Surface dual redox cycles of Mn(III)/Mn(IV) and Cu(I)/Cu(II) for heterogeneous peroxymonosulfate activation to degrade diclofenac: Performance, mechanism and toxicity assessment

Abstract

Advanced oxidation processes (AOPs) based on heterogeneous catalytic activated peroxymonosulfate (PMS) have been becoming alternatives to conventional wastewater treatment technologies to directly degrade chemical contaminants. To build dual/multi redox cycles of different metal ions may be an effective means for better PMS activation. Herein, this study designed Mn3O4/CuBi2O4 with dual redox cycles of Mn(III)/Mn(IV) and Cu(I)/Cu(II) to activate PMS for efficiently decomposing and mineralizing diclofenac sodium (DCF). Under optimal reaction conditions, DCF (50 mg/L) was degraded totally within 10 min, and TOC removal rate reached up to 74.3%. The possible mechanism of PMS activation by Mn3O4/CuBi2O4 was proposed, wherein dual redox cycles of Mn(III)/Mn(IV) and Cu(I)/Cu(II) on Mn3O4/CuBi2O4 effectively facilitated PMS activation to generate ·O2−, 1O2, SO4·− and ·OH, which was responsible for DCF degradation. Moreover, combined with degraded products detected by high resolution liquid chromatography coupled to mass spectrometry and corresponding toxic assessment results, the possible degradation pathways of DCF were proposed and the relative toxicity of degraded products was evaluated. This work may be useful for developing stronger heterogeneous activators of PMS to construct more efficient AOPs for purifying wastewater.