Ultrasonic treatment enhances the formation of oxygen vacancies and trivalent manganese on α-MnO2 surfaces: Mechanism and application.

Catalytic activity is the main obstacle limiting the application of peroxymonosulfate (PMS) activation on transition metal oxide catalysts in organic pollutant removal. Herein, ultrasonic treatment was applied to α-MnO2 to fabricate a new u-α-MnO2 catalyst for PMS activation. Dimethyl phthalate (DMP, 10 mg/L) was almost completely degraded within 90 min, and the pseudofirst-order rate constant for DMP degradation in the u-α-MnO2/PMS system was ∼7 times that in the initial α-MnO2/PMS system. The ultrasonic treatment altered the crystalline and pore structures of α-MnO2 and produced defects on the u-α-MnO2 catalyst. According to the XPS, TG, and EPR results, higher contents of trivalent Mn and oxygen vacancies (OVs) were produced on the catalyst surfaces. The OVs induced the decomposition of PMS to produce 1O2, which was identified as the main reactive oxygen species (ROS) responsible for DMP degradation. The u-α-MnO2 catalyst presented great reusability, especially by ultrasonic regeneration of OVs toward the used catalyst. This study provides new insights into regulating OVs generation and strengthening catalyst activity in the PMS activation process for its application in water purification.