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

Abstract

AbstractDeveloping 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 (CuNiAC@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 CuNiAC@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.