High-Performance of Electrocatalytic CO2 Reduction on Defective Graphene-Supported Cu4S2 Cluster

Electrochemical CO2 reduction reaction (CO2RR) to high-value chemicals is one of the most splendid approaches mitigating environmental threats and energy shortage. In this study, catalytic performance CO2RR on defective graphene-supported Cu4S2 clusters as well isolated Cu4Xn (X = O, S, Se; n 2, 4) was systematically investigated based density functional theory (DFT) computations. Calculation results revealed that thermodynamically feasible product CH3OH among C1 products Cu4X2 clusters, in which cluster has best activity concerning synthesis with a limiting potential −0.48 V. When further supported graphene, strong interaction between substrate could greatly improve via tuning electronic structure improving stability cluster. The calculated free diagram indicated it also more energetically preferable for production low −0.35 Besides, graphene support significant ability suppress competing reactions, such hydrogen evolution (HER) CO HCOOH production. Geometric structures, potentials, pathways were discussed gain insight into mechanism find minimum-energy pathway products. We hope work will provide theoretical reference designing developing advanced Cu-based electrocatalysts reduction.