Major issues in photocatalysis include improving charge carrier separation efficiency at the interface of semiconductor photocatalysts and rationally developing efficient hierarchical heterostructures. Surface continuous growth deposition is used to make hollow Cu2‐xS nanoboxes, and then simple hydrothermal reaction is used to make core‐shell Cu2‐xS@ZnIn2S4 S‐scheme heterojunctions. The photothermal and photocatalytic performance of Cu2‐xS@ZnIn2S4 is improved. In an experimental hydrogen production test, the Cu2‐xS@ZnIn2S4 photocatalyst produces 4653.43 µmol h−1 g−1 of hydrogen, which is 137.6 and 13.8 times higher than pure Cu2‐xS and ZnIn2S4, respectively. Furthermore, the photocatalyst exhibits a high tetracycline degradation efficiency in the water of up to 98.8%. For photocatalytic reactions, the hollow core‐shell configuration gives a large specific surface area and more reactive sites. The photocatalytic response range is broadened, infrared light absorption enhanced, the photothermal effect is outstanding, and the photocatalytic process is promoted. Meanwhile, characterizations, degradation studies, active species trapping investigations, energy band structure analysis, and theoretical calculations all reveal that the S‐scheme heterojunction can efficiently increase photogenerated carrier separation. This research opens up new possibilities for future S‐scheme heterojunction catalyst design and development.

Metal-organic framework (MOF)-5/CuO@ZnIn2S4 core-shell Z-scheme tandem heterojunctions with photothermal effects are prepared by solvothermal and oxidative composite methods to promote spatial charge separation and light utilization.

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Polyoxometalate-based yolk@shell dual Z-scheme superstructure tandem heterojunction nanoreactors exhibit excellent photocatalytic performance, which is ascribed to the dual Z-scheme heterojunction and encapsulation and confinement effects.

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The development of heterojunction composite photocatalysts with sophisticated charge transfer mechanisms and interfaces is a promising approach to enhance photocatalytic efficiency. Herein, for the first time, a peanut‐like Zn0.5Cd0.5S/BiVO4 S‐scheme heterostructure visible‐light composite photocatalyst via a two‐step hydrothermal method is synthesized. S‐scheme heterostructures, which can maintain the maximum redox capacity in the conduction and valence bands of the catalyst, have been established as an effective charge transfer mode in the field of photocatalysis. The Zn0.5Cd0.5S/BiVO4 heterojunction photocatalyst exhibits 99.52% degradation efficiency for tetracycline‐based organic pollutants under visible light irradiation. In addition, the photocatalytic hydrogen production efficiency of the composite catalyst is as high as 8969.58 μmol g−1 h−1, which is 69.24 and 4.35 times higher than that of single BiVO4 and Zn0.5Cd0.5S, respectively. Through density functional theory calculations and experimental studies, the material conformed to the charge transfer mode of the S‐scheme heterojunction is determined. The improved photocatalytic efficiency can be attributed to the formation of S‐scheme heterogeneous interface, which bends the energy band at the interfacial contact, and the formation of an internal electric field, which hinders rapid charge recombination and prolongs the lifetime of charge carriers.

Bi2Fe4O9@ZnIn2S4 laminated heterojunction photocatalysts exhibit excellent photocatalytic performance, which is ascribed to the formation of S-scheme laminated heterojunctions and strong 2D/2D laminated interface interactions.

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