Mn-MOF derived manganese sulfide as peroxymonosulfate activator for levofloxacin degradation: An electron-transfer dominated and radical/nonradical coupling process

Recently, transition metal sulfides have attracted much attention due to their better catalytic capacities as peroxymonosulfate (PMS) activator than their metal oxide counterparts. However, the systematic studies on PMS activation using transition metal sulfides are still lacking. In this work, manganese sulfide (MnS) materials were synthesized via a MOFs-derived method and utilized for PMS activation to degrade levofloxacin (LVF) in water for the first time. As expected, MnS exhibited remarkable LVF degradation efficiency by PMS activation, which was distinctly higher than Mn₂O₃. The results of quenching experiments, electro spin resonance identification and electrochemical tests indicated that electron-transfer progress was the dominant mechanism in α-MnS/PMS system. Meanwhile, the presence of ¹O₂ and radicals further became the removal of LVF by α-MnS/PMS system into a radical/nonradical coupling process. The superior electrical conductivity of α-MnS than α-Mn₂O₃ was revealed by DFT calculations, which resulted in the higher catalytic capacity of α-MnS. The result of XPS also indicated the S species in MnS accelerated the recycle of Mn(IV)/Mn(II) and then promoted the generation of radicals. Furthermore, the influence of various environmental conditions on LVF removal and the reusability of α-MnS were also investigated, which demonstrated the high application potential of α-MnS/PMS system. Finally, six possible pathways of LVF oxidation in the system were proposed based on the identified byproducts and their ecotoxicity was evaluated with ECOSAR method. This work promotes the fundamental understanding of PMS activation by α-MnS and provides useful information for practical application of manganese sulfide in water treatment.