First-principles insights into sulfur oxides (SO2 and SO3) adsorption and dissociation on layered iron sulfide (FeS) catalyst

The adsorption of sulfur oxides (SOx) represents the fundamental step towards their conversion to lower-risk sulfur-containing species. Herein, we investigate the adsorption and dissociation mechanism of sulfur dioxide (SO2) and sulfur trioxide (SO3) on layered iron sulfide (FeS) nanocatalyst (001), (011), and (111) surfaces using density functional theory methodology. Both SO2 and SO3 exhibit strong reactivity towards the (011) and (111) surfaces, with the most stable geometry for SO2 and SO3 on the (011) surface predicted to be a tridentate η23(S,O,O) and a bidentate η22(O,O) configuration, respectively, whereas on the (111) surface, they are predicted to be coordinated in a monodentate η21(S) and η21(O) geometry, respectively. Significant charge donation from the FeS surface to the SOx species is observed, which resulted in elongation of S−O bond lengths, confirmed by vibrational frequency analyses. Favourable reaction energy and activation barrier is predicted for SO2 dissociation at the (111) surface. [Display omitted] •Sulfur oxides (SO2 and SO3) adsorption on layered FeS surfaces are characterized.•The adsorption process is driven by significant charge donation from the interacting surface Fe sites to the SOx species.•S−O bond activation and elongation is observed and confirmed via vibrational frequency analyses.•The thermodynamics and kinetics of SOx dissociation are analyzed.