Orderly Drawing Photo‐Thermal Synergistic Electron Flow for Efficient CO2 Reduction under Natural Sunlight

Abstract Photocatalysis is a green promising approach for CO 2 reduction. Metal sulfides are widely studied in this field due to the high‐efficiency, however, most of them are prone to photo‐corrosion. Herein, a stable and efficient Z‐scheme heterojunction catalyst is reported, Fe x In y S z /TiO 2 owing an orderly drawing photo‐thermal synergistic electron flow for CO 2 reduction in a field experiment. The tests under natural sunlight conditions demonstrated that Fe x In y S z /TiO 2 has a stability of 4 natural days. The maximum photothermal energy conversion efficiency is 1.16%, which is the highest record under concentrated natural sunlight for CO 2 reduction with pure water. The in situ rapid‐scan XANES and XPS show the raising temperature and photo‐irradiation synergistically stretch electrons from O to Fe, revealing the mechanism of thermal modulation to optimize the active sites for efficient and stable photocatalytic CO 2 reduction. This work pioneers the stable and efficient reduction of CO 2 under outdoor sunlight conditions, providing a theoretical foundation for the outdoor application of this technology.