Assessing the photocatalytic degradation of fluoroquinolone norfloxacin by Mn:ZnS quantum dots: Kinetic study, degradation pathway and influencing factors

Abstract

Norfloxacin (NOFX), a broadly used fluoroquinolone antibiotic, has been a subject of great concern in the past few years due to its undesirable effect on human beings and aquatic ecosystems. In this study, novel Mn doped ZnS (Mn:ZnS) quantum dots (QDs) were prepared through a facile chemical precipitation method and used as photocatalysts for NOFX degradation. Prior to photodegradation experiments, morphological and optical parameters of the QDs were examined through transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, fluorescence spectroscopy, Brunauer–Emmett–Teller analysis, and differential thermal and thermogravimetric analyses. Mn:ZnS QDs exhibited excellent properties of photodegradation, not only under UV irradiation but also in sunlight, which induced NOFX to photodegrade. The utmost photodegradation efficiency was obtained under optimal conditions (25 mL of NOFX, 15 mg/L, pH 10, 60 min UV irradiation, 60 mgs QDs), adopting first order kinetics. In addition, hydroxyl radicals produced by the conduction band electrons were found to be the primary reason dominating the transformation of NOFX in basic conditions, while holes, oxygen atoms, as well as the doped metal (Mn) enhanced the degradation. The QDs showed excellent reusability and stability in four repeated cycles. Finally, four different pathways were predicted, derived from the identified intermediates, with piperazinyl ring transformation being the primary one. It is expected that the synthesized Mn:ZnS QDs could be utilized as efficient photocatalytic materials for energy conversion and ecological remediation.