Mechanisms and degradation pathways of doxycycline hydrochloride by Fe3O4 nanoparticles anchored nitrogen-doped porous carbon microspheres activated peroxymonosulfate

Peroxymonosulfate (PMS) based advanced oxidation processes have gained widespread attention in refractory antibiotics treatment. In this study, Fe3O4 nanoparticles anchored nitrogen-doped porous carbon microspheres (Fe3O4/NCMS) were synthesized and applied to PMS heterogeneous activation for doxycycline hydrochloride (DOX-H) degradation. Benefitting from synergy effects of porous carbon structure, nitrogen doping, and fine dispersion of Fe3O4 nanoparticles, Fe3O4/NCMS showed excellent DOX-H degradation efficiency within 20 min via PMS activation. Further reaction mechanisms revealed that the reactive oxygen species including hydroxyl radicals (•OH) and singlet oxygen (1O2) played the dominant role for DOX-H degradation. Moreover, Fe(II)/Fe(III) redox cycle also participated in the radical generation, and nitrogen-doped carbonaceous structures served as the highly active centers for non-radical pathways. The possible degradation pathways and intermediate products accompanying DOX-H degradation were also analyzed in detail. This study provides key insights into the further development of heterogeneous metallic oxides-carbon catalysts for antibiotic-containing wastewater treatment.