Reduction: Role and Influence of the Substrate*

The strong electron acceptor nature of certain metal coordinated molecules, together with their ability to form two-dimesional structures on supports, has recently been exploited for catalytic reactions. In this work we study two-dimensional cobalt-coordinated Tetracyanoquinodimethane (Co-TCNQ) using density functional theory with GGA-PBE+D3 level of theory. Previous studies have shown Co-TCNQ has a lower predicted overpotential for CO₂RR compared to other transition metal TCNQ coordination networks. The CO₂ reduction reaction (CO₂RR) performance is determined by calculating the free energy reaction pathways, where we identify the role and influence of the substrate material. We consider copper, graphene, pristine and defective diamond supports and study their impact on the electronic properties of the cobalt active site which directly impacts the reaction performance.