CoTCNQ as a Catalyst for CO Electroreduction: A First Principles rSCAN Meta-GGA Investigation.

Using first principles calculations we investigate cobalt-coordinated tetracyanoquinodimethane (R-CoTCNQ) as a potential catalyst for the CO electroreduction reaction (COERR). We determine that exchange-correlation functionals beyond the generalized gradient approximation (GGA) are required to accurately describe the spin properties of R-CoTCNQ, therefore, the meta-GGA rSCAN functional is used in this study. The free energy COERR reaction pathways are calculated for the reduced catalyst ([R-CoTCNQ]) with reaction products HCOOH and HCHO predicted depending on our choice of electrode potential. Calculations are also performed for [R-CoTCNQ] supported on a H-terminated diamond (1 1 0) surface with reaction pathways being qualitatively similar to the [R-CoTCNQ] monolayer. The inclusion of boron-doping in the diamond support shows a slightly improved COERR reaction pathway. Furthermore, structurally, supported R-CoTCNQ provide a high specific area of active Co active sites and could be promising catalysts for future experimental consideration.