Mn-based catalysts for sulfate radical-based advanced oxidation processes: A review

Sulfate radical-based advanced oxidation processes (AOPs) have drawn increasing attention during the past two decades, and Mn-based materials have been proven to be effective catalysts for activating peroxymonosulfate (PMS) and peroxydisulfate (PDS) to degrade many contaminants. This article presents a comprehensive review of various Mn-based materials to activate PMS and PDS. The activation mechanisms of different Mn-based catalysts (i.e., Mn oxides MnO_x, MnO_x hybrids, and MnO_x‑carbonaceous material composites) were first summarized and discussed in detail. Besides the commonly reported free radicals (SO₄^-• and ^•OH), non-radical mechanisms such as singlet oxygen and direct electron transfer have also been discovered for selected materials. The effects of pH, inorganic ions, natural organic matter (NOM), dissolved oxygen content, temperature, and the crystallinity of the materials on the catalytic reactivity were also discussed. Then, important instrumentations and technologies employed to characterize Mn-based materials and to understand the reaction mechanisms were concisely summarized. Three common overlooks in the experimental designs for examining the PMS/PDS-MnO_x systems were also discussed. Finally, future research directions were suggested to further improve the technology and to provide a guidance to develop cost-effective Mn-based materials to activate PMS/PDS.