Unraveling the intrinsic mechanism behind the selective oxidation of sulfonamide antibiotics in the Mn(II)/periodate process: The overlooked surface-mediated electron transfer process.

Mn(II) exhibits a superb ability in activating periodate (PI) for the efficient degradation of aqueous organic contaminants. Nevertheless, ambiguous conclusions regarding the involved reactive species contributing to the removal of organic contaminants remain unresolved. In this work, we found that the Mn(II)/PI process showed outstanding and selective reactivity for oxidizing sulfonamides with the removal ranging from 57.1% to 100% at pH 6.5. Many lines of evidence suggest that the in-situ formed colloidal MnO2 (cMnO2) served as a catalyst to mediate electron transfer from sulfonamides to PI on its surface via forming cMnO2-PI complex (cMnO2-PI*) for the efficient oxidation of sulfonamides in the Mn(II)/PI process. Experimental results and density functional theory (DFT) calculations verify that the inclusive aniline moiety was the key site determining the electron transfer-dominated oxidation of sulfonamides. Furthermore, DFT calculation results reveal that the discrepancies in the removal of sulfonamides in the Mn(II)/PI process were attributed to different kinetic stability and chemical reactivity of sulfonamides caused by their heterocyclic substituents. In addition, a high utilization efficiency of PI was achieved in the Mn(II)/PI process owing to the surface-mediated electron transfer mechanism. This work provides deep insights into the surface-promoted mechanism in the cMnO2-involved oxidation processes.