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CO2 interaction with violarite (FeNi2S4) surfaces: a dispersion-corrected DFT study

Santos Carballal, David, Posada-Pérez, Sergio, Terranova, Umberto, Roldan Martinez, Alberto, Illas, Francesc and De Leeuw, Nora 2018. CO2 interaction with violarite (FeNi2S4) surfaces: a dispersion-corrected DFT study. Physical Chemistry Chemical Physics 20 (31) , pp. 20439-20446. 10.1039/C8CP03430C

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Abstract

The unbridled emissions of gases derived from the use of fossil fuels have led to an excessive concentration of carbon dioxide (CO2) in the atmosphere with concomitant problems to the environment. It is therefore imperative that new cost-effective catalysts are developed to mitigate the resulting harmful effects through the activation and conversion of CO2 molecules. In this paper, we have used calculations based on the density functional theory (DFT), including two semi-empirical approaches for the long-range dispersion interactions (-D2 and -D3), to explore the interaction of CO2 with the surfaces of spinel-structured violarite (FeNi2S4). This ternary sulfide contains iron ions in the highest possible oxidation state, while the nickel atoms are in the mixed 2+/3+ valence state. We found that CO2 interaction with violarite is only moderate due to the repulsion between the oxygen lone pairs and the electronic clouds of the sulfur surface atoms. This suggests that the CO2 activation is not dictated by the presence of nickel, as compared to the pure iron-isomorph greigite (Fe3S4). These results differ from findings in (Ni,Fe) ferredoxin enzymes, where the Ni/Fe ratio influences the redox potential, which suggests that the periodic crystal structure of violarite may hinder its redox capability.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Advanced Research Computing @ Cardiff (ARCCA)
Publisher: Royal Society of Chemistry
ISSN: 1463-9076
Funders: EPSRC
Date of First Compliant Deposit: 31 July 2018
Date of Acceptance: 16 July 2018
Last Modified: 14 Aug 2019 14:16
URI: http://orca-mwe.cf.ac.uk/id/eprint/113786

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