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Adsorption and desulfurization mechanism of thiophene on layered FeS (001), (011) and (111) surfaces: A DFT-D2 study

Dzade, Nelson ORCID: and De Leeuw, Nora H. ORCID: 2018. Adsorption and desulfurization mechanism of thiophene on layered FeS (001), (011) and (111) surfaces: A DFT-D2 study. Journal of Physical Chemistry C 122 (1) , pp. 359-370. 10.1021/acs.jpcc.7b08711

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Layered transition-metal chalcogenides have emerged as a fascinating new class of materials for catalysis. Here, we present periodic density functional theory (DFT) calculations of the adsorption of thiophene and the direct desulfurization reaction pathways on the (001), (011), and (111) surfaces of layered FeS. The fundamental aspects of the thiophene adsorption, including the initial adsorption geometries, adsorption energies, structural parameters, and electronic properties, are presented. From the calculated adsorption energies, we show that the flat adsorption geometries, wherein the thiophene molecule forms multiple π-bonds with the FeS surfaces, are energetically more favorable than the upright adsorption geometries, with the strength of adsorption decreasing in the order FeS(111) > FeS(011) > FeS(001). The adsorption of the thiophene onto the reactive (011) and (111) surfaces is shown to be characterized by charge transfer from the interacting Fe d-band to the π-system of the thiophene molecule, which causes changes of the intramolecular structure including loss of aromaticity and elongation of the C–S bonds. The thermodynamic and kinetic analysis of the elementary steps involved in the direct desulfurization of thiophene on the reactive FeS surfaces is also presented. Direct desulfurization of thiophene occurs preferentially on the (111) surface, as reflected by the overall exothermic reaction energy calculated for the process (ER = −0.15 eV), with an activation energy of 1.58 eV.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 1932-7447
Funders: EPSRC
Date of First Compliant Deposit: 30 November 2017
Date of Acceptance: 28 November 2017
Last Modified: 07 Nov 2023 06:50

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