Structure-activity relationship of Cu-based catalysts for the highly efficient CO 2 electrochemical reduction reaction.

Electrocatalytic carbon dioxide reduction (CORR) is a relatively feasible method to reduce the atmospheric concentration of CO. Although a series of metal-based catalysts have gained interest for CORR, understanding the structure-activity relationship for Cu-based catalysts remains a great challenge. Herein, three Cu-based catalysts with different sizes and compositions (Cu@CNTs, Cu@CNTs, and CuNi@CNTs) were designed to explore this relationship by density functional theory (DFT). The calculation results show a higher degree of CO molecule activation on CuNi@CNTs compared to that on Cu@CNTs and Cu@CNTs. The methane (CH) molecule is produced on both Cu@CNTs and CuNi@CNTs, while carbon monoxide (CO) is synthesized on Cu@CNTs. The Cu@CNTs showed higher activity for CH production with a low overpotential value of 0.36 V compared to CuNi@CNTs (0.60 V), with *CHO formation considered the potential-determining step (PDS). The overpotential value was only 0.02 V for *CO formation on the Cu@CNTs, and *COOH formation was the PDS. The limiting potential difference analysis with the hydrogen evolution reaction (HER) indicated that the Cu@CNTs exhibited the highest selectivity of CH among the three catalysts. Therefore, the sizes and compositions of Cu-based catalysts greatly influence CORR activity and selectivity. This study provides an innovative insight into the theoretical explanation of the origin of the size and composition effects to inform the design of highly efficient electrocatalysts.