Sulfur Loading and Speciation Control the Hydrophobicity, Electron Transfer, Reactivity, and Selectivity of Sulfidized Nanoscale Zerovalent Iron

Sulfidized nanoscale zerovalent iron (SNZVI) is a promising material for groundwater remediation. However, the relationships between sulfur content and speciation and the properties of SNZVI materials are unknown, preventing rational design. Here, the effects of sulfur on the crystalline structure, hydrophobicity, sulfur speciation, corrosion potential, and electron transfer resistance are determined. Sulfur incorporation extended the nano‐Fe0 BCC lattice parameter, reduced the Fe local vacancies, and lowered the resistance to electron transfer. Impacts of the main sulfur species (FeS and FeS2) on hydrophobicity (water contact angles) are consistent with density functional theory calculations for these FeSx phases. These properties well explain the reactivity and selectivity of SNZVI during the reductive dechlorination of trichloroethylene (TCE), a hydrophobic groundwater contaminant. Controlling the amount and speciation of sulfur in the SNZVI made it highly reactive (up to 0.41 L m−2 d−1) and selective for TCE degradation over water (up to 240 moles TCE per mole H2O), with an electron efficiency of up to 70%, and these values are 54‐fold, 98‐fold, and 160‐fold higher than for NZVI, respectively. These findings can guide the rational design of robust SNZVI with properties tailored for specific application scenarios. The amount and speciation of sulfur incorporated into the crystalline structure of nano‐Fe° controls the materials' hydrophobicity, electron transfer resistance, and adsorbed H, and the rate of reaction with trichloroethylene and water. This work can guide the rational design of robust sulfidized nano‐Fe0 with optimal properties for groundwater treatment.