Mn2O3 as an Electron Shuttle between Peroxymonosulfate and Organic Pollutants: The Dominant Role of Surface Reactive Mn(IV) Species

The environmentally benign Mn oxides play a crucial role in the transformation of organic contaminants, either through catalytically decomposing oxidants, e.g., peroxymonosulfate (PMS), or through directly oxidizing the target pollutants. Because of their dual roles and the complex surface chemical reactions, the mechanism involved in Mn oxide-catalyzed PMS activation processes remains obscure. Here, we clearly elucidate the mechanism involved in the Mn₂O₃ catalyzed PMS activation process by means of separating the PMS activation and the pollutant oxidation process. Mn₂O₃ acts as a shuttle that mediates the electron transfer from organic substrates to PMS, accompanied by the redox cycle of surface Mn(IV)/Mn(III). Multiple experimental results indicate that PMS is bound to the surface of Mn₂O₃ to form an inner-sphere complex, which then decomposes to form long-lived surface reactive Mn(IV) species, without the generation of sulfate radicals (SO₄^•-) and hydroxyl radicals (HO^•). The surface reactive Mn(IV) species are proposed to be responsible for the degradation of organic contaminants (e.g., phenol) and the formation of singlet oxygen (¹O₂), followed by the regeneration of the surface Mn(III) sites on Mn₂O₃. This study advances the fundamental understanding of the underlying mechanism involved in transition metal oxide-catalyzed PMS activation processes.