Supported 2D-coordinated networks for CO₂ 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.

*We gratefully acknowledge financial support from the Australian research council (ARC) disocvery project DP901013720. We acknowledge computional support from the National Computational Infastructure (NCI) and access to computional resources which is supported by the Australian Government. Lastly we acknowledge scientific and technical support provided by the Sydney Informatics Hub and access to the Artemis high performance computing facility.