CoTCNQ as a Catalyst for CO₂ Electroreduction: A First Principles r²SCAN Meta‐GGA Investigation

Abstract

Using first principles calculations we investigate cobalt‐coordinated tetracyanoquinodimethane (R‐CoTCNQ) as a potential catalyst for the CO2 electroreduction reaction (CO2ERR). 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 r2SCAN functional is used in this study. The free energy CO2ERR reaction pathways are calculated for the reduced catalyst ([R‐CoTCNQ]−1e) with reaction products HCOOH and HCHO predicted depending on our choice of electrode potential. Calculations are also performed for [R‐CoTCNQ]−1e supported on a H‐terminated diamond (1 1 0) surface with reaction pathways being qualitatively similar to the [R‐CoTCNQ]−1e monolayer. The inclusion of boron‐doping in the diamond support shows a slightly improved CO2ERR 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.