Iron and Sulfur Precursors Affect Crystalline Structure, Speciation, and Reactivity of Sulfidized Nanoscale Zerovalent Iron

摘要

The reactivity of sulfidized nanoscale zerovalent iron (SNZVI) is affected by the amount and species of sulfur in the materials. Here, we assess the impact of the Fe (Fe~(2+) and Fe~(3+)) and S (S_2O_4~(2-), S~(2-), and S_6~(2-)) precursors used to synthesize both NZVI and SNZVI on the resulting physicochemical properties and reactivity and selectivity with water and trichloroethene (TCE). X-ray diffraction indicated that the Fe precursors altered the crystalline structure of both NZVI and SNZVI. The materials made from the Fe~(3+) precursor had an expanded lattice in the Fe~0 body-centered-cubic (BCC) structure and lower electron-transfer resistance, providing higher reactivity with water (～2-3 fold) and TCE (～5-13 fold) than those made from an Fe~(2+) precursor. The choice of the S precursor controlled the S speciation in the SNZVI particles, as indicated by X-ray absorption spectroscopy. Iron disulfide (FeS_2) was the main S species of SNZVI made from S_2O_4~(2-), whereas iron sulfide (FeS) was the main S species of SNZVI made from S~(2-)/S_6~(2-). The former SNZVI was more hydrophobic, reactive with, and selective for TCE compared to the latter SNZVI. These results suggest that the Fe and S precursors can be used to select the conditions of the synthesis process and provide selected physicochemical properties (e.g., S speciation, hydrophobicity, and crystalline structure), reactivity, and selectivity of the SNZVI materials.