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