Enhancing carbon dioxide reduction electrocatalysis by tuning metal-support interactions: a first principles study

The electrochemical reduction of CO2 is an extremely potential technique to achieve the goal of carbon neutrality, but the development of electrocatalysts with high activity, excellent product selectivity, and long-term durability remains a great challenge. Herein, the role of metal-supports interaction (MSI) between different active sites (including single and bimetallic atom sites consisting of Cu and Ni atoms) and carbon-based supports (including C2N, C3N4, N-coordination graphene, and graphdiyne) on catalytic activity, product selectivity, and thermodynamic stability towards CO2 reduction reaction (CRR) is systematically investigated by first principles calculations. Our results show that MSI is mainly related to the charge transfer behavior from metal sites to supports, and different MSI leads to diverse magnetic moments and d-band centers. Subsequently, the adsorption and catalytic performance can be efficiently improved by tuning MSI. Notably, the bimetallic atom supported graphdiyne not only exhibits a better catalytic activity, higher product selectivity, and higher thermodynamic stability, but also effectively inhibits the hydrogen evolution reaction. This finding provides a new research idea and optimization strategy for the rational design of high-efficiency CRR catalysts. [Display omitted] •The CRR activity of carbon-based materials embedded with metal sites is investigated.•The product selectivity can be significantly improved by constructing bimetallic atom sites.•The bimetallic atom supported graphdiynes are proved to be promising catalysts for CRR.•The metal-supports interaction is mainly related to the charge transfer behavior from metal sites to supports.•The adsorption and catalytic performance can be efficiently improved by tuning metal-supports interaction.