Regulating Photocatalytic CO2 Reduction Kinetics through Modification of Surface Coordination Sphere

Abstract Solar‐driven reduction of CO 2 to value‐added products represents a sustainable strategy for mitigating the greenhouse effect and addressing the related green‐energy crisis. Herein, it is demonstrated that modifying the surface coordination sphere can significantly enhance the reaction kinetics and overall efficiency of CO 2 reduction. More specifically, the decoration of isolated Mn atoms over the multi‐edged TiO 2 nano‐pompons (Mn/TONP) upshifts the d‐band center that allows favorable CO 2 adsorption. Ultrafast spectroscopy demonstrates the greatly accelerated charge transfer between photoexcited multi‐edged TONP and the newly implanted Mn reactive centers, supplying long‐lifetime electrons to reduce absorbed CO 2 molecules. By integrating adsorption and activation functions into the newly decorated Mn sites, the developed photocatalyst demonstrate impressive capacity for CO 2 reduction (80.51 mmol g −1 h −1 ). The surface modulation strategy at the atomic level not only opens new avenues for regulating the reaction kinetics toward photocatalytic CO 2 reduction, but also paves the way for the rational design of highly efficient and selective photocatalysts for clean energy conversion.