Investigating the interplay between charge transfer and CO 2 insertion in the adsorption of a NiFe catalyst for CO 2 electroreduction on a graphite support through DFT computational approaches.

Autor: Arjunan S; Université Grenoble Alpes, DCM, CNRS, Grenoble, France.; Université Grenoble Alpes, CEA, CNRS, Grenoble INP, IRIG, SyMMES, Grenoble, France., Sims JM; Université Grenoble Alpes, DCM, CNRS, Grenoble, France.; ENSL, CNRS, Lab Chim, UMR 5182, Lyon, France., Duboc C; Université Grenoble Alpes, DCM, CNRS, Grenoble, France., Maldivi P; Université Grenoble Alpes, CEA, CNRS, Grenoble INP, IRIG, SyMMES, Grenoble, France., Milet A; Université Grenoble Alpes, DCM, CNRS, Grenoble, France.
Jazyk: angličtina
Zdroj: Journal of computational chemistry [J Comput Chem] 2024 Jul 15; Vol. 45 (19), pp. 1690-1696. Date of Electronic Publication: 2024 Apr 02.
DOI: 10.1002/jcc.27355
Abstrakt: This article describes a density functional theory (DFT) study to explore a bio-inspired NiFe complex known for its experimental activity in electro-reducing CO 2 to CH 4 when adsorbed on graphite. The coordination properties of the complex are investigated in isolated form and when physisorbed on a graphene surface. A comparative analysis of DFT approaches for surface modeling is conducted, utilizing either a finite graphene flake or a periodic carbon surface. Results reveal that the finite model effectively preserves all crucial properties. By examining predicted structures arising from CO 2 insertion within the mono-reduced NiFe species, whether isolated or adsorbed on the graphene flake, a potential species for subsequent electro-reduction steps is proposed. Notably, the DFT study highlights two positive effects of complex adsorption: facile electron transfers between graphene and the complex, finely regulated by the complex state, and a lowering of the thermodynamic demand for CO 2 insertion.
(© 2024 Wiley Periodicals LLC.)
Databáze: MEDLINE
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