Design of metal-organic frameworks (MOFs)-based photocatalyst for solar fuel production and photo-degradation of pollutants

doi:10.1016/S1872-2067(20)63715-9

Abstract

Abstract:

Metal organic frameworks (MOFs) is a research hotspot in the solar fuel production and photo-degradation of pollutants field due to high surface area, rich metal/organic species, large pore volume, and adjustability of structures and compositions. Therefore, in this review, we first summarized the design factors of photocatalytic materials based on MOF from the perspective of "star" MOF. The modification strategies of MOFs-based photocatalysts were discussed to improve its photocatalytic activity and specific applications were summarized as well, including photocatalytic CO₂ reduction, photocatalytic water splitting and photo-degradation of pollutants. Finally, the advantages and disadvantages of MOFs-based photocatalysts were discussed, the current challenges were highlighted, and suggestions for future research directions were proposed.

Key words: Design, Metal organic framework, Photocatalytic performance, Degradation of organic pollutants, CO₂ reduction, H₂ production

Xiaoxue Zhao, Jinze Li, Xin Li, Pengwei Huo, Weidong Shi. Design of metal-organic frameworks (MOFs)-based photocatalyst for solar fuel production and photo-degradation of pollutants[J]. Chinese Journal of Catalysis, 2021, 42(6): 872-903.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63715-9

https://www.cjcatal.com/EN/Y2021/V42/I6/872

Figures/Tables 45

Fig. 1. (a) Applications of MOFs; (b) Number of papers for different applications of MOF reported during 2010-2020.

Fig. 2. The structures of UiO-66, UiO-67 and UiO-68. Reprinted with permission from Ref. [47]. Copyright (2008) American Chemical Society.

Fig. 3. (a) ZIFs and zeolites have similar bond angles; (b) A schematic illustration of photocatalytic reaction mechanism of ZIF-67(9h)(Ar). Reprinted from Ref. [62]. Copyright (2019) Elsevier.

Fig. 4. Mechanism for the photocatalytic hydroxylation of benzene by MIL-100(Fe). Reprinted with permission from Ref. [49]. Copyright (2015) the Royal Society of Chemistry.

Fig. 5. (a) View of the 3D network of PCN-222; (b) UV-Vis spectra of H2TCPP and PCN-222. Reprinted with permission from Ref. [75]. Copyright (2015) American Chemical Society.

Fig. 6. Mechanism for photocatalytic CO2 reduction over PCN-136 under visible-light irradiation. Reprinted with permission from Ref. [76]. Copyright (2019) American Chemical Society.

Fig. 7. The mechanism for the photocatalytic process by Pt/MIL-125(Ti)/Ag. Reprinted with permission from Ref. [132]. Copyright (2020) Elsevier.

Fig. 8. Photoluminescence (PL) spectra of samples. Reprinted with permission from Ref. [139]. Copyright (2018) Elsevier.

Fig. 9. Possible mechanism for photocatalytic H2 production. Reprinted with permission from Ref. [140]. Copyright (2018) American Chemical Society.

Fig. 10. Different heterojunction types.

Fig. 11. Photocatalytic mechanism of the g-C3N4/PDI/NH2-MIL-53(Fe). Reprinted with permission from Ref. [148]. Copyright (2019) Elsevier.

Fig. 12. Transient absorption spectroscopy study of TiO2, NH2-UiO-66 and TiO2/NH2-UiO-66 composite (2-TiMOF). Reprinted with permission from Ref. [150]. Copyright (2017) Elsevier.

Fig. 13. (a) Photoreduction of the Cr(VI) at pH = 2 using various photocatalysts; (b) Illustration of plausible mechanism of photocatalysis reduction of Cr(VI) over BB-100 under white light. Reprinted with permission from Ref. [151]. Copyright (2020) Elsevier.

Fig. 14. The charge transfer in Z-scheme photocatalytic mechanism systems.

Fig. 15. The charge transfer in UiO-66-NH2/Ag2CO3. Reprinted with permission from Ref. [152]. Copyright (2019) Elsevier.

Fig. 16. (a) HR-TEM images 46TiO2@54NM; (b) Photocatalytic activities of 46TiO2@54NM, 46TiO2/54NM-Mech and 46TiO2/54NM-Evap. Reprinted with permission from Ref. [157]. Copyright (2019) Elsevier.

Fig. 17. Photocatalytic process for AgI/UiO-66(NH2). Reprinted with permission from Ref. [161]. Copyright (2020) Elsevier.

Fig. 18. Proposed photocatalytic mechanism and charge transfer scheme of the Ag3VO4/Cu-MOF/rGO. Reprinted with permission from Ref. [162]. Copyright (2020) Elsevier.

Fig. 19. (a) Schematic diagram of the visible light active MOFs; (b) UV/Vis spectra of the samples; (c) Proposed mechanism for the photocatalytic N2 fixation over NH2-MIL-125(Ti). Reprinted with permission from Ref. [166]. Copyright (2020) Elsevier.

Fig. 20. Photocatalytic mechanism of Cr(VI) reduction and TC-HCl oxidation in water with NH2-MIL-68 (InαFe1-α). Reprinted with permission from Ref. [169]. Copyright (2020) Elsevier.

Fig. 21. Schematic illustration of the main five steps in photocatalytic CO2 reduction.

Fig. 22. Bandgap energy, CB and VB potential of various photocatalysts. Reprinted with permission from Ref. [180]. Copyright (2018) Elsevier.

Table 1 Reduction potentials of some reactions related to CO2 reduction.

Reactions	E⁰_redox/(V vs NHE)
CO₂ + 2H⁺ + 2e^- → HCOOH	-0.61 V
CO₂ + 2H⁺ + 2e^- → CO + H₂O	-0.53 V
CO₂ + 4H⁺ + 4e^- → HCHO + H₂O	-0.48 V
CO₂ + 6H⁺ + 6e^- → CH₃OH + H₂O	-0.38 V
CO₂ + 8H⁺ + 8e^- → CH₄ + H₂O	-0.24 V

Table 2 Performances of some MOF-based photocatalysts for photocatalytic CO2 reduction.

Photocatalyst	Light	Sacrificial agent	Products	Yield (μmol·g^-1·h^-1)	Ref.
NH₂-MIL-125(Ti)	Visible light	MeCN/TEOA	HCOOH	16.28	[106]
Eu-Ru(phen)₃-MOF	Visible light	TEOA	HCOOH	102.47	[187]
AUBM-4	Visible light	MeCN/TEOA	HCOOH	366	[188]
Ir-CP	Visible light	MeCN/TEOA	HCOOH	158.3	[189]
Rh-PMOF-1(Zr)	Visible light	MeCN/TEOA	HCOOH	33.8	[190]
PCN-138	Visible light	TIPA	HCOOH	6.6	[17]
PCN-222	Visible light	TEOA	HCOOH	60	[75]
PCN-136	Visible light	TIPA	HCOOH	46.29	[76]
NNU-28	Visible light	MeCN/TEOA	HCOOH	149.88	[191]
NNU-31-Zn	Visible light	—	HCOOH	26.3	[192]
UiO-66-CrCAT	Visible light	MeCN/TEOA	HCOOH	1724.3	[193]
UiO-66-NH₂/2.0GR	Visible light	TEOA	HCOOH	443.75	[137]
CdS/ZIF-8	Visible light	MeCN	CO	803.25	[194]
Co-ZIF-67@α-TiO₂	Visible light	MeCN/TEOA	CO	7300	[195]
TiO₂/C@ZnCo-ZIF-L	UV-vis light	—	CO	28.6	[196]
PCN-250-Fe₂Mn	Visible light	MeCN/TIPA	CO	21510	[9]
MIL-101-EN	Visible light	—	CO	47.2	[197]
MOF-Ni	Visible light	MeCN/TIPA	CO	371.6	[198]
NH₂‑MIL-101(Fe)/g‑C₃N₄	Visible light	TEOA	CO	22.13	[199]
CdS/MIL-101(Cr)	Visible light	—	CO	16.35	[200]
Zn-MOF	Visible light	MeCN/MeOH/TEOA	CO	—	[201]
Co-ZIF-9/CdS	Visible light	MeCN/TEOA	CO	1426	[202]
TiO₂/MOF	Visible light	—	CO	4.24	[150]
Co-UiO-67	Visible light	MeCN/TEOA	CO	3292.5	[203]
PCN-224(Cu)/TiO₂	Visible light	—	CO	37.21	[204]
CuTCPP/UiO-66/TiO₂	Visible light	—	CO	31.32	[205]
Ni₃(HITP)₂/[Ru(bpy)₃]Cl₂·6H₂O	Visible light	MeCN/TEOA	CO	3.45 × 10⁴	[206]
Ni₃(HITP)₂/rGO	Visible light	MeCN/TEOA	CO	3.8 × 10⁴	[207]
In-Fe_1.91TCPP-MOF	Visible light	Ethyl acetate	CO	144.54	[208]
In-Co_1.71TCPP-MOF	Visible light	Ethyl acetate	CO	38.70	[208]
In-InTCPP-MOF	Visible light	Ethyl acetate	CO	22.95	[208]
Bi₂S₃/UiO-66	UV-vis light	—	CO	25.6	[209]
CdS/ZIF-67	Visible light	TEOA	CO	183.964	[210]
Zn₂GeO₄/Mg-MOF-74	UV-vis light	MECN	CO	1.45	[211]
HKUST-1/TiO₂	Visible light	—	CO	256.35	[212]
TiO₂/UiO-66	UV-vis light	—	CH₄	17.9	[213]
TiO₂/NH₂-MIL-125(Ti)	Visible light	—	CH₄	1.18	[216]
Zn/PMOF	UV light	—	CH₄	8.69	[217]
S_Cu	Visible light	TEA	CH₃OH	262.6 ppm·g^-1·h^-1	[108]
NNU-13	Visible light	TEOA	CH₄	117.33	[218]
NNU-14	Visible light	TEOA	CH₄	52	[219]

Table 2 Performances of some MOF-based photocatalysts for photocatalytic CO2 reduction.

Photocatalyst	Light	Sacrificial agent	Products	Yield (μmol·g^-1·h^-1)	Ref.
NH₂-MIL-125(Ti)	Visible light	MeCN/TEOA	HCOOH	16.28	[106]
Eu-Ru(phen)₃-MOF	Visible light	TEOA	HCOOH	102.47	[187]
AUBM-4	Visible light	MeCN/TEOA	HCOOH	366	[188]
Ir-CP	Visible light	MeCN/TEOA	HCOOH	158.3	[189]
Rh-PMOF-1(Zr)	Visible light	MeCN/TEOA	HCOOH	33.8	[190]
PCN-138	Visible light	TIPA	HCOOH	6.6	[17]
PCN-222	Visible light	TEOA	HCOOH	60	[75]
PCN-136	Visible light	TIPA	HCOOH	46.29	[76]
NNU-28	Visible light	MeCN/TEOA	HCOOH	149.88	[191]
NNU-31-Zn	Visible light	—	HCOOH	26.3	[192]
UiO-66-CrCAT	Visible light	MeCN/TEOA	HCOOH	1724.3	[193]
UiO-66-NH₂/2.0GR	Visible light	TEOA	HCOOH	443.75	[137]
CdS/ZIF-8	Visible light	MeCN	CO	803.25	[194]
Co-ZIF-67@α-TiO₂	Visible light	MeCN/TEOA	CO	7300	[195]
TiO₂/C@ZnCo-ZIF-L	UV-vis light	—	CO	28.6	[196]
PCN-250-Fe₂Mn	Visible light	MeCN/TIPA	CO	21510	[9]
MIL-101-EN	Visible light	—	CO	47.2	[197]
MOF-Ni	Visible light	MeCN/TIPA	CO	371.6	[198]
NH₂‑MIL-101(Fe)/g‑C₃N₄	Visible light	TEOA	CO	22.13	[199]
CdS/MIL-101(Cr)	Visible light	—	CO	16.35	[200]
Zn-MOF	Visible light	MeCN/MeOH/TEOA	CO	—	[201]
Co-ZIF-9/CdS	Visible light	MeCN/TEOA	CO	1426	[202]
TiO₂/MOF	Visible light	—	CO	4.24	[150]
Co-UiO-67	Visible light	MeCN/TEOA	CO	3292.5	[203]
PCN-224(Cu)/TiO₂	Visible light	—	CO	37.21	[204]
CuTCPP/UiO-66/TiO₂	Visible light	—	CO	31.32	[205]
Ni₃(HITP)₂/[Ru(bpy)₃]Cl₂·6H₂O	Visible light	MeCN/TEOA	CO	3.45 × 10⁴	[206]
Ni₃(HITP)₂/rGO	Visible light	MeCN/TEOA	CO	3.8 × 10⁴	[207]
In-Fe_1.91TCPP-MOF	Visible light	Ethyl acetate	CO	144.54	[208]
In-Co_1.71TCPP-MOF	Visible light	Ethyl acetate	CO	38.70	[208]
In-InTCPP-MOF	Visible light	Ethyl acetate	CO	22.95	[208]
Bi₂S₃/UiO-66	UV-vis light	—	CO	25.6	[209]
CdS/ZIF-67	Visible light	TEOA	CO	183.964	[210]
Zn₂GeO₄/Mg-MOF-74	UV-vis light	MECN	CO	1.45	[211]
HKUST-1/TiO₂	Visible light	—	CO	256.35	[212]
TiO₂/UiO-66	UV-vis light	—	CH₄	17.9	[213]
TiO₂/NH₂-MIL-125(Ti)	Visible light	—	CH₄	1.18	[216]
Zn/PMOF	UV light	—	CH₄	8.69	[217]
S_Cu	Visible light	TEA	CH₃OH	262.6 ppm·g^-1·h^-1	[108]
NNU-13	Visible light	TEOA	CH₄	117.33	[218]
NNU-14	Visible light	TEOA	CH₄	52	[219]

Fig. 23. (a) Schematic light-induced dynamics of Eu-Ru(phen)3-MOF; (b) Mechanism of photocatalytic CO2 reduction to HCOOH over Eu-Ru(phen)3-MOF. Reprinted with permission from Ref. [187]. Copyright (2018) Nature.

Fig. 24. Preparation of UiO-66-CrCAT photocatalyst by post-synthesis exchange (PSE) and metallization. Reprinted with permission from Ref. [193]. Copyright (2015) the Royal Society of Chemistry.

Fig. 25. (a) Before (blue curve) and in (red curve) photocatalytic CO2 reduction; (b) The CO adsorption energy on TiO2, ZnCo-ZIF-L, and TiO2/C@ZnCo-ZIF-L, respectively. Reprinted with permission from Ref. [196]. Copyright (2020) Elsevier.

Fig. 26. (a) Synthetic scheme of Co-UiO-67 or Re-UiO-67; (b) Reaction free energy of CO2 reduction to CO over Co-UiO-67 and Re-UiO-67. Reprinted with permission from Ref. [203]. Copyright (2020) American Chemical Society.

Fig. 27. Mechanism of photocatalytic CO2 reduction to CO with Ni3(HITP)2. Reprinted with permission from Ref. [206]. Copyright (2018) Elsevier.

Fig. 28. XPS and XANES analyses of elemental electronic states on Ni3HITP2 and NHPG-2: (a) high-resolution Ni 2p spectra; (b) Ni L3 edge X-ray absorption near edge structure spectra. Reprinted with permission from [207]. Copyright (2020) Elsevier.

Fig. 29. The reaction pathways of CO2 photoreduction. Reprinted with permission from Ref. [217]. Copyright (2016) Elsevier.

Fig. 30. Proposed mechanism for photocatalytic CO2 reduction. Reprinted with permission from Ref. [218]. Copyright (2019) Oxford University Press.

Table 3 Photocatalytic hydrogen production of MOF-based photocatalysts.

Photocatalyst	Co-catalyst	Photosensitizer	Products	Activity (mmol·g^-1·h^-1)	Ref.
Al-ATA-Ni MOF	—	—	H₂ and O₂	5.16 and 1.2	[224]
MIL-125(Ti)-NH₂	—	—	H₂ and O₂	0.002 and 0.001	[225]
MIL-125(Ti)-NH₂	CoO_x	—	H₂ and O₂	0.007 and 0.003	[225]
MIL-125(Ti)-NH₂	Pt	—	H₂ and O₂	0.003 and 0.001	[225]
MIL-125(Ti)-NH₂	RuO_X	—	H₂ and O₂	0.003 and 0.001	[225]
MIL-125(Ti)-NH₂	Pt/RuO_X	—	H₂ and O₂	0.01 and 0.004	[225]
UiO-66(Zr/Ce/Ti)	—	—	H₂ and O₂	0.009 and 0.003	[226]
MoS₂/UiO-66-NH₂	—	—	H₂ and O₂	25.65 and 13.18	[227]
Ru-MIL-125-NH₂	—	—	H₂	0.426	[229]
UiO-67-Ce	—	—	H₂	10.784	[230]
MIL-125-NH₂@TiO₂	—	—	H₂	0.496	[231]
TiO₂@NH₂-MIL-125	—	—	H₂	0.44	[232]
NH₂-MIL-125(Ti)/RGO	—	—	H₂	0.091	[140]
ZnIn₂S₄@NH₂-MIL-125(Ti)	—	—	H₂	2.204	[233]
Ti₃C₂@UiO-66-NH₂	—	—	H₂	0.204	[240]
Ti₃C₂/TiO₂/UiO-66-NH₂	—	—	H₂	1.980	[241]
CdS QD/UiO-66-(SH)₂	—	—	H₂	15.32	[242]
NH₂-UiO-66-d/ZnIn₂S₄	—	—	H₂	7.3	[243]
CdLa₂S₄/MIL-88A(Fe)	—	—	H₂	7.677	[155]
CdS/ZIF-67	—	—	H₂	3.08	[244]
CdS/Ni-MOF	—	—	H₂	2.508	[245]
3Cu/BiOI/4MOF	—	—	H₂	0.269	[246]
CuO@HKUST-1	—	—	H₂	0.667	[247]
UNiMOF/gC₃N₄	—	—	H₂	0.4	[248]
Zn_0.2Cd_0.8S@h-MOF-5	—	—	H₂	15.08	[249]
Zn_0.5Cd_0.5S/ZIF-67	—	—	H₂	23.264.6	[250]
CFB/NH₂-MIL-125(Ti)	Pt	—	H₂	1.123	[251]
Pt@UiO-66-NH₂	Pt	—	H₂	0.257	[252]
Pt/UiO-66-NH₂	Pt	—	H₂	0.05	[252]
ZnIn₂S₄@NH₂-MIL-53	Pt	—	H₂	26.95	[253]
Bi-TBAPy	Pt	—	H₂	0.14	[254]
ZIF-8/g-C₃N₄	Pt	—	H₂	0.31	[255]
Pt@PMOF	Pt	—	H₂	8.52	[256]
NH₂-MIL-125/TiO₂/CdS	Pt	—	H₂	2.997	[257]
NH₂-MIL-125(Ti)/CTF-1	Pt	—	H₂	0.36	[258]
g-C₃N₄/UMOFNs	Pt	—	H₂	1.91	[259]
g-C₃N₄@TiATA/Pt	Pt	—	H₂	0.265	[260]
CdS/UiO-66	Pt	—	H₂	47	[261]
BP/R-Ti-MOFs/Pt	Pt	—	H₂	1.24	[262]
UiO-66/CdS	MoS₂	—	H₂	32.5	[263]
UiO-66(COOH)₂/ZnIn₂S₄	MoS₂	—	H₂	18.794	[264]
NH₂-MIL-125(Ti)@ZnIn₂S₄/CdS	CdS	—	H₂	2.367	[265]
UiO-66-NH₂	Pt	Calix-3	H₂	0.516	[266]
UiO-66	Pt	ErB	H₂	0.46	[267]
UiO-66	NiS₂	ErB	H₂	1.84	[268]
g-C₃N₄/UiO-66	Ni₂P	EY	H₂	2	[269]
Pt-SACs/MBT	Pt	EY	H₂	68.33	[270]
g-C₃N₄@ZIF-67/NiS_x	NiS_x	EY	H₂	2.77	[271]
g-C₃N₄/ZIF-67/MoS₂	MoS₂	EY	H₂	4.0125	[272]
MoS₂ QDs/UiO-66-NH₂/GO	MoS₂	EY	H₂	2.074	[273]

Table 3 Photocatalytic hydrogen production of MOF-based photocatalysts.

Photocatalyst	Co-catalyst	Photosensitizer	Products	Activity (mmol·g^-1·h^-1)	Ref.
Al-ATA-Ni MOF	—	—	H₂ and O₂	5.16 and 1.2	[224]
MIL-125(Ti)-NH₂	—	—	H₂ and O₂	0.002 and 0.001	[225]
MIL-125(Ti)-NH₂	CoO_x	—	H₂ and O₂	0.007 and 0.003	[225]
MIL-125(Ti)-NH₂	Pt	—	H₂ and O₂	0.003 and 0.001	[225]
MIL-125(Ti)-NH₂	RuO_X	—	H₂ and O₂	0.003 and 0.001	[225]
MIL-125(Ti)-NH₂	Pt/RuO_X	—	H₂ and O₂	0.01 and 0.004	[225]
UiO-66(Zr/Ce/Ti)	—	—	H₂ and O₂	0.009 and 0.003	[226]
MoS₂/UiO-66-NH₂	—	—	H₂ and O₂	25.65 and 13.18	[227]
Ru-MIL-125-NH₂	—	—	H₂	0.426	[229]
UiO-67-Ce	—	—	H₂	10.784	[230]
MIL-125-NH₂@TiO₂	—	—	H₂	0.496	[231]
TiO₂@NH₂-MIL-125	—	—	H₂	0.44	[232]
NH₂-MIL-125(Ti)/RGO	—	—	H₂	0.091	[140]
ZnIn₂S₄@NH₂-MIL-125(Ti)	—	—	H₂	2.204	[233]
Ti₃C₂@UiO-66-NH₂	—	—	H₂	0.204	[240]
Ti₃C₂/TiO₂/UiO-66-NH₂	—	—	H₂	1.980	[241]
CdS QD/UiO-66-(SH)₂	—	—	H₂	15.32	[242]
NH₂-UiO-66-d/ZnIn₂S₄	—	—	H₂	7.3	[243]
CdLa₂S₄/MIL-88A(Fe)	—	—	H₂	7.677	[155]
CdS/ZIF-67	—	—	H₂	3.08	[244]
CdS/Ni-MOF	—	—	H₂	2.508	[245]
3Cu/BiOI/4MOF	—	—	H₂	0.269	[246]
CuO@HKUST-1	—	—	H₂	0.667	[247]
UNiMOF/gC₃N₄	—	—	H₂	0.4	[248]
Zn_0.2Cd_0.8S@h-MOF-5	—	—	H₂	15.08	[249]
Zn_0.5Cd_0.5S/ZIF-67	—	—	H₂	23.264.6	[250]
CFB/NH₂-MIL-125(Ti)	Pt	—	H₂	1.123	[251]
Pt@UiO-66-NH₂	Pt	—	H₂	0.257	[252]
Pt/UiO-66-NH₂	Pt	—	H₂	0.05	[252]
ZnIn₂S₄@NH₂-MIL-53	Pt	—	H₂	26.95	[253]
Bi-TBAPy	Pt	—	H₂	0.14	[254]
ZIF-8/g-C₃N₄	Pt	—	H₂	0.31	[255]
Pt@PMOF	Pt	—	H₂	8.52	[256]
NH₂-MIL-125/TiO₂/CdS	Pt	—	H₂	2.997	[257]
NH₂-MIL-125(Ti)/CTF-1	Pt	—	H₂	0.36	[258]
g-C₃N₄/UMOFNs	Pt	—	H₂	1.91	[259]
g-C₃N₄@TiATA/Pt	Pt	—	H₂	0.265	[260]
CdS/UiO-66	Pt	—	H₂	47	[261]
BP/R-Ti-MOFs/Pt	Pt	—	H₂	1.24	[262]
UiO-66/CdS	MoS₂	—	H₂	32.5	[263]
UiO-66(COOH)₂/ZnIn₂S₄	MoS₂	—	H₂	18.794	[264]
NH₂-MIL-125(Ti)@ZnIn₂S₄/CdS	CdS	—	H₂	2.367	[265]
UiO-66-NH₂	Pt	Calix-3	H₂	0.516	[266]
UiO-66	Pt	ErB	H₂	0.46	[267]
UiO-66	NiS₂	ErB	H₂	1.84	[268]
g-C₃N₄/UiO-66	Ni₂P	EY	H₂	2	[269]
Pt-SACs/MBT	Pt	EY	H₂	68.33	[270]
g-C₃N₄@ZIF-67/NiS_x	NiS_x	EY	H₂	2.77	[271]
g-C₃N₄/ZIF-67/MoS₂	MoS₂	EY	H₂	4.0125	[272]
MoS₂ QDs/UiO-66-NH₂/GO	MoS₂	EY	H₂	2.074	[273]

Fig. 31. Frontier molecular orbitals and HOMO/LUMO gaps of Ti8O8(OH)4(COOH)11(COOC6H5NH2), Ti8O8(OH)4(COOH)11(COOC6H5NH2) Ru and Ti8O8(OH)4(COOH)10(COOC6H5NH2)2Ru2. Reprinted with permission from Ref. [229]. Copyright (2019) American Chemical Society.

Fig. 32. (a) Synthetic process of monodisperse TiO2@MOF FS; (b) Schematic illustration for the enhanced photocatalytic process of TiO2@MOF FS. Reprinted with permission from Ref. [232]. Copyright (2020) Elsevier.

Fig. 33. (a) Schematic chart for the fabrication of Ti3C2/UiO-66-NH2; (b) Energy level structure diagram of Ti3C2/UiO-66-NH2 for photocatalytic HER process, Reprinted from Ref. [240], Copyright (2019), with permission from Elsevier; (c) Schematic chart for the fabrication of Ti3C2/TiO2/UiO-66-NH2; (d) The charge-transfer pathways for Ti3C2/TiO2/UiO-66-NH2. Reprinted with permission from Ref. [241]. Copyright (2019), Elsevier.

Fig. 34. Photocatalytic mechanism of the charge transfer for hydrogen evolution over the 10CFBM. Reprinted with permission from Ref. [251]. Copyright (2018) Elsevier.

Fig. 35. (a) Charge transfer path of MoS2/UiO-66/CdS; (b) The rate of H2 production over samples loaded with 1 wt% MoS2 or Pt. Reprinted with permission from Ref. [263]. Copyright (2015) Elsevier.

Fig. 36. The mechanism of photocatalytic hydrogen production of NH2-MIL-125(Ti)@ZnIn2S4/CdS. Reprinted with permission from Ref. [265]. Copyright (2020) Elsevier.

Fig. 37. Mechanism of dye-sensitized MOFs for photocatalysis for H2 production.

Fig. 38. (a) Hydrogen production of photocatalysts with diferent con-tents of Ni2P; (b) The photocatalytic hydrogen production mechanism by the EY sensitized g-C3N4/Ui0-66/Ni2P. Reprinted with permission from Ref. [269]. Copyright (2018) Elsevier.

Fig. 39. Simplified schematic for the charge-transfer transitions.

Table 4 Photocatalytic degradation of organic pollutants over MOF-based photocatalysts.

Photocatalyst	Light	Pollutants	Reactive species	Activity (%)	Ref.
In₂S₃/UiO-66	Visible light	MO	O₂^•-	96.2	[281]
In₂S₃/UiO-66	Visible light	TCH	O₂^•-	84.8	[281]
S-TiO₂/UiO-66-NH₂	Visible light	BPA	O₂^•-	97.5	[282]
C-dots/TiO₂/UiO-66-NH₂	Visible light	KET	O₂^•-	90	[283]
Ag₃VO₄/Cu-MOF/rGO	Visible light	AB92	O₂^•-	—	[162]
MOF/CuWO₄	Visible light	MB	O₂^•-	98	[284]
MOF/CuWO₄	Visible light	4-NP	O₂^•-	81	[284]
ZIF-8@TiO₂	UV-vis light	TC	O₂^•-	90	[285]
AgBr/ZIF-8	Visible light	MB	O₂^•-	99.5	[286]
NH₂-MIL-125(Ti)/BiOCl	Visible light	TC	O₂^•-	78	[287]
NH₂-MIL-125(Ti)/BiOCl	Visible light	BPA	O₂^•-	65	[287]
CdS/MIL-53(Fe)	Visible light	RhB	O₂^•-	92.5	[288]
NH₂-MIL-68(In_αFe_1-α)	Visible light	TC	O₂^•-	72	[169]
MIL-125(Ti)/g-C₃N₄	UV-vis light	Cefixime	O₂^•-	—	[289]
TiO₂@MIL-101(Cr)	UV light	BPA	O₂^•-	99.4	[290]
MIL-68(In)-NH₂/GrO	Visible light	AMX	h⁺	93	[291]
g-C₃N₄/MIL-68(In)-NH₂	Visible light	IBP	h⁺	93	[292]
CQDs/NH₂-MIL-125	Visible light	RhB	h⁺	100	[293]
Pt/MIL-125(Ti)/Ag	Visible light	KP	•OH	95.5	[132]
Ag NPs@MIL-100(Fe)/GG	Visible light	MB	•OH	100	[294]
Ag/AgCl@MIL-88A(Fe)	Visible light	IBP	h⁺	100	[295]
TiO₂-MIL-101(Cr)	Visible light	TC	h⁺	99.7	[296]
TiO₂@MIL-100(Fe)	Visible light	MB	h⁺ and •OH	100	[297]
MIL-53(Al)/ZnO	UV light	TMP	•OH	93.5	[298]
UiO-66-NH₂/Bi₂WO₆	Visible light	RhB	h⁺	100	[299]
CoTiO₃/UiO-66-NH₂	Visible light	NFX	•OH	90.13	[300]
NH₂-UiO-66/ZnIn₂S₄	UV-vis light	MG	h⁺	98	[301]
MWCNT/N-TiO₂/UiO-66-NH₂	Visible light	KET	•OH	96	[302]
Cu-NH₂-MIL-125(Ti)	Visible light	MO	h⁺ and •OH	86.9	[303]
Cu-NH₂-MIL-125(Ti)	Visible light	Phenol	h⁺ and •OH	63.5	[303]
CdS/MIL-53(Fe)	Visible light	KTC	•OH	80	[304]
In₂S₃/MIL-100(Fe)	Visible light	TC	h⁺	88	[305]
Ag₃VO₄@MIL-125-NH₂	UV-vis light	MB	•OH	95.2	[306]
Ag₃PO₄@UMOFNs	Visible light	Phenol	h⁺	100	[307]
Ag₃PO₄@UMOFNs	Visible light	BPA	h⁺	98.9	[307]
UMOFN/Ag₃PO₄	Visible light	2-CP	h⁺	—	[308]

Fig. 40. Photocatalysis mechanism for the photodegradation of MO over ISU-40%. Reprinted with permission from Ref. [281]. Copyright (2019) Elsevier.

Fig. 41. Photocatalytic mechanism of AgBr/ZIF-8. Reprinted with permission from Ref. [286]. Copyright (2020) Elsevier.

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