50 mg	350W Xe lamp (λ ≥ 420 nm); 240 min	97 %	[168]
Bi₂MoO₆/ZnIn₂S₄	NO (400 ppm NO, 7% O₂ and N₂ balance gas mixture fed at rate of 100 mL min^-1)	100 mg	350W Xe lamp; 80 min	84.94 %	[169]

Fig. 15. (a) PL spectra of bare ZnIn2S4 and 2.5 %wt-Bi2S3/ZnIn2S4 (b) Photocurrent density versus applied voltage under the dark and visible light irradiation of pure ZnIn2S4 and 12.5 %wt-Bi2S3/ ZnIn2S4 photoelectrodes. Reprinted with permission from Elsevier (Licence No. 4,914,710,607,793) [141].

Fig. 16. (a-c) Optimisation using degradation study with CR using various photocatalyst; (d) Degradation of MTZ using optimised photocatalyst; (e-h) Schematic illustration of the probable electron transfer mechanism. Reprinted with permission from Elsevier (Licence No. 4,914,720,733,162) [164].

Fig. 17. (a) Rate of hydrogen evolution for samples for two cycles; (b) PL spectra of samples; (c) EIS Nyquist plots of the bare and composite photocatalysts (d) proposed type-II mechanism of binary CN/ ZnIn2S4; and (e) Z-Scheme for CN/C/ ZnIn2S4 ternary nanocomposite. Reproduced with permission from RSC (licence no. 1,065,023-1) [131].

Fig. 18. (a) Amount of hydrogen evolved with irradiation time for bare and nanocomposites (b) comparison of the rate of hydrogen evolved for various samples (c) Photocurrent response with an irradiation time of WO3, ZnIn2S4 and WO3/ ZnIn2S4-2 (d) EIS Nyquist plots of WO3, ZnIn2S4and WO3/ ZnIn2S4-2 (e, f) Schematic illustration of H2 evolution over WO3/ZnIn2S4 via type-II and Z-scheme charge transfer. Reproduced with permission from RSC (licence no. 1,065,204-1) [174].

Table 2 Summary of ZnIn2S4 based Z-Scheme photocatalysts for hydrogen evolution.

Photocatalyst	Co-catalyst	Sacrificial reagent	Light Source	Optimal H₂ evolution or photocurrent	Enhancement factor to bare ZnIn₂S₄	Refs.
ZnIn₂S₄/LaNiO₃	-	TEOA	300W Xe lamp, λ > 420 nm	1600 μmol g^-1 h^-1	3	[134]
ZnIn₂S₄/VS₂	-	-	300 W tungsten halogen lamp	∼56 μA cm^-2	18	[136]
ZnIn₂S₄/Nb₂O₅	Pt	TEOA	-	6026 μmol g^-1 h^-1		[177]
WO₃/ZnIn₂S₄	Pt	Na₂SO₃/Na₂S	300 W xenon arc lamp λ ≥ 420 nm	1945.88 μmol g^-1 h^-1	7.9	[176]
2D/2D WO₃/ZnIn₂S₄	-	0.35 M Na₂S and 0.25 M Na₂SO₃	300 W xenon arc lamp λ ≥ 420 nm	2202.9 μmol g^-1 h^-1	5.2	[174]
UiO-66- (COOH)₂/ZnIn₂S₄	MoS2	0.50 M Na₂SO₃ and 0.70 M Na₂S	300W Xe	18.794 mmol g^-1 h^-1	15	[145]
PtS-ZnIn₂S₄/WO₃-MnO₂	PtS, MnO₂	-	300W Xe lamp	5.94 × 2.5 μmol g^-1 h^-1	-	[119]
2D/2D NiS/Vs-ZnIn₂S₄/WO₃	-	lactic acid	300W Xe lamp, λ > 400 nm	11.09 mmol g^-1 h^-1	29.6	[178]
WO₃/ZnIn₂S₄	-	TEOA	300W Xe lamp, λ > 400 nm	3900 μmol g^-1 h^-1	5.13	[143]
ZnIn₂S₄/Er³⁺:Y₃Al₅O₁₂@ZnTiO₃/CaIn₂S₄	-	Acid Orange Ⅱ	300 W Xe lamp	358.2 mmol g^-1	-	[25]
ZnIn₂S₄-RGO-RuO₂/BiVO₄	Pt	-	-	649.3 μmol g^-1 h^-1	-	[179]
ZnIn₂S₄-Au-TiO₂	-	NA	300W Xe lamp	186.3 μmol g^-1 h^-1	-	[130]
g-C₃N₄/nanocarbon/ZnIn₂S₄	-	0.5 M Na₂S and 0.5 M Na₂SO₃.	Four low power UV-LEDs (3 W, 420 nm)	50.32 μmol h^-1	3.4	[131]
CdS/QDs/ZnIn₂S₄	-	Lactic acid	300W Xe lamp	2107.5 μmol g^-1 h^-1	62	[180]

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Novel Z-Scheme ZnIn₂S₄-based photocatalysts for solar-driven environmental and energy applications: Progress and perspectives

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