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

MetadataDetails
Publication Date2024-12-16
JournalJournal of Computational Chemistry
AuthorsOliver J. Conquest, Yijiao Jiang, Catherine Stampfl
InstitutionsMacquarie University, The University of Sydney
Citations2

ABSTRACT Using first principles calculations we investigate cobalt‐coordinated tetracyanoquinodimethane (R‐CoTCNQ) as a potential catalyst for the CO 2 electroreduction reaction (CO 2 ERR). 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 r 2 SCAN functional is used in this study. The free energy CO 2 ERR reaction pathways are calculated for the reduced catalyst ([R‐CoTCNQ] −1 e ) with reaction products HCOOH and HCHO predicted depending on our choice of electrode potential. Calculations are also performed for [R‐CoTCNQ] −1 e supported on a H‐terminated diamond (1 1 0) surface with reaction pathways being qualitatively similar to the [R‐CoTCNQ] −1 e monolayer. The inclusion of boron‐doping in the diamond support shows a slightly improved CO 2 ERR 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.