S-scheme charge transfer and photoinduced self-heating effect synergistically enhance the solar-driven CO2 reduction over Cs3Bi2Br9/Bi2S3 hybrid.

• A Cs 3 Bi 2 Br 9 /Bi 2 S 3 hybrid catalyst is constructed by electrostatic self-assembly. • Bi 2 S 3 serves as a photothermal material to elevate the temperature of catalyst. • An S-scheme heterojunction is constructed between Cs 3 Bi 2 Br 9 QDs and Bi 2 S 3 nanorods. • Cs 3 Bi 2 Br 9 /Bi 2 S 3 delivers remarkable photothermal CO 2 conversion rate without any extra heat input. Photothermocatalytic CO 2 reduction, which harnesses the solar power to not only supply heat input but also generate charge carriers, represents an attractive and sustainable approach for solar-to-fuel conversion. Herein, an innovative Cs 3 Bi 2 Br 9 /Bi 2 S 3 (CBB/Bi 2 S 3) hybrid catalyst was elaborately designed by an electrostatic-driven self-assembling approach, which can achieve the effect of "kill two birds with one stone". On the one hand, Bi 2 S 3 functions as a photothermal material owing to its photoinduced self-heating effect, which elevates the temperature of the catalyst for accelerating the catalytic reaction. On the other hand, Bi 2 S 3 synchronously boosts charge separation by forming an S-scheme heterojunction with CBB, as revealed by first-principle simulation and a series of experimental techniques. Remarkably, the developed CBB/Bi 2 S 3 hybrid affords an impressive CO production rate (R CO = 153.82 μmol g−1h−1) without any extra heat input. The present study can provide some enlightening guidance for developing high-performance photothermal catalysts for efficient CO 2 conversion. [ABSTRACT FROM AUTHOR]