Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

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

Roldan Martinez, Alberto and de Leeuw, Nora H. 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

[img]
Preview
PDF - Published Version
Available under License Creative Commons Attribution.

Download (2MB) | Preview

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: Chemistry
Cardiff Catalysis Institute (CCI)
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: 30 Apr 2019 16:49
URI: http://orca-mwe.cf.ac.uk/id/eprint/118611

Actions (repository staff only)

Edit Item Edit Item

Downloads

Downloads per month over past year

View more statistics