Effect of phosphate on peroxymonosulfate activation: Accelerating generation of sulfate radical and underlying mechanism

Effect of phosphate on pollutant removal was widely investigated in various peroxumonosulfate-based advanced oxidation processes (AOPs) but the role of phosphate was controversial. Many studies also used phosphate as buffer in PMS-based AOPs. This study shows that phosphate promoted PMS activation for pollutants removal. Therefore, PMS activation capacity of some strategies may be overestimated when conducted in the phosphate buffer. Importantly, the results of radical quenching tests, radical probes and reaction stoichiometries indicated that the yields of SO4 center dot- was elevated by the presence of phosphate and linearly depended on phosphate concentration, while the yields of .OH remained constant. Density Functional Theory (DFT) calculation confirmed that PO43- and HPO42- could efficiently break O-O bond of PMS, promoting the generation of SO4 center dot- for contaminants decomposition. These results illuminated the role of phosphate in AOPs utilizing PMS and uncovered the underlying mechanism of PMS activation by phosphate.

Automated summary

The presence of phosphate was found to increase the effectiveness of PMS activation for pollutants removal in AOPs, promoting the generation of SO4 center dot- through efficient breaking of the O-O bond of PMS. The yields of SO4 center dot- were linearly dependent on phosphate concentration, while the yields of .OH remained constant.