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Article

Changes in CO2 Adsorption Affinity Related to Ni Doping in FeS Surfaces: A DFT-D3 Study

1
Department of Earth Sciences, Utrecht University, Princetonlaan 8a, 3584CB Utrecht, The Netherlands
2
School of Chemistry, University of Leeds, Leeds LS2 9JT, UK
3
School of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, UK
*
Authors to whom correspondence should be addressed.
Academic Editor: Francis Verpoort
Catalysts 2021, 11(4), 486; https://doi.org/10.3390/catal11040486
Received: 19 March 2021 / Revised: 7 April 2021 / Accepted: 8 April 2021 / Published: 10 April 2021
Metal sulphides constitute cheap, naturally abundant, and environmentally friendly materials for energy storage applications and chemistry. In particular, iron (II) monosulphide (FeS, mackinawite) is a material of relevance in theories of the origin of life and for heterogenous catalytic applications in the conversion of carbon dioxide (CO2) towards small organic molecules. In natural mackinawite, Fe is often substituted by other metals, however, little is known about how such substitutions alter the chemical activity of the material. Herein, the effect of Ni doping on the structural, electronic, and catalytic properties of FeS surfaces is explored via dispersion-corrected density functional theory simulations. Substitutional Ni dopants, introduced on the Fe site, are readily incorporated into the pristine matrix of FeS, in good agreement with experimental measurements. The CO2 molecule was found to undergo deactivation and partial desorption from the doped surfaces, mainly at the Ni site when compared to undoped FeS surfaces. This behaviour is attributed to the energetically lowered d-band centre position of the doped surface, as a consequence of the increased number of paired electrons originating from the Ni dopant. The reaction and activation energies of CO2 dissociation atop the doped surfaces were found to be increased when compared to pristine surfaces, thus helping to further elucidate the role Ni could have played in the reactivity of FeS. It is expected that Ni doping in other Fe-sulphides may have a similar effect, limiting the catalytic activity of these phases when this dopant is present at their surfaces. View Full-Text
Keywords: iron sulphides; mackinawite; density functional theory; carbon dioxide (CO2) adsorption; nickel doping iron sulphides; mackinawite; density functional theory; carbon dioxide (CO2) adsorption; nickel doping
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MDPI and ACS Style

Živković, A.; Somers, M.; Camprubi, E.; King, H.E.; Wolthers, M.; de Leeuw, N.H. Changes in CO2 Adsorption Affinity Related to Ni Doping in FeS Surfaces: A DFT-D3 Study. Catalysts 2021, 11, 486. https://doi.org/10.3390/catal11040486

AMA Style

Živković A, Somers M, Camprubi E, King HE, Wolthers M, de Leeuw NH. Changes in CO2 Adsorption Affinity Related to Ni Doping in FeS Surfaces: A DFT-D3 Study. Catalysts. 2021; 11(4):486. https://doi.org/10.3390/catal11040486

Chicago/Turabian Style

Živković, Aleksandar, Michiel Somers, Eloi Camprubi, Helen E. King, Mariette Wolthers, and Nora H. de Leeuw 2021. "Changes in CO2 Adsorption Affinity Related to Ni Doping in FeS Surfaces: A DFT-D3 Study" Catalysts 11, no. 4: 486. https://doi.org/10.3390/catal11040486

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