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Photocatalytic technology, which is regarded as a green route to transform solar energy into chemical fuels, plays an important role in the fields of energy and environmental protection. An emerging S-scheme heterojunction with the tightly coupled interface, whose photocatalytic efficiency exceeds those of conventional type II and Z-scheme photocatalysts, has received much attention due to its rapid charge carrier separation and strong redox capacity. This review provides a systematic description of S-scheme heterojunction in the photocatalysis, including its development, reaction mechanisms, preparation, and characterization methods. In addition, S-scheme photocatalysts for CO2 reduction are described in detail by categorizing them as 0D/1D, 0D/2D, 0D/3D, 2D/2D, and 2D/3D. Finally, some defects of S-scheme heterojunctions are pointed out, and the future development of S-scheme heterojunctions is proposed. [ABSTRACT FROM AUTHOR]

[Display omitted] • A full-spectrum available photothermal S-scheme heterojunction is prepared. • Synergy of defects and IEF improves charge transport and separation efficiency. • The inverse opal structure with slow-light effect enhances light-capturing ability. • IO-B-TiO 2 /In 2 O 3 performs superior CO yield of 251.25 μmol·g−1·h−1. • DFT and experiments explored the reaction mechanism and S-scheme structure. The conversion of greenhouse gases such as carbon dioxide (CO 2) into fuel and high-value chemical materials using solar energy is considered as a viable solution to the environmental pollution and the alleviation of the energy crisis. Herein, a black titanium dioxide/indium oxide S-scheme heterojunction (IO-B-TiO 2 /In 2 O 3) with a three-dimensional porous inverse opal structure was prepared. In the photocatalytic reduction of CO 2 , IO-B-TiO 2 /In 2 O 3 exhibited an excellent CO production rate (251.25 μmol·g−1·h−1), being 8.62 and 1.55 times of pure IO-TiO 2 and IO-B-TiO 2 /In 2 O 3 under non-photothermal conditions, respectively. A series of characterizations and theoretical calculations (DFT) systematically demonstrated that the excellent photocatalytic performance results from the full spectral response of the material, fast charge separation and transport efficiency, and superior photothermal conversion efficiency of the infrared light. This work will provide a promising insight to the design of S-scheme catalysts with outstanding photocatalytic performance via photothermal assistance and the improved solar energy conversion efficiency. [ABSTRACT FROM AUTHOR]