Enhanced photocatalysis using metal-organic framework MIL-101(Fe) for organophosphate degradation in water

Metal-organic frameworks (MOFs) are attractive novel classes of porous materials with diverse potentiality and easily tailored structures. It is desirable to evaluate the performance of MOFs as photocatalysts for organic contaminant removal in aqueous matrixes. In this study, iron-based MIL-101(Fe) was synthesized and a photo-Fenton reaction system (multiple wavelength light + MIL-101(Fe) + H₂O₂) was developed for elimination of tris(2-chloroethyl) phosphate (TCEP). Degradation pattern of TCEP followed an S-shape curve, which included a slow induction period and a rapid radical oxidation process. Transport of reactants into MIL-101(Fe) and the activation of electron transport within Fe-O clusters of MIL-101(Fe) may be the dominant mechanisms in the induction period, while a pseudo-first-order kinetics was observed in the hydroxyl radical oxidation process. Removal efficiencies in these two stages highly depended on the reaction conditions. Irradiation at 420 nm and acid condition were conductive, while high temperature and high [H₂O₂]:[MIL-101(Fe)] mass ratio accelerated the reaction. Before complete mineralization, eleven degradation products were generated, and the dominant degradation pathways included cleavage, hydroxylation, carbonylation, and carboxylation. Under acid condition (pH = 3), only 1% mass loss was observed after 60-min reaction, but the iron leakage was aggravated when pH increased. Furthermore, this MOF-photo-Fenton system demonstrated a robust performance on TCEP degradation in actual wastewater matrixes under acid condition. Generally, the MOF-photo-Fenton system is a potential technology for elimination of organic pollutants in aqueous solution.