Construction of Cu─Ni Atomic Pair with Bimetallic Atom‐Cluster Sites for Enhanced CO₂ Electroreduction

Abstract Developing atomically dispersed metal on nitrogen‐doped carbon (M─N─C) catalyst provides a promising strategy to convert CO₂ into high‐valued chemicals and achieve artificially closed carbon cycles. However, it is challenging to tune the structure and coordination of N─M bond that further improve the intrinsic activity and selectivity of CO₂RR. Herein, CuNi atomic clusters embedded in Ni/Cu dual atomic sites catalysts (CuNi_AC@Ni/Cu─N─C) are designed and successfully manipulated to regulate the coordination environment for M─N─C catalysts to enhance the CO₂ electroreduction reaction (CO₂RR). The most active configuration in CuNi_AC@Ni/Cu─N─C catalyst is CuNi atomic cluster connected with 2N‐bridged (Ni‐Cu)N₅, in which two N atoms are shared with NiN₄ and CuN₃ moieties verified by both systematic advanced characterizations and density function theory (DFT) calculations. The results have revealed the integration between CuNi atomic cluster and N₄Ni/CuN₃ dual‐metal atomic sites that optimize the electronic redistribution and narrow the bandgap, thereby decreasing the energy barrier of the potential determination step and promoting CO production.