Efficient degradation of aqueous organic contaminants in manganese(II)/peroxymonosulfate system assisted by pyridine organic ligands

Although manganese(II) is known to have no role in peroxymonosulfate (PMS) activation, through a series of sulfamethoxazole (SMX) oxidation experiments, we found that the addition of pyridine organic ligands can improve the catalytic activity and accelerate SMX oxidation. For the organic ligands to be effective: the stability constant of the Mn(III) complex should be higher than that of the Mn(II) complex. A positive correlation was observed between the SMX oxidation rate and Mn(II) concentration, and the maximum PMS utilization efficiency was achieved. Many shreds of evidence verified that neither •SO4- nor •OH was associated with SMX oxidation. The enhanced effect of phenanthroline on the Mn(II)/PMS system was attributed to the highly oxidative intermediate manganese species (Mn(V)), originating from the two-electron transfer reaction of complexed Mn(III) and PMS. Notably, the main oxidizing species did not change (η-(PMSO2) ∼ 100%) regardless of the initial PMSO concentration or pH value. Additionally, the analysis of SMX degradation products revealed that the oxygen transfer oxidation pathway was dominant in the Mn(II)/phenanthroline/PMS system, while the N radical coupling pathway also contributed significantly to SMX oxidation. This work offers new insights into the formation of high-valent manganese species and provides a potential strategy for applying low-concentration Mn(II) to wastewater treatment.