Abstract
Manganese tetroxide (Mn3O4) nanomaterials were prepared by green tea extract and applied to catalyze sodium peroxydisulfate (PDS) for the simultaneous degradation of estriol/17a-ethinylestradiol (E3/EE2) with removal efficiencies of 97.5 and 96.4% for E3 and EE2, respectively. XPS also showed that before and after the reaction the divalent manganese content decreased from 50.2 to 34.8%, indicating divalent manganese plays a major role in the catalytic process. EPR quenching and electrochemical studies showed that while initially singlet oxygen (1O2), sulfate (SO4•-), superoxide (O2•-) and hydroxyl (•OH) radicals were all generated in the system, thereafter, the oxidation of E3/EE2 mainly depended on 1O2 and O2•-, where O2•- intermediates participated in the generation of 1O2 in the Fenton-like process. LC-MS analysis showed that degradation products of E3/EE2 were mainly produced via hydroxyl and sulfate degradation pathways. Finally, a mechanism of Fenton-like oxidation of E3/EE2 was proposed.
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