Amorphous zirconium oxide activates peroxymonosulfate for selective degradation of organic compounds: Performance, mechanisms and structure-activity relationship

Application of heterogeneous advanced oxidation processes (AOPs) for wastewater treatment suffers from the low oxidant utilization efficiency, slow catalytic cycling and severe matrix interference. Herein, we report that amorphous zirconium dioxide (aZrO2), a redox-inert metal oxide, can efficiently activate peroxymonosulfate (PMS) to degrade organic micropollutants under very low oxidant doses and complex coexisting matrices. Distinct from conventional AOPs where radicals are formed, the surface Zr(IV)-PMS* complex was identified as the principal reactive species, and primarily conducted oxygen-atom-transfer route with selected molecules. Quantitative structure-activity relationship analysis indicated that the formation of Zr(IV)-PMS* complex was governed by the density of the surface hydroxyl groups. The strong interaction between the Zr atom and PMS caused the deviation of the negative charge from ---Zr(IV) metal sites to the oxidant. As a result, the O-O bond of the adsorbed PMS was prolonged and its oxidation potential elevated, which enabled it to directly react with contaminants. This study indicates the potential of aZrO2 as a novel and eco-friendly catalyst that activates PMS to selectively tackle organic contaminants, and sheds light on the designing of Fenton-like catalysts using redoxinert metals.

Automated summary

The application of heterogeneous advanced oxidation processes (AOPs) in wastewater treatment is hindered by low oxidant utilization efficiency, slow catalytic cycling, and matrix interference. This study demonstrates that amorphous zirconium dioxide (aZrO2), a redox-inert metal oxide, can efficiently activate peroxymonosulfate (PMS) to degrade organic micropollutants even under low oxidant doses and complex matrices. The surface Zr(IV)-PMS* complex is identified as the principal reactive species, and the interaction between Zr atom and PMS leads to prolonged O-O bond and elevated oxidation potential for direct reaction with contaminants.