摘要：Oxygen vacancy (V_O) engineering can efficiently improve the catalytic activity of metal oxides. This work developed a solvent-free mechanochemical method to tailor V_O levels on the surface of commercial MnO₂ under ambient conditions. After a typical ball milling treatment at 350 rpm for 20 min, the obtained V_O-rich MnO₂ activated peroxymonosulfate (PMS) to completely degrade tetrabromobisphenol (TBBPA) with a pseudo-first-order rate constant of 0.21 min⁻¹, being 22 times larger than that for non-milled MnO₂. ¹⁸O-labeling tests confirmed that singlet oxygen was generated from both PMS and lattice oxygen of MnO₂ as dominant active species for the TBBPA degradation. It was clarified that the catalytic activity of MnO₂ depends on not only V_O levels, but also the local environment of V_O, i.e., V_O-associated cations. The Mn⁴⁺/Mn³⁺ redox couple is more important than Mn³⁺/Mn²⁺, and V_O improves the oxygen mobility in/on MnO₂ and Mn⁴⁺/Mn³⁺ redox reactions for the activation of PMS.

关键词：磺胺类抗生素；水溶剂；加速溶剂萃取；土壤