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

Developing atomically dispersed metal on nitrogen‐doped carbon (M─N─C) catalyst provides a promising strategy to convert CO 2 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 CO 2 RR. 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 CO 2 electroreduction reaction (CO 2 RR). The most active configuration in CuNi AC @Ni/Cu─N─C catalyst is CuNi atomic cluster connected with 2N‐bridged (Ni‐Cu)N 5 , in which two N atoms are shared with NiN 4 and CuN 3 moieties verified by both systematic advanced characterizations and density function theory (DFT) calculations. The results have revealed the integration between CuNi atomic cluster and N 4 Ni/CuN 3 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.