Sulfate radicals induced from peroxymonosulfate by magnetic ferrospinel MFe2O4 (M = Co, Cu, Mn, and Zn) as heterogeneous catalysts in the water

Abstract

Magnetic ferrospinel MFe2O4 (M=Co, Cu, Mn, and Zn) prepared in a sol–gel process was introduced as catalyst to generate powerful radicals from peroxymonosulfate (PMS) for refractory di-n-butyl phthalate (DBP) degradation in the water. Various catalysts were described and characterized, and the catalytic activities in PMS oxidation system were investigated. Most important of all, the mechanism of different catalysts in the catalytic PMS solution was illustrated. The results showed that the incorporation of CoFe2O4 had the highest catalytic performance in PMS oxidation for DBP degradation. All catalysts presented favorable recycling and stability in the repeated batch experiment. The catalytic process showed a dependence on initial pH, and an uncharged surface of the catalyst was more profitable for sulfate radical generation. H2-TPR and CVs analysis indicated that the sequence of the catalyst's reducibility in PMS solution was CoFe2O4>CuFe2O4>MnFe2O4>ZnFe2O4, which had a close connection with the activity of metal ion in A site of the catalysts. The surface hydroxyl sites played an important role in the catalytic process, and its quantity determined the degradation of DBP. Moreover, the reactive species in PMS/MFe2O4 system were identified as sulfate radical and hydroxyl radical. The promotion of these radical's reaction was due to the fact that a balance action in the process of M2+/M3+, O2−/O2, occurred, and at the same time, PMS was catalyzed.