Mechanochemically tailoring oxygen vacancies of MnO2 for efficient degradation of tetrabromobisphenol A with peroxymonosulfate

Oxygen vacancy (VO) engineering can efficiently improve the catalytic activity of metal oxides. This work developed a solvent-free mechanochemical method to tailor VO levels on the surface of commercial MnO2 under ambient conditions. After a typical ball milling treatment at 350 rpm for 20 min, the obtained VO-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 VO levels, but also the local environment of VO, i.e., VO-associated cations. The Mn4+/Mn3+ redox couple is more important than Mn3+/Mn2+, and VO improves the oxygen mobility in/on MnO2 and Mn4+/Mn3+ redox reactions for the activation of PMS.