Sulfurized nano zero-valent iron prepared via different methods: Effect of stability and types of surface corrosion products on removal of 2,4,6-trichlorophenol

Sulfurization improves the stability and activity of nano zero-valent iron (nZVI). The sulfurized nZVI (S-nZVI) were prepared with ball milling, vacuum chemical vapor deposition (CVD) and liquid-phase reduction techniques and the corresponding products were the mixture of FeS₂ and nZVI (nZVI/FeS₂), well-defined core-shell structure (FeS_x@Fe) or seriously oxidized (S-nZVI(aq)), respectively. All these materials were applied to eliminate 2,4,6-trichlorophenol (TCP) from water. The removal of TCP was irrelevant with the structure of S-nZVI. Both nZVI/FeS₂ and FeS_x@Fe showed remarkable performance for the degradation of TCP. S-nZVI(aq) possessed poor mineralization efficiency to TCP due to its bad crystallinity degree and severe leaching of Fe ions, which retarded the affinity of TCP. Desorption and quenching experiments suggested that TCP removal by nZVI and S-nZVI was based on surface adsorption and subsequent direct reduction by Fe⁰, oxidation by in-situ produced ROS and polymerization on the surface of these materials. In the reaction process, the corrosion products of these materials transformed into crystalline Fe₃O₄ and α/β-FeOOH, which enhanced the stability of nZVI and S-nZVI materials and was conductive to the electron transferring from Fe⁰ to TCP and strong affinity of TCP onto Fe or FeS_x phases. All these were contributed to high performance of nZVI and sulfurized nZVI in removal and minerazilation of TCP in continuous recycle test.