Atomic‐level Ag─Sn Coordination Engineering in Laser‐Synthesized Cu ₆ Sn ₅ Alloys for Energy‐Efficient Electroreduction CO ₂ to Formate

Abstract Cu‐Sn alloy (Cu x Sn y ) has emerged as a promising category of catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) to produce formate. Introducing heteroatoms to regulate the electronic structure of the active site is a common method to further improve the catalytic performance. However, owing to the existence of multiple active sites on the alloy surface, realizing the fine‐tuned coordination environment in Cu x Sn y remains a persistent challenge through heteroatom doping. Here precise Ag─Sn and Ag─Cu coordinated Cu 6 Sn 5 alloys are developed by a laser‐induced nonequilibrium synthesis strategy. Compared to Cu 6 Sn 5 and Ag─Cu coordinated Cu 6 Sn 5 (Ag─Cu’ 6 Sn 5 ), Ag─Sn coordinated Cu 6 Sn 5 catalyst (Ag─Cu 6 Sn’ 5 ) achieves a superior formate conversion performance in CO 2 RR by optimizing the electronic structure at the d‐band center, which enhances the concentration of CO 2 on the catalyst surface and reduces the activation barrier of rate‐determining step, i.e., the electron transfer step of adsorbed CO 2 to generate the intermediate * CO 2 − as validated by electrokinetic, in situ spectroscopic and theoretical investigations. Furthermore, integrating the Ag─Cu 6 Sn’ 5 catalyst with glycerol oxidation instead of conventional oxygen evolution lowers energy consumption by 68.57% while effectively increasing formate production rate. This work provides a laser‐driven strategy for precise coordination modulation in alloy catalysts, advancing energy‐efficient CO 2 conversion systems.