Unraveling Different Reaction Characteristics of Alkoxy Radicals in a Co(II)-Activated Peracetic Acid System Based on Dynamic Analysis of Electron Distribution

Peracetic acid (PAA)-based advanced oxidation processes (AOPs) have shown broad application prospects in organic wastewater treatment. Alkoxy radicals including CH3COO• and CH3COOO• are primary reactive species in PAA-AOP systems; however, their reaction mechanism on attacking organic pollutants still remains controversial. In this study, a Co(II)/PAA homogeneous AOP system at neutral pH was constructed to generate these two alkoxy radicals, and their different reaction mechanisms with a typical emerging contaminant (sulfacetamide) were explored. Dynamic electron distribution analysis was applied to deeply reveal the radical-meditated reaction mechanism based on molecular orbital analysis. Results indicate that hydrogen atom abstraction is the most favorable route for both CH3COO• and CH3COOO• attacking sulfacetamide. However, both radicals cannot react with sulfacetamide via the radical adduct formation route. Interestingly, the single-electron transfer reaction is only favorable for CH3COO• due to its lower ESUMO. In comparison, CH3COOO• can react with sulfacetamide via a similar radical self-sacrificing bimolecular nucleophilic substitution (SN2) route owing to its high ESOMO and easy escape of unpaired electrons from n orbitals of O atoms in the peroxy bond. These findings can significantly improve the knowledge of reactivity of CH3COO• and CH3COOO• on attacking organic pollutants at the molecular orbital level.