A density functional theory study of the hydrogenation and reduction of the thio-spinel Fe3S4{111} surface

Roldan Martinez, Alberto ORCID: https://orcid.org/0000-0003-0353-9004 and de Leeuw, Nora H. ORCID: https://orcid.org/0000-0002-8271-0545 2019. A density functional theory study of the hydrogenation and reduction of the thio-spinel Fe3S4{111} surface. Physical Chemistry Chemical Physics 10.1039/C8CP06371K

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Abstract

The mineral greigite, Fe3S4, shows promising electro-reduction activity, especially towards carbon dioxide conversion to small organic molecules. We have employed density functional theory calculations with correction for the long-range dispersion forces to investigate the behavior of hydrogen on the greigite{111} surface. We have studied the adsorption, diffusion, surface reduction and associative (i.e. Volmer–Tafel mechanism) and molecular desorption of hydrogen as a function of its coverage. We found that (i) the H ad-atoms adsorb on S sites far from metallic centres in the topmost surface layer; (ii) the reduction of greigite by hydrogen is energetically unfavorable at any surface coverage; and (iii) molecular hydrogen evolution has a transition state at ∼0.5 eV above the energy of the reactants on Fe3S4{111}, which is very similar to the barrier found experimentally on Pt{111}. We have also determined the electrode potential under room conditions at which the H2 evolution reaction becomes energetically barrierless.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Cardiff Catalysis Institute (CCI) Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Funders:	EPSRC
Date of First Compliant Deposit:	22 January 2019
Date of Acceptance:	16 November 2018
Last Modified:	05 Aug 2024 15:17
URI:	https://orca.cardiff.ac.uk/id/eprint/118611

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