The design and preparation of PDI modified NH2-MIL-101(Fe) for high efficiency removal of dimethoate in peroxymonosulfate system: Performance, mechanism, pathway and toxicity assessment.

Abstract

The widespread use of organophosphorus pesticide dimethoate (DMT) in agriculture poses a threat to human health. In this work, the perylene tetracarboxylic diimide (PDI) modified NH₂-MIL-101(Fe) (PDI/MIL) with strong covalent bond C(=O)-N were designed and prepared by a step solvothermal method. The synergistic effect between photocatalytic and peroxymonosulfate (PMS) activation for the DMT elimination over PDI/MIL was gained. Interestingly, PDI/MIL(1:10)/PMS showed boosting degradation efficiency (95.6%) for DMT under 18 min simulated sunlight irradiation. Its apparent reaction rate constant was 24.7 times higher than that of NH₂-MIL-101(Fe)/PMS. Moreover, its reusability, stability and mineralization ability were evaluated, and a remarkable mineralization rate of 95.3% with 90 min was achieved. The enhanced activity were attributed to the formation of amide bond that exhibited superior charger transport ability and amount of produced active species. Combined the results obtained from the HPLC-MS and molecular structure characteristics of DMT analyzed by Fukui index, the degradation pathways were proposed. The toxicity of intermediates were predicted by Ecological Structure Activity Relationship (ECOSAR), Toxicity Estimation Software Tool (T.E.S.T.), and Vibrio fischeri experiments. Our work provided deep insights into the mechanisms of DMT degradation via photocatalysis-activated PMS over organic semiconductor modified metal organic frameworks.