Critical roles of sulfidation solvent in controlling surface properties and the dechlorination reactivity of S-nZVI.

Sulfidation of nanoscale zero-valent iron (nZVI) has been frequently applied to enhance its reactivity, selectivity, and electron utilization efficiency. However, sulfidation of nZVI is generally carried out in aqueous solution, and formation of passivated iron (hydro)oxide species on the surface of S-nZVI due to the reaction between nZVI and water is inevitable. To mitigate this issue, sulfidation of nZVI with hydrogen sulfide dissolved in absolute ethanol was developed. The properties of the resultant S-nZVI, denoted as S-nZVI-HS-Ethanol, were compared with S-nZVIs prepared through sulfidation of nZVI with aqueous hydrogen sulfide (S-nZVI-HS-Water) and aqueous sodium sulfide (S-nZVI-NaS-Water). S-nZVI-HS-Ethanol shows increased BET specific surface, reduced susceptibility to incidental oxidation, increased reduction potential, decreased electron-transfer resistance, and improved reactivity toward the reduction of trichloroethylene, compared with S-nZVI-NaS-Water and S-nZVI-HS-Water. The results highlight the critical roles of sulfidation solvent in controlling the structure, the physicochemical and electrochemical properties, and the dechlorination reactivity of S-nZVI. In addition, these findings offer fundamental mechanistic insights into the sulfidation processes of nZVI by sulfides, suggesting that solvent-iron (hydro)oxide and sulfide-iron (hydro)oxide interactions at the solvent/nZVI interface play key roles in regulating the sulfidation of nZVI and the properties of S-nZVI.