Partial aging can counter-intuitively couple with sulfidation to improve the reactive durability of zerovalent iron

Abstract

Sulfated zero-valent iron (SZVI) has shown promising applications in wastewater treatment. However, the rapid decline in the reactivity of SZVI with time limits its real practice. To mediate this problem, partial aging was proposed to improve the reactive durability of SZVI. Taking Cr(VI) as the target contaminant, we found that the aged ZVI (AZVI) gradually lost reactivity as aging time increased from 0.5 to 2 d. Counter-intuitively, the partially aged SZVI (ASZVI) showed greater reactivity than SZVI when exposed to oxygenated water for a period ranging from 0.5 to 14 d. In addition, the ASZVI with 0.5 d of aging time (ASZVI-0.5) not only maintained reactivity in successive runs but also increased the Cr(VI) removal capacity from 9.1 mg/g by SZVI to 19.1 mg/g by ASZVI-0.5. Correlation analysis further revealed that the electron transfer from the Fe0 core to the shell was mediated by the conductive FeS and FeS2 in the subshell of ASZVI. Meanwhile, the lepidocrocite and magnetite on the surface of ASZVI facilitated Cr(VI) adsorption and subsequent electron transfer for Cr(VI) reduction. Moreover, the iron (hydr)oxide shell could retain the conductive FeS and FeS2 in the subshell, allowing ASZVI to reduce Cr(VI) efficiently and sustainably. In general, partial aging can enhance the reactive durability of ZVI when coupled with sulfidation and this synergistic effect will be beneficial to the application of SZVI-based technology for wastewater treatment.