Rapid degradation of organic pollutants by enhanced persulfate activation using CeO2-MnFe2O4 nanostructures: A polymetallic synergistic effect

Persulfate-based advanced oxidation processes (AOPs) have attracted considerable attention in the treatment of organic wastewater with high performance and long lifetime. The construction of efficient, environmentally-friend, and stable nanocatalysts has been recognized as a promising approach to activate persulfate. Herein, magnetic CeO2-MnFe2O4 nanomaterials fabricated via a simple sol-gel method were used for the first time to enhanced activate persulfate (PS) for the removal of the organic pollutant enrofloxacin (ENR). It was demonstrated that 97.2% of ENR (10 mg L−1) was efficiently degraded. 63.3% of TOC decreased within 35 min under a neutral solution (pH 6.81) in the PS+CeO2-0.2MnFe2O4 system using a catalyst dosage of 0.25 g L−1 and 0.18 mM PS. The magnetic CeO2-MnFe2O4 nanostructures maintained excellent recovery as well as recyclability ENR removal efficiency was 90% after recycling five times. EPR and quenching tests indicated that sulfate radicals (SO4•−) and hydroxyl radicals (•OH) significantly contributed to ENR removal. XPS analysis showed that the synergistic redox cycles of Ce3+/Ce4+, Mn2+/Mn3+, and Fe2+/Fe3+ are essential to activate PS for ENR degradation. DFT calculations also revealed that PS molecules preferred to adsorb to and dissociate on CeO2-MnFe2O4 surfaces rather than just CeO2 and MnFe2O4 surfaces. CeO2 plays a dual role in the charge transfer from CeO2-MnFe2O4 to PS molecules, i.e., both electron storage and donor. This work also provides a new interpretation to explain the activation mechanism of PS. The developed CeO2-MnFe2O4 nanostructures with rapid removal efficiency, high degradation efficiency and good recyclability may provide potential guidance for the design of polymetallic oxide nanocatalysts in PS-based AOPs.