Next Article in Journal
A Comprehensive Study of Coke Deposits on a Pt-Sn/SBA-16 Catalyst during the Dehydrogenation of Propane
Next Article in Special Issue
Theoretical Insights into the Hydrogen Evolution Reaction on the Ni3N Electrocatalyst
Previous Article in Journal
Efficient Photocatalytic Degradation of Gaseous Benzene and Toluene over Novel Hybrid [email protected]2/m-GO Composites
Previous Article in Special Issue
Electrooxidation of Urea in Alkaline Solution Using Nickel Hydroxide Activated Carbon Paper Electrodeposited from DMSO Solution
Article

Activating the FeS (001) Surface for CO2 Adsorption and Reduction through the Formation of Sulfur Vacancies: A DFT-D3 Study

by 1,2,* and 1,2,3,*
1
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
2
Department of Earth Sciences, Utrecht University, Princetonlaan 8A, 3584 CB Utrecht, The Netherlands
3
School of Chemistry, University of Leeds, Leeds LT2 9JT, UK
*
Authors to whom correspondence should be addressed.
Catalysts 2021, 11(1), 127; https://doi.org/10.3390/catal11010127
Received: 30 December 2020 / Revised: 12 January 2021 / Accepted: 12 January 2021 / Published: 15 January 2021
(This article belongs to the Special Issue Catalysts in Energy Applications)
As a promising material for heterogeneous catalytic applications, layered iron (II) monosulfide (FeS) contains active edges and an inert basal (001) plane. Activating the basal (001) plane could improve the catalytic performance of the FeS material towards CO2 activation and reduction reactions. Herein, we report dispersion-corrected density functional theory (DFT-D3) calculations of the adsorption of CO2 and the elementary steps involved in its reduction through the reverse water-gas shift reaction on a defective FeS (001) surface containing sulfur vacancies. The exposed Fe sites resulting from the creation of sulfur vacancies are shown to act as highly active sites for CO2 activation and reduction. Based on the calculated adsorption energies, we show that the CO2 molecules will outcompete H2O and H2 molecules for the exposed active Fe sites if all three molecules are present on or near the surface. The CO2 molecule is found to weakly physisorb (−0.20 eV) compared to the sulfur-deficient (001) surface where it adsorbs much strongly, releasing adsorption energy of −1.78 and −1.83 eV at the defective FeS (001) surface containing a single and double sulfur vacancy, respectively. The CO2 molecule gained significant charge from the interacting surface Fe ions at the defective surface upon adsorption, which resulted in activation of the C–O bonds confirmed via vibrational frequency analyses. The reaction and activation energy barriers of the elementary steps involved in the CO2 hydrogenation reactions to form CO and H2O species are also unraveled. View Full-Text
Keywords: iron sulfides (Fes); carbon dioxide (CO2); adsorption; activation; reaction mechanisms iron sulfides (Fes); carbon dioxide (CO2); adsorption; activation; reaction mechanisms
Show Figures

Graphical abstract

MDPI and ACS Style

Dzade, N.Y.; de Leeuw, N.H. Activating the FeS (001) Surface for CO2 Adsorption and Reduction through the Formation of Sulfur Vacancies: A DFT-D3 Study. Catalysts 2021, 11, 127. https://doi.org/10.3390/catal11010127

AMA Style

Dzade NY, de Leeuw NH. Activating the FeS (001) Surface for CO2 Adsorption and Reduction through the Formation of Sulfur Vacancies: A DFT-D3 Study. Catalysts. 2021; 11(1):127. https://doi.org/10.3390/catal11010127

Chicago/Turabian Style

Dzade, Nelson Y., and Nora H. de Leeuw 2021. "Activating the FeS (001) Surface for CO2 Adsorption and Reduction through the Formation of Sulfur Vacancies: A DFT-D3 Study" Catalysts 11, no. 1: 127. https://doi.org/10.3390/catal11010127

Find Other Styles
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Back to TopTop