Graphene/MoS2-assisted alum sludge electrode induces selective oxidation for organophosphorus pesticides degradation: Co-oxidation and detoxification mechanism

Abstract

Designing an electrode that can generate abundant free radicals and 1O2, which can effectively degrade and detoxify organophosphorus pesticides (OPPs) through a co-oxidation pathway, is important. In this study, we prepared a electrode GO/MoS2@AS by supporting MoS2 on alum sludge (AS) under graphene oxide (GO) nanoconfinement. The results show that the dominant role of 1O2 at the cathode and •OHads at the anode for degradation, in addition to the involvement of 1O2 in the cathodic degradation mechanism, can be attributed to the abundant precursor •O2– and H2O2. Furthermore, calculations using density functional theory and toxicity prediction of products show that the energy (∆E) requirements of •OHfree to break the C–O bond of the pyridine ring and phosphate group are higher than that required for 1O2, and this non-radical oxidation plays a key role in detoxification. In contrast, accelerating ring opening and oxidation processes are attributed to radical oxidation. Above all, the cathodic detoxification is more effective than anodic detoxification. Three prevalent OPPs, chlorpyrifos, glyphosate, and trichlorfon, were degraded in the GO/MoS2@AS system by over 90 %, with mineralization rates of 76.66 %, 85.46 %, and 82.18 %, respectively. This study provides insights into the co-oxidation degradation and detoxification mechanism mediated by 1O2 and •OHfree.