Bimetallic Active Sites Accelerate Electrons Transfer for Photo‐Thermal Catalytic CO ₂ Reduction

Abstract Photo‐thermal conversion of CO 2 into value‐added fuels or chemicals is one of the crucial and promising paths to alleviate the global climate change and energy crisis. However, it is still challenging to achieve higher CO 2 conversion and products yield due to the inherent chemical inertness. Herein, bimetallic active sites are constructed on iron‐based perovskite to design highly efficient photo‐thermal catalysts for achieving excellent CO 2 conversion efficiency via accelerating electrons transfer. Fe‐decorated Ni particle loaded on CaFeO 3 exhibits the optimum photo‐thermal catalytic performance with a total products yield of 74.7 mmol g −1 h −1 , surpassing the state‐of‐the‐art catalysts reported so far. Fe decoration enhanced the CO 2 adsorption capacity of the catalyst. In situ characterizsation and theoretical calculations finds that *HCOO‐dominated pathway governs photo‐thermal CO 2 reduction. Fe addition effectively shifts the 3d orbital of Ni atom to the lower energy level, accelerating the electron transfer of d z2 orbital for CO 2 activation and further reducing the energy barriers of subsequent reduction reaction. This work provides a new way for designing the highly effective catalysts of photo‐thermal CO 2 reduction.