Oxygen vacancies-dominated reactive species generation from peroxymonosulfate activated by MoO_3-x for pollutant...

Interface oxygen vacancies (OVs) are commonly used to improve the catalytic performance of activators in persulfate-based advanced oxidation processes, but the underlying mechanism was not fully explored. This work reports a facile heat treatment method to regulate OVs in MoO_3-x to elucidate the mechanism of peroxymonosulfate (PMS) activated by OVs to degrade 2,4,4-Trichlorobiphenyl (PCB28). Electron spin resonance, free radical quenching, X-ray photoelectron spectroscopy, and Raman spectroscopy confirmed that both reducing Mo species and OVs of MoO_3-x surface were responsible for PMS activation. Further experiments and Density Function Theory (DFT) calculation suggest that OVs in MoO_3-x induced the formation of superoxide radical (O₂^•-), and then O₂^•- was transformed into singlet oxygen (¹O₂) or mediated PMS activation to generate radicals, which contritbued to 70.2% of PCB28 degradation. The steady-state concentrations of free radical calculated with the kinetics model show that OVs were more favorable to mediate PMS to generate hydroxyl radicals (^•OH) under oxic conditions, while reducing Mo species would like to induce PMS to produce sulfate radicals (SO₄^•-). Overall, this study is dedicated to a new insight into the in-depth mechanism of PMS activation by OVs-rich catalysts and provides a novel strategy for reactive species regulation in PMS based oxidation process.