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

Photo-thermal conversion of CO₂ 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 CO₂ 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 CO₂ conversion efficiency via accelerating electrons transfer. Fe-decorated Ni particle loaded on CaFeO₃ 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 CO₂ adsorption capacity of the catalyst. In situ characterizsation and theoretical calculations finds that *HCOO-dominated pathway governs photo-thermal CO₂ 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 CO₂ 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 CO₂ reduction.