Enhanced Reactivity and Electron Selectivity of Sulfidated Zerovalent Iron toward Chromate under Aerobic Conditions

When zerovalent iron (ZVI) is used in reductive removal of contaminants from industrial wastewater, where dissolved oxygen (DO) competes with target contaminant for the electrons donated by ZVI, both the reactivity and the electron selectivity (ES) of ZVI toward target contaminant are critical. Thus, the reactivity and ES of two sulfidated ZVI (S-ZVI) samples, synthesized by ball-milling with elemental sulfur (S-ZVI^bm) and reacting with Na₂S (S-ZVI^Na2S), toward Cr­(VI) under aerobic conditions were investigated. Sulfidation appreciably increased the reactivity of ZVI and the ratio of the rate constants for Cr­(VI) removal by S-ZVI^bm or S-ZVI^Na2S to their counterparts without sulfur fell in the range of 1.4–29.9. ES of S-ZVI^bm and S-ZVI^Na2S toward Cr­(VI) were determined to be 14.6% and 13.3%, which were 10.7- and 7.5-fold greater than that without sulfidation, respectively. This was mainly ascribed to the greater improving effect of sulfidation on the reduction rate of Cr­(VI) than that of DO by ZVI. The improving effects of sulfidation on the performance of ZVI were mainly due to the following mechanisms: sulfidation increased the specific surface area of ZVI, the FeS_<i>x</i> layer facilitated the enrichment of Cr­(VI) anions on S-ZVI surface because of its anions selective property and favored the electron transfer from Fe⁰ core to Cr­(VI) at the surface because of its role as efficient electron conductor