Hybrid photocatalysis with halide perovskite materials

doi:10.1016/S1872-2067(26)65112-1

Abstract

Abstract:

ABSTRACT: Halide perovskites (HPs) have emerged as compelling candidates for photocatalysis, owing to their exceptional optoelectronic properties, including tunable bandgaps, high optical absorption coefficients, and long charge carrier lifetimes. Nevertheless, the reliance on light alone can constrain their catalytic efficiency and utilization of solar energy. To address this challenge, hybrid photocatalysis, where additional stimuli such as electric or (photo)thermal fields are integrated with the pristine light field, has garnered increasing attention. This review systematically evaluates hybrid catalytic strategies for HP-based photocatalysis, with a particular emphasis on enhancement mechanisms arising from synergistic multi-physical field interactions. Subsequently, we highlight recent advances in HPs-based photothermal catalysis (PTC) and photoelectrocatalysis (PEC), critically assessing persistent technical challenges and summarizing design principles for materials and device configurations, while other multi-field strategies including piezo- and magnetic -assisted photocatalysis are also discussed. Finally, we outline the key challenges facing HP-based hybrid photocatalysis and propose future research directions spanning from micro-level material design to macro-scale system integration. This review aims to offer fundamental insights and theoretical guidelines for designing stable and high-performance hybrid photocatalytic systems, thereby advancing the practical application of HP-based technologies.

Key words: Halide perovskites, Hybrid photocatalysis, Performance optimization, Scalable application

Xiangfeng Chen, Siyu Huang, Yuhang Yang, Jiahao Ni, Cheng Fang, Yang-Fan Xu, Dai-Bin Kuang. Hybrid photocatalysis with halide perovskite materials[J]. Chinese Journal of Catalysis, 2026, 88: 9-34.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65112-1

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Figures/Tables 17

Fig. 1. Schematic diagram of hybrid catalytic reaction strategy.

Table 1 Comparison of hybrid photocatalysis systems.

Hybrid catalysis type	Energy form	Core mechanisms and advantages
Photothermal catalysis	synergy of light and thermal fields	full-spectrum utilization kinetics enhancement
Photoelectrocatalysis	synergy of light and electric fields	efficient charge separation overcoming light intermittency
Piezo-photocatalysis	synergy of light and mechanical fields	piezopotential-mediated charge regulation strain engineering for band tuning
Magnetic-photocatalysis	synergy of light and magnetic fields	prolonged charge carrier lifetime "zero-energy-consumption" magnetic synergy
Photo-thermal-electrocatalysis	triadic synergy of light, thermal, and electric fields	breaking the limitations of single fields maximized energy utilization

Fig. 2. Structural and mechanistic insights into halide perovskite photocatalysts. (a) ABX3 framework with A-site cations (Cs+, MA+, FA+), B-site metals (Pb2+, Sn2+, Bi3+), and X-site halides (Cl?, Br?, I?), enabling charge-carrier photogeneration (CB: reduction; VB: oxidation). (b) Band alignment (pH = 0): VBM/CBM comparison for traditional photocatalysts (g-C3N4 [62], CdS [45], SrTiO3 [63], TiO2 [44], Fe2O3 [64], BiVO4 [65]) organic-inorganic perovskites (MAGeI3 [31], MAPbBr3 [66], FAPbBr3 [67], PMA2PbI4 [68], MAPbI3 [11], MASnI3* [22], MA3Bi2I9 [69]) and all-inorganic perovskites (CsPbBr3 [70], Cs3Sb2I9 [35], Cs2AgBiBr6 [36], CsPbI3 [71], Cs3Bi2Br9 [72], CsPbCl3* [22], Cs2SnI6 [37], Cs3Bi2I9 [73]). Note: The materials marked with an asterisk (*) indicate that their band structure data are obtained from theoretical calculations, while the rest are experimentally measured values, which may be influenced by factors such as raw materials, synthesis conditions, crystal morphology, and size. (c) Schematic of the challenges posed by instability and insufficient active sites in halide perovskites: (Center) lattice degradation triggered by environmental stressors (H2O, O2, light, heat); (Center) restricted reactant access to active sites due to halide capping effect; and (Right) stressor-driven degradation pathways, such as hydration, phase transformation, decomposition and complete dissolution.

Fig. 3. Mechanistic insights into photothermal catalysts.

Table 2 The catalytic performance of halide perovskite-based photothermal catalysis.

Catalyst	Reaction type	Light source	Performance [μmol g^-1 h^-1]	Selective	Stability	Ref.
Cs₃Bi₂Br₉/MoS₂	CO₂RR	Xe Lamp	CO: 172.79	CO: 100%	> 5 cycles	[79]
Cs₃Bi₂Br₉@Co₃O₄	CO₂RR	Xe Lamp	CO: 168.56	CO: 100%	> 5 cycles	[81]
Cs₃Bi₂Br₉/Bi₂S₃	CO₂RR	Xe Lamp	CO: 153.82	CO: 100%	> 5 cycles	[80]
Cu: CsPbBr₃	CO₂RR	Xe Lamp	CH₄: 14.72	CH₄:96.9%	> 5 h	[91]
m-CN@CsPbBr₃ NC	CO₂RR	Xe Lamp	CO: 42.8	CO: ~100%	> 5 h	[85]
MF/CsPbBr₃	CO₂RR	Xe Lamp	CO: 29.13 CH₄: 12.95	CO & CH₄	> 104 h	[84]
Cs₃Sb₂I₉	CO₂RR	Xe Lamp	CO+CH₄: 95.7	CO & CH₄	> 3 cycles	[35]
CsPbBr₃@PCN-224(Zr)	CO₂RR	Xe Lamp	CO:73.85	CO: ~100%	repeatable cycles	[82]
CsPbBr₃@CsPb₂Br₅	CO₂RR	white light	CO: 69	CO: 100%	> 8 cycles	[93]
MF/CsPbBr_3‒_xI_x	CO₂RR	Xe Lamp	CO: 173.09 CH₄: 22.88	CO: ~88% CH₄: ~12%	> 42 h	[94]
CsPbBr₃@Pb-TCPP	CO₂RR+benzoylamine oxidation	Xe Lamp	CO: 143.3 CH₄: 18.6	CO & BDA	> 4 cycles	[88]
Pd-SA/Cs₂MoCl₆	semi-hydrogenation	Xe Lamp	100% Conversion rate of phenylacetylene/40min	styrene: ~96%	—	[92]
Cs₄CuSb₂Cl₁₂	dehydrogenation	Xe Lamp	2.0 equivalent H₂/30min	—	> 4 cycles	[86]

Fig. 4. (a) UV-vis DRS spectra of CBB and CBB/MoS2 composites. (b) Thermal images of CBB/MoS2, CBB/Bi2S3 and CBB/Co2O3 under UV-Vis-NIR irradiation. (c) CO production rates of CBB, CBB/Bi2S3, CBB/MoS2, and CBB@Co3O4 under UV-Vis-NIR irradiation. (a-c) Adapted with permission [79-81]. (a-c) Adapted with permission [79]. Copyright 2025, Elsevier. Adapted with permission [80]. Copyright 2024, Elsevier. Adapted with permission [81]. Copyright 2024, Wiley-VCH. (d) Solar-thermal-induced dehydrogenation mechanism of solid-state ammonia borane. (e) Temperature profiles and (f) hydrogen release under varying light power densities. (g) Full-spectrum photothermal conversion via halide perovskite (light absorber/converter) and energy efficiency analysis for ammonia borane-based fuel cell applications. (d-g) Reproduced with permission [86]. Copyright 2024, ACS.

Fig. 5. (a) Photographs of CsPbBr3@PCN-224(Zr)-10 composite (left) and hexane-dispersed PCN-224(Zr), CsPbBr3 QDs, and CsPbBr3@PCN-224(Zr)-10 under visible/UV light (right). (b) S-scheme charge transfer mechanism when PCN-224(Zr) and CsPbBr3 QDs contact under irradiation. (c) PL spectra of PCN-224(Zr), CsPbBr3 QDs, and CsPbBr3@PCN-224(Zr). (a-c) Reproduced with permission [82]. Copyright 2023, The Royal Society of Chemistry. (d) Illustration of Simultaneous CO2RR and selective BA oxidation over CPB⊆Pb-TCPP photocatalyst. (e) S-scheme mechanism with interfacial IEF between CPB nanocrystals and Pb-TCPP. (d,e) Reproduced with permission [88]. Copyright 2024, Elsevier. (f) Illustration of microstructure of m-CN@CsPbBr3 heterojunction. (g) Band alignment and CO2 photoreduction pathways for m-CN@CsPbBr3. (h) Transient absorption decay kinetics at 520 nm with lifetime fitting parameters. (f-h) Reproduced with permission [85]. Copyright 2022, The Royal Society of Chemistry.

Fig. 6. (a) Photothermal CO2 reduction mechanism in Cs3Sb2I9. (b) Comparative CO2 reduction performance of Cs3Sb2I9 under photocatalysis, thermocatalysis, and photothermal conditions. (a,b) Reproduced with permission [35]. Copyright 2021, Elsevier. (c) Proposed CO2 reduction pathways for CsPbBr3 (left) and Cu: CsPbBr3 (right). (d) Steady-state and (e) time-resolved PL spectra of CsPbBr3 vs. Cu:CsPbBr3. (c-e) Reproduced with permission [91]. Copyright 2022, Elsevier. (f) Pd single atoms (PdSA) anchored on Cs2MoCl6 NCs via Pd-Cl coordination. (g) Light-driven semihydrogenation of various alkynes using PdSA/Cs2MoCl6 NCs. (f,g) Reproduced with permission [92]. Copyright 2024, ACS. (h) CO2 hydrogenation performance of CPB@CP2B5 (inset: synthesis schematic). Reproduced with permission [93]. Copyright 2022, Wiley-VCH. (i) Contact angle comparison: MF/CsPbBr3 vs. pristine MF. (j) 104 h stability test for MF/CsPbBr3 under continuous illumination. (i,j) Reproduced with permission [84]. Copyright 2021, Wiley-VCH. (k) DRS spectra of MF/CsPbBrI2 (IPA) under fresh, high-humidity (90%, 2 h), and reheated (24 h) conditions. Reproduced with permission [94]. Copyright 2022, Elsevier.

Fig. 7. Schematic illustrations of Photoelectrocatalysis and Photothermal catalysis based on halide perovskites: (a) PV-EC system, (b) PV-PEC systemand, (c) DPEC system.

Fig. 8. (a) Integration of NiFe LDH/Ni foam electrodes with perovskite tandem cells for water splitting. (b) Energy band diagram of perovskite tandem cell. (a,b) Reproduced with permission [107]. Copyright 2014, The American Association for the Advancement of Science. (c) Cross-sectional schematic of p-i-n perovskite tandem cell structure. (d) MEA flow reactor design with perovskite tandem cell. (c,d) Reproduced with permission [108]. Copyright 2025, Springer Nature. (e) Dual-junction α-Fe2O3 photoanode/perovskite tandem configuration for enhanced high-energy photon harvesting. Reproduced with permission [109]. Copyright 2015, ACS. (f) Schematic diagram of the tandem BiVO4-CH3NH3PbI3 device for solar fuels generation. Reproduced with permission [111]. Copyright 2015, ACS. (g) Dual photoanode (BVO-FeOOH/NiOOH) integration with encapsulated perovskite solar cell architecture. (h) IPCE comparison between 2-BVO-1.5h photoanode and BVO-S. (g,h) Reproduced with permission [112]. Copyright 2018, Wiley-VCH.

Fig. 9. Optical absorption contrast: nanoporous Mo:BiVO4 on planar (a) vs. inverse-conical antenna (b) substrates. FDTD simulations (c,d) show concentrated absorption near electrode surface (250 nm capping layer) in ICA versus deep penetration (900 nm) in planar substrates. (a-d) Reproduced with permission [120]. Copyright 2017, The Royal Society of Chemistry. (e) Architecture of conventional PV-PEC water splitting device. (f) Reflective-spectrum-splitting light management system replacing conventional PV-PEC design. (e,f) Reproduced with permission [115]. Copyright 2022, Frontiers. (g) Novel LED-driven reactor design: Visible light delivered through POF-ITO/ABI optoelectrode immersed in aqueous medium. (h) Conventional reactor design with photons traversing water layer before reaching ITO-supported photocatalysts. (g,h) Reproduced with permission [117]. Copyright 2024, Elsevier.

Fig. 10. Design and performance of advanced photoelectrocatalytic devices. (a) Schematic of Wireless artificial leaf solar hydrogen generator: Co-Ci/H-modified Mo:BiVO4 photoanode coupled with TiO2/CH3NH3PbI3 perovskite tandem cell. (b) Photographs of epoxy-encapsulated tandem cell assembly used in experiment. (c) Unbiased photocurrent and gas evolution (H2/O2) for Co-Ci/H-Mo: BiVO4/perovskite tandem (0.42 cm2) vs Pt counter electrode. (d) STH efficiency and gas yield for 1.3 cm2 artificial leaf under identical conditions. (a-d) Reproduced with permission [97]. Copyright 2015, ACS. (e) NiFeOOH/Ni/FAPbI3 photoanode architecture. (f) Scalable all-perovskite en-PEC system: Parallel-connected NiFeOOH/Ni-FAPbI3 photoanode arrays (7.68 cm2 single cell; 30.8 cm2 mini-module). (g) Stability of encapsulated FAPbI3 PV cell in air. (h) Photographs of 2 × 2 en-PEC mini-module (123.2 cm2) in multi-reactor demonstration setup. (e-h) Reproduced with permission [114]. Copyright 2024, Springer Nature.

Fig. 11. (a) Outdoor test of Flexible 100 cm2 perovskite-BiVO4 artificial leaf. (b) Apparatus for characterizing large-scale floating leaves (devices). (c) Working principle: under illumination, gas bubbles evolve, enabling buoyancy of the lightweight photoelectrochemical (PEC) device. The integrated photocathode is irradiated through the transparent PET substrate. (d) Depiction of the Ti|BiVO4 photoanode and the corresponding EDX elemental maps. (e) Structure of the wired perovskite photocathode and a false-color SEM image of the corresponding layers. (f) Depiction of the CoMTPP molecular catalyst attached to a carbon nanotube, and an SEM cross-sectional image of the carbon nanotube sheet. (g) Light-intensity-dependent performance of perovskite photocathodes. (h) Syngas production stability of photocathode. (a-h) Reproduced with permission [123]. Copyright 2022, Springer Nature. (i) Schematic of bifunctional PEC-EC hybrid device. (j) The energy-level diagram of perovskite components. EDX elemental mapping of perovskite PV cell (k) and BiVO4 photoanode (l). (m) Long-term chronoamperometry of PEC and EC modes. (i-m) Reproduced with permission [124]. Copyright 2020, Wiley-VCH.

Table 3 The performance of halide perovskite-based photoelectrocatalysis, piezo-photocatalysis and magnetic-photocatalysis systems.

Hybrid type	Reaction type	PVK material	Condition	Performance	Product	Conversion efficiency	Stability	Ref.
PEC	water splitting	Cs_0.05(FA_0.83MA_0.17)_0.95Pb(I_0.83Br_0.17)₃	100 mW cm^-2, AM 1.5G	5.87 mA cm^-2 @1.23 V vs. RHE	H₂: O₂≈2:1	STH^b: 6.5%	100 h	[112]
PEC	CO₂RR	Cs_0.07(FA)(MA)_0.22Pb_1.32I_2.27Br_0.66	100 mW cm^-2, AM 1.5G	Formate: 40 μmol h^-1 cm^-2	HCOOH: ~100%	STF: 0.8%	>10 h	[122]
PEC	CO₂RR	Cs_0.07(FA)(MA)_0.22Pb_1.32I_2.27Br_0.66	100 mW cm^-2, AM 1.5G	16.5 mA cm^-2 @0V vs RHE	CO:H₂ = 7.2	STF: 0.58%	>24 h	[123]
PEC	organic degradation	TAB₃Bi₂Br₇I₂	395 nm LED, 29 μW cm^-2	0.66 mA cm^-2@1.2 V vs. Ag/AgCl	—	degradation rate of benzoic acid: >90%	5 cycles, 92%	[117]
PV-PEC	water splitting	MAPbI₃(PSC)^a	100 mW cm^-2, AM 1.5G	3.12 mA cm^-2@1.23 V vs. RHE	H₂&O₂ FE: ~100%	STH: 3.4%	—	[110]
PV-PEC	water splitting	MAPbI₃+ FA_0.83Cs0_0.17PbI₂Br (PSC)	100 mW cm^-2, AM 1.5G	6.01 mA cm^-2@1.23 V vs. RHE	H₂: O₂≈2:1	STH: 6.3%	> 6 h	[120]
PV-PEC	water splitting	MAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	4.8 mA cm^-2@1.23 V vs. RHE	H₂: O₂≈2:1	STH: 4.3%	> 12 h	[97]
PV-PEC	water splitting	MAPbI_3‒_xBr_x (PSC)	100 mW cm^-2, AM 1.5G	3.16 mA cm^-2@1.23 V vs. RHE	H₂: O₂≈2:1	STH: 3.25%	> 10 h	[118]
PV-PEC	water splitting	MAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	2.5 mA cm^-2@0 V vs. RHE	H₂: O₂≈2:1	STH: 2.5%	—	[111]
PV-EC	water splitting	FAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	10.7 mA cm^-2@1 sun	H₂: O₂≈2:1	STH: 13.2%	> 2 h	[119]
PV-EC	water splitting	MAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	10 mA cm^-2@1 sun	H₂: O₂≈2:1	STH: 12.3%	> 10 h	[107]
PV-EC	water splitting	Cs_0.2FA_0.8Pb(I_0.6Br_0.4)₃+ Cs_0.05FA_0.7MA_0.25Pb_0.5Sn_0.5I₃ (PSC)	100 mW cm^-2, AM 1.5G	14.7 mA cm^-2@1 sun	H₂ >99.9%	STH: 17.8%	> 192 h	[108]
PPC	water splitting	CH₃NH₃PbI₃	100 mW/cm² & 70W ultrasonic vibration	H₂: 466 μmol g^-1 h^-1	H₂: ~100%	—	3 cycles	[19]
MPC	CO₂RR	Mn-CsPbBr₃	100 mW cm^-2 & 400mT	CO: 17.6 μmol g^-1 h^-1 CH₄: 0.81 μmol g^-1 h^-1	CO: ~96% CH₄: ~4%	—	—	[133]
MPC	CO₂RR	Fe-CsPbBr₃	100 mW cm^-2 & 300mT	CO: 33.26 μmol g^-1 h^-1	CO: ~100%	—	—	[20]

Table 3 The performance of halide perovskite-based photoelectrocatalysis, piezo-photocatalysis and magnetic-photocatalysis systems.

Hybrid type	Reaction type	PVK material	Condition	Performance	Product	Conversion efficiency	Stability	Ref.
PEC	water splitting	Cs_0.05(FA_0.83MA_0.17)_0.95Pb(I_0.83Br_0.17)₃	100 mW cm^-2, AM 1.5G	5.87 mA cm^-2 @1.23 V vs. RHE	H₂: O₂≈2:1	STH^b: 6.5%	100 h	[112]
PEC	CO₂RR	Cs_0.07(FA)(MA)_0.22Pb_1.32I_2.27Br_0.66	100 mW cm^-2, AM 1.5G	Formate: 40 μmol h^-1 cm^-2	HCOOH: ~100%	STF: 0.8%	>10 h	[122]
PEC	CO₂RR	Cs_0.07(FA)(MA)_0.22Pb_1.32I_2.27Br_0.66	100 mW cm^-2, AM 1.5G	16.5 mA cm^-2 @0V vs RHE	CO:H₂ = 7.2	STF: 0.58%	>24 h	[123]
PEC	organic degradation	TAB₃Bi₂Br₇I₂	395 nm LED, 29 μW cm^-2	0.66 mA cm^-2@1.2 V vs. Ag/AgCl	—	degradation rate of benzoic acid: >90%	5 cycles, 92%	[117]
PV-PEC	water splitting	MAPbI₃(PSC)^a	100 mW cm^-2, AM 1.5G	3.12 mA cm^-2@1.23 V vs. RHE	H₂&O₂ FE: ~100%	STH: 3.4%	—	[110]
PV-PEC	water splitting	MAPbI₃+ FA_0.83Cs0_0.17PbI₂Br (PSC)	100 mW cm^-2, AM 1.5G	6.01 mA cm^-2@1.23 V vs. RHE	H₂: O₂≈2:1	STH: 6.3%	> 6 h	[120]
PV-PEC	water splitting	MAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	4.8 mA cm^-2@1.23 V vs. RHE	H₂: O₂≈2:1	STH: 4.3%	> 12 h	[97]
PV-PEC	water splitting	MAPbI_3‒_xBr_x (PSC)	100 mW cm^-2, AM 1.5G	3.16 mA cm^-2@1.23 V vs. RHE	H₂: O₂≈2:1	STH: 3.25%	> 10 h	[118]
PV-PEC	water splitting	MAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	2.5 mA cm^-2@0 V vs. RHE	H₂: O₂≈2:1	STH: 2.5%	—	[111]
PV-EC	water splitting	FAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	10.7 mA cm^-2@1 sun	H₂: O₂≈2:1	STH: 13.2%	> 2 h	[119]
PV-EC	water splitting	MAPbI₃ (PSC)	100 mW cm^-2, AM 1.5G	10 mA cm^-2@1 sun	H₂: O₂≈2:1	STH: 12.3%	> 10 h	[107]
PV-EC	water splitting	Cs_0.2FA_0.8Pb(I_0.6Br_0.4)₃+ Cs_0.05FA_0.7MA_0.25Pb_0.5Sn_0.5I₃ (PSC)	100 mW cm^-2, AM 1.5G	14.7 mA cm^-2@1 sun	H₂ >99.9%	STH: 17.8%	> 192 h	[108]
PPC	water splitting	CH₃NH₃PbI₃	100 mW/cm² & 70W ultrasonic vibration	H₂: 466 μmol g^-1 h^-1	H₂: ~100%	—	3 cycles	[19]
MPC	CO₂RR	Mn-CsPbBr₃	100 mW cm^-2 & 400mT	CO: 17.6 μmol g^-1 h^-1 CH₄: 0.81 μmol g^-1 h^-1	CO: ~96% CH₄: ~4%	—	—	[133]
MPC	CO₂RR	Fe-CsPbBr₃	100 mW cm^-2 & 300mT	CO: 33.26 μmol g^-1 h^-1	CO: ~100%	—	—	[20]

Fig. 12. (a) Schematic diagram of integrated ST-PSC + EC system for water splitting. (b) Temperature profiles of CNTs and CNTs@NiFe LDH under AM1.5G illumination (100 mW cm-2). (c) J-V curves of CNTs@NiFe LDH//Pt/C two-electrode system with/without infrared irradiation. (a-c) Reproduced with permission [119]. Copyright 2023, Elsevier. (d) Device assembly of the TEG-PEC integrated reactor. (e) Solar spectrum utilization (AM1.5G) in tandem light-harvesting devices. Inset: TE-PEC integration (BiVO4-perovskite-Pt series wiring with 127-pair TEG). (f) Steady-state photocurrents for Pt-PVK-BiVO4 and Pt-TE-PVK-BiVO4 in unassisted water splitting. (g) Performance of TEG-integrated Pt-PVK-BiVO4 under varied light intensities. (h) Photocurrent comparison for Pt-PVK-Fe2O3 and Pt-TE-PVK-Fe2O3 systems. (d-h) Reproduced with permission [127]. Copyright 2023, ACS.

Fig. 13. Product yields of CO and CH4 gases over CsPbBr3 (a) and Mn-CsPbBr3 (b) NPLs with and without an external magnetic field (0 and 300 mT) during 6 h under light irradiation. Schematic illustration of the electron spin polarization induced a longer photoexcited carrier lifetime under an external magnetic field in Mn-CsPbBr3 NPLs (c) and Fe-CsPbBr3 PNCs (d). (a-c) Reproduced with permission [133]. Copyright 2023, ACS. (e) Photocatalytic CO production rate of CsPbBr3 PNCs and Fe-CsPbBr3 PNCs with and without external magnetic field for 4 h. (d,e) Reproduced with permission [20]. Copyright 2024, Elsevier.

Fig. 14. Schematic diagram of the outlook for halide perovskite hybrid photocatalysis.

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