A review on ZnO-based S-scheme heterojunction photocatalysts

doi:10.1016/S1872-2067(23)64502-4

Chinese Journal of Catalysis ›› 2023, Vol. 52: 32-49.DOI: 10.1016/S1872-2067(23)64502-4

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A review on ZnO-based S-scheme heterojunction photocatalysts

Zicong Jiang^a, Bei Cheng^a, Liuyang Zhang^b, Zhenyi Zhang^c, Chuanbiao Bie^b^,^*()

^aState Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, Hubei, China
^bLaboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, Hubei, China
^cKey Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission, Key Laboratory of Photosensitive Materials and Devices of Liaoning Province, School of Physics and Materials Engineering, Dalian Minzu University, Dalian 116600, Liaoning, China

Received:2023-07-11 Accepted:2023-08-09 Online:2023-09-18 Published:2023-09-25
Contact: *E-mail: biechuanbiao@cug.edu.cn (C. Bie).
About author:Chuanbiao Bie (Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences) received his Ph.D. from Wuhan University of Technology in 2021. He is now a postdoctoral researcher at China University of Geosciences (Wuhan). His research interests focus on semiconductor photocatalysis, including photocatalytic H₂ evolution, H₂O₂ production, CO₂ reduction, and organic synthesis.
Supported by:
National Key Research and Development Program of China(2022YFB3803600);National Key Research and Development Program of China(2022YFE0115900);National Natural Science Foundation of China(22278383);National Natural Science Foundation of China(52073223);National Natural Science Foundation of China(22278324);National Natural Science Foundation of China(51932007);National Natural Science Foundation of China(22238009);National Natural Science Foundation of China(22261142666);National Natural Science Foundation of China(U1905215);National Natural Science Foundation of China(22202187);Natural Science Foundation of Hubei Province of China(2022CFA001);National Postdoctoral Program for Innovative Talents(BX2021275);China Postdoctoral Science Foundation(2022M712957)

Abstract

Abstract:

ZnO, a typical photocatalyst, has aroused great attention due to its nontoxicity, biocompatibility, and earth abundance. However, its performance is hindered by insufficient light absorption capacity, limited reduction ability, and fast recombination of photogenerated carriers (PC). To overcome these challenges, the construction of ZnO-based S-scheme heterojunctions has emerged as an effective solution, enabling the simultaneous realization of spatially separated PC and enhanced redox abilities. Given the notable progress in ZnO-based S-scheme heterojunctions, it is crucial to review the current achievements and provide guidance for future development. This paper presents the development and representative characterization methods of S-scheme heterojunctions, outlines the design principles of ZnO-based S-scheme heterojunctions, and exemplifies the applications of ZnO-based S-scheme heterojunctions in environmental remediation, hydrogen evolution, H₂O₂ production, and CO₂ reduction. Finally, the significant challenges and potential improvements for ZnO-based S-scheme heterojunction photocatalysts are proposed.

Key words: Photocatalysis, Step-scheme heterojunction, Zinc oxide, Interfacial internal electric field, Photocatalytic application

Zicong Jiang, Bei Cheng, Liuyang Zhang, Zhenyi Zhang, Chuanbiao Bie. A review on ZnO-based S-scheme heterojunction photocatalysts[J]. Chinese Journal of Catalysis, 2023, 52: 32-49.

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Figures/Tables 19

Fig. 1. (a) Spectral distribution of solar light. (b) Microscopic view of photocatalytic reactions over ZnO semiconductor.

Fig. 2. Proposed carrier transfer pathway in type-II heterojunction and its problems.

Fig. 3. Assumed (a) and thermodynamically favorable (b) PE transfer pathway in TZS. Challenges arising from the Brownian motion and thermal motion (c) and redox couple ions transfer from P1 to P2 in TZS (d).

Fig. 4. Assumed (a) and thermodynamically favorable (b) PE transfer path in ASSZH. Band diagrams of CdS, TiO2, and Au before contact (c) and after contact (d).

Fig. 5. Schematic illustrations of an S-scheme heterojunction. (a) The staggered band configurations of OS and RS before their contact. (b) The formation of IIEF after their contact. (c) The migration route of PE under light irradiation.

Fig. 6. Band alignments of typical reduction and oxidation photocatalysts for constructing ZnO-based S-scheme heterojunctions.

Fig. 7. Different types of ZnO-based S-scheme heterojunctions. (a) n-n junction with ZnO as the OS. (b) n-n junction with ZnO as the RS. (c) p-n junction with ZnO as the RS. (d) n-p junction with ZnO as the OS.

Table 1 The summarization of the preparation methods of ZnO-based S-scheme heterojunctions.

Method	Advantage	Disadvantage	Interfacial property
Hydrothermal/solvothermal	controllable size, high crystallinity, easy operation, mass production	required high temperature and pressure, high cost in solvent for solvothermal method	strong interaction and intimate interface
Deposition-precipitation	narrow size distributions of particles, relatively rapid reaction rate	poor reproducibility, required post-calcination treatment	strong interaction and intimate interface
Self-assembly	easy operation	low yield, poor stability	moderate interaction
Thermal annealing	high synthetic efficiency, simple process	high energy consumption, particles aggregation	strong interaction and intimate interface
Mechanical agitation	easy operation, low cost	poor reproducibility, uncontrollable size	weak interaction

Fig. 9. (a) Band configurations of N-ZnO/C and Bi2MoO6 before contact. (b) The transfer route of PC in N-ZnO/C@Bi2MoO6 S-scheme heterojunction under light irradiation. (c) DMPO-?OH and (d) DMPO-?O2? signals of samples. Reproduced with permission from Ref. [92]. Copyright 2021, Elsevier B.V.

Fig. 10. The optimized composite models, charge density difference, and IIEF strength of S-scheme g-C3N4/SnS2 (a,c,e) and O-C3N4/SnS2 (b,d,f) heterojunctions. Reproduced with permission from Ref. [105]. Copyright 2021, Elsevier B.V.

Fig. 11. UV-vis diffuse reflectance spectra (a), transient photocurrent responses (b), electrochemical impedance spectra (c), PL spectra (d), TRPL spectra (e), and the photocatalytic degradation curves (f) of SMX over different samples. (g) The stability test of N-ZnO/C@BiM for SMX degradation; (h) XPS spectra and (i) XRD patterns and SEM image (inset) of N-ZnO/C@BiM before and after four tests. Reproduced with permission from Ref. [48]. Copyright 2021, Elsevier B.V.

Fig. 12. SEM images of Ga2O3/ZnO/WO3 composite nanofibers before (a?c) and after (d?f) calcination. (g) Transfer pathways of PC in Ga2O3/ZnO/WO3 dual S-scheme heterojunction. Reproduced with permission from Ref. [132]. Copyright 2021, Springer Science+Business Media, LLC part of Springer Nature.

Table 2 Recent reports of ZnO-based S-scheme heterojunctions in the field of environmental remediation.

S-scheme heterojunction	Pollutant (Concentration)	pH	Dosage (mg mL^‒1)	Light source (wavelength)	Photodegradation efficiency (%)		Active	Degradation	Ref.
S-scheme heterojunction	Pollutant (Concentration)	pH	Dosage (mg mL^‒1)	Light source (wavelength)	ZnO	Optimal sample	species	product	Ref.
ZnO-CoTe	methylene blue (20 mg L^‒1)	7	0.1	Sunlight	56.1	99.8	•O₂⁻	—	[24]
g-C₃N₄/ZnO	azophloxine (10 mg L^‒1)	7	1	500 W Xe lamp	—	95	•O₂⁻, h⁺	—	[74]
SrTiO₃/porous ZnO	methyl orange (5 mg L^‒1)	7	0.1	300 W Xe lamp	32.4	48.8	•O₂⁻	CO₂, H₂O	[75]
N-ZnO/g-C₃N₄	norfloxacin (10 mg L^‒1)	7	0.2	300 W Xe lamp (λ > 420 nm)	57.7	96.4	h⁺	CO₂, H₂O, F⁻, NO₃⁻	[80]
CuO/ZnO	mercury ions (368.3 µmol L^‒1)	4	1	300 W Xe lamp (λ > 420 nm)	6	100	e⁻	Mercury	[83]
ZnO-V₂O₅-WO₃	methylene blue (10 μmol L^‒1)	7	0.6	Sunlight	78.8	99.8	•O₂⁻	—	[86]
C-ZnO/Ag₃PO₄	ciprofloxacin (10 mg L^‒1)	7	2	300 W Xe lamp (λ > 420 nm)	—	96.7	h⁺, •O₂⁻	—	[89]
ZnO/ZnMn₂O₄/ ZnS-PVA	Co-trimoxazole (5 mg L^‒1)	7	0.05	500 W Visible lamp	—	90	—	—	[90]
N-ZnO/C@Bi₂MoO₆	sulfamethoxazole (5 mg L^‒1)	9	1	300 W Xe lamp (λ > 420 nm)	—	92.9	h⁺	—	[92]
ZnO/Zn₃(PO₄)₂	tetracycline (20 mg L^‒1)	7	1	400 W Osram lamps (400 nm< λ <700 nm)	17	82	•O₂⁻	—	[93]
ZnO/gC₃N₄	methyl orange (10 mg L^‒1)	7	0.5	Mercury lamp (Visible light)	49	99	—	—	[101]
ZnO-g-C₃N₄@PET	methylene blue (15 mg L^‒1)	7	—	350 W Xe lamp (λ > 420 nm)	16.2	92.5	•OH, h⁺	—	[107]
WO₃/Ag/ZnO	cephalexin (30 mg L^‒1)	7	—	Blue LED lamps	13.9	98.8	•O₂⁻, •OH	—	[111]
ZnO-NiO	azophloxine (20 ppm)	7	0.2	—	~27	82	•O₂⁻, •OH	—	[113]
LaFeO₃/ZnO	mercury ions (100 ppm)	4	1.25	300 W Xe lamp (λ > 420 nm)	6	100	e⁻	Mercury	[117]
Bi₂O₃-ZnO/ bentonite clay	congo red (200 mg L^‒1)	7	8	UV light	—	100	—	—	[120]
Curcumin/ZnO	amaranth (0.5 mol L^‒1)	7	1	300 W Solar simulator	42	93	•O₂⁻	—	[121]
NiS/ZnO	P-nitrophenol (101 μM)	7	0.12	8 W Phillips UV light (λ = 254 nm)	65	96	•OH	—	[122]
Ga₂O₃/ZnO/WO₃	Rhodamine B (100 mg L^‒1)	7	0.6	300 W Xe lamp	—	98.4	h⁺, •O₂⁻	CO₂, H₂O	[132]
CuO/ZnO	mercury ions (100 mg L^‒1)	4	1.8	Xe lamp	4.1	100	e⁻	Mercury	[136]

Table 2 Recent reports of ZnO-based S-scheme heterojunctions in the field of environmental remediation.

S-scheme heterojunction	Pollutant (Concentration)	pH	Dosage (mg mL^‒1)	Light source (wavelength)	Photodegradation efficiency (%)		Active	Degradation	Ref.
S-scheme heterojunction	Pollutant (Concentration)	pH	Dosage (mg mL^‒1)	Light source (wavelength)	ZnO	Optimal sample	species	product	Ref.
ZnO-CoTe	methylene blue (20 mg L^‒1)	7	0.1	Sunlight	56.1	99.8	•O₂⁻	—	[24]
g-C₃N₄/ZnO	azophloxine (10 mg L^‒1)	7	1	500 W Xe lamp	—	95	•O₂⁻, h⁺	—	[74]
SrTiO₃/porous ZnO	methyl orange (5 mg L^‒1)	7	0.1	300 W Xe lamp	32.4	48.8	•O₂⁻	CO₂, H₂O	[75]
N-ZnO/g-C₃N₄	norfloxacin (10 mg L^‒1)	7	0.2	300 W Xe lamp (λ > 420 nm)	57.7	96.4	h⁺	CO₂, H₂O, F⁻, NO₃⁻	[80]
CuO/ZnO	mercury ions (368.3 µmol L^‒1)	4	1	300 W Xe lamp (λ > 420 nm)	6	100	e⁻	Mercury	[83]
ZnO-V₂O₅-WO₃	methylene blue (10 μmol L^‒1)	7	0.6	Sunlight	78.8	99.8	•O₂⁻	—	[86]
C-ZnO/Ag₃PO₄	ciprofloxacin (10 mg L^‒1)	7	2	300 W Xe lamp (λ > 420 nm)	—	96.7	h⁺, •O₂⁻	—	[89]
ZnO/ZnMn₂O₄/ ZnS-PVA	Co-trimoxazole (5 mg L^‒1)	7	0.05	500 W Visible lamp	—	90	—	—	[90]
N-ZnO/C@Bi₂MoO₆	sulfamethoxazole (5 mg L^‒1)	9	1	300 W Xe lamp (λ > 420 nm)	—	92.9	h⁺	—	[92]
ZnO/Zn₃(PO₄)₂	tetracycline (20 mg L^‒1)	7	1	400 W Osram lamps (400 nm< λ <700 nm)	17	82	•O₂⁻	—	[93]
ZnO/gC₃N₄	methyl orange (10 mg L^‒1)	7	0.5	Mercury lamp (Visible light)	49	99	—	—	[101]
ZnO-g-C₃N₄@PET	methylene blue (15 mg L^‒1)	7	—	350 W Xe lamp (λ > 420 nm)	16.2	92.5	•OH, h⁺	—	[107]
WO₃/Ag/ZnO	cephalexin (30 mg L^‒1)	7	—	Blue LED lamps	13.9	98.8	•O₂⁻, •OH	—	[111]
ZnO-NiO	azophloxine (20 ppm)	7	0.2	—	~27	82	•O₂⁻, •OH	—	[113]
LaFeO₃/ZnO	mercury ions (100 ppm)	4	1.25	300 W Xe lamp (λ > 420 nm)	6	100	e⁻	Mercury	[117]
Bi₂O₃-ZnO/ bentonite clay	congo red (200 mg L^‒1)	7	8	UV light	—	100	—	—	[120]
Curcumin/ZnO	amaranth (0.5 mol L^‒1)	7	1	300 W Solar simulator	42	93	•O₂⁻	—	[121]
NiS/ZnO	P-nitrophenol (101 μM)	7	0.12	8 W Phillips UV light (λ = 254 nm)	65	96	•OH	—	[122]
Ga₂O₃/ZnO/WO₃	Rhodamine B (100 mg L^‒1)	7	0.6	300 W Xe lamp	—	98.4	h⁺, •O₂⁻	CO₂, H₂O	[132]
CuO/ZnO	mercury ions (100 mg L^‒1)	4	1.8	Xe lamp	4.1	100	e⁻	Mercury	[136]

Fig. 13. (a) Band structures of ZnxCd1-xS-DETA and ZnO. (b) The transfer route of PC in the ZnO/Zn0.5Cd0.5S-DETA S-scheme heterojunction under light irradiation. (c) Charge density difference of ZnO (100)/Zn0.5Cd0.5S (101), the charge accumulation is denoted by yellow, and the charge depletion is denoted by cyan; time courses of photocatalytic H2 production (d) and corresponding H2 evolution rates (e) of the S-scheme photocatalysts. Reproduced with permission. (f) Cycling stability test results for Zn0.5Cd0.5S-DETA and ZOZCS-2. Reproduced with permission from Ref. [31]. Copyright 2022, Wiley-VCH GmbH.

Fig. 14. (a) The transfer route of PC in ZnO/CdS/MoS2 heterojunctions under light irradiation; electrochemical impedance spectroscopy spectra (b), transient photocurrent spectra (c), and photocatalytic H2 evolution activities (d) of samples; stability tests for H2 evolution (e) and XRD patterns before and after 5 cycles (f) over ZCM-3 sample. Reproduced with permission from Ref. [27]. Copyright 2021, Elsevier B.V.

Fig. 15. SEM (a) and transmission electron microscope (TEM) (b) images of ZnO/WO3 composites; Photocatalytic H2O2 production activities (c) and fitted rate constants (d) of H2O2 decomposition (Kd) and formation (Kf) values of different samples. Reproduced with permission from Ref. [13]. Copyright 2021, Elsevier Ltd.

Fig. 16. Schematic illustrations of the ZnMn2O4/ZnO S-scheme heterojunction. (a) Staggered band configurations before contact. (b) Band bending and formation of IIEF after contact. (c) Transfer route of PC under light irradiation. (d) CO2 photoreduction performance of photocatalysts. (e) Recycling performance of ZZM30. Reproduced with permission from Ref. [91]. Copyright 2020, Elsevier B.V.

Fig. 17. Schematic diagram of the U(VI) extraction process from natural seawater using ZnO/Znln2S4 S-scheme heterojunctions. Reproduced with permission from Ref. [73]. Copyright 2022, Elsevier B.V.

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A review on ZnO-based S-scheme heterojunction photocatalysts

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