Structuresand Properties of As(OH)3 AdsorptionComplexes on Hydrated Mackinawite (FeS) Surfaces: A DFT-D2 Study

摘要

Reactive mineral–water interfaces exert control on the bioavailability of contaminant arsenic species in natural aqueous systems. However, the ability to accurately predict As surface complexation is limited by the lack of molecular-level understanding of As–water–mineral interactions. In the present study, we report the structures and properties of the adsorption complexes of arsenous acid (As(OH)3) on hydrated mackinawite (FeS) surfaces, obtained from density functional theory (DFT) calculations. The fundamental aspects of the adsorption, including the registries of the adsorption complexes, adsorption energies, and structural parameters are presented. The FeS surfaces are shown to be stabilized by hydration, as is perhaps to be expected because the adsorbed water molecules stabilize the low-coordinated surface atoms. As(OH)3 adsorbs weakly at the water–FeS(001) interface through a network of hydrogen-bonded interactions with water molecules on the surface, with the lowest-energy structure calculated to be an As–up outer-sphere complex. Compared to the water–FeS(001)interface, stronger adsorption was calculated for As(OH)3 on the water–FeS(011) and water–FeS(111) interfaces,characterized by strong hybridization between the S-p and O-p states of As(OH)3 and the surfaceFe-d states. The As(OH)3 molecule displayeda variety of chemisorption geometries on the water–FeS(011)and water–FeS(111) interfaces, where the most stable configurationat the water–FeS(011) interface is a bidentate Fe–AsO–Fecomplex, but on the water–FeS(111) interface, a monodentateFe–O–Fe complex was found. Detailed information regardingthe adsorption mechanisms has been obtained via projected densityof states (PDOS) and electron density difference iso-surface analysesand vibrational frequency assignments of the adsorbed As(OH)3 molecule.