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Degradation of ciprofloxacin by persulfate activated by Fe (Ⅲ) doped BiOCl composite photocatalyst
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This study synthesized iron-doped BiOCl composite photocatalysts (Fe-BOC-X) via solvothermal method and evaluated their ability to degrade ciprofloxacin (CIP) antibiotic under sunlight with persulfate activation. The optimized Fe-BOC-3 catalyst (50 wt% iron) achieved 81.4% CIP removal within 90 minutes, outperforming pure BiOCl, with hydroxyl radicals and sulfate radicals identified as the dominant degradation species. Iron doping enhanced visible-light absorption, photocarrier transfer, and surface area compared to the unmodified material.
Abstract Fe-BOC-X photocatalyst was successfully prepared by solvothermal method. The photocatalytic activity of Fe-BOC-X was determined by ciprofloxacin (CIP), a typical fluoroquinolone antibiotic. Under sunlight irradiation, all Fe-BOC-X showed better CIP removal performance than original BiOCl. In comparison, the photocatalyst with iron content of 50 wt% (Fe-BOC-3) has excellent structural stability and the best adsorption photodegradation efficiency. The removal rate of CIP (10 mg/l) by Fe-BOC-3 (0.6 g/L) reached 81.4% within 90 min. At the same time, the effects of photocatalyst dosage, pH, persulfate, persulfate concentration and combinations of different systems (PS, Fe-BOC-3, Vis/PS, Vis/Fe-BOC-3, Fe-BOC-3/PS and Vis/Fe-BOC-3/PS) on the reaction were systematically discussed. Reactive species trapping experiments, electron spin resonance (ESR) signals revealed that the photo-generated holes (\({h^+}\)), hydroxyl radical (\(\bullet OH\)), sulfate radical (\(\bullet S{O_4}^{ - }\)) and superoxide radical (\(\bullet {O_2}^{ - }\)) played an important role in CIP degradation, hydroxyl radicals (\(\bullet OH\)) and sulfate radicals (\(\bullet S{O_4}^{ - }\)) play a major role. Various characterization methods have demonstrated that Fe-BOC-X has larger specific surface area and pore volume than original BiOCl. UV-vis DRS indicate that Fe-BOC-X has wider visible light absorption and faster photocarrier transfer, and provides abundant surface oxygen absorption sites for effective molecular oxygen activation. Accordingly, a large number of active species were produced and participated in the photocatalytic process, thus effectively promoting the degradation of ciprofloxacin. Based on HPLC-MS analysis, two possible decomposition pathways of CIP were finally proposed. The main degradation pathways of CIP are mainly due to the high electron density of piperazine ring in CIP molecule, which is mainly attacked by various free radicals. The main reactions include piperazine ring opening, decarbonylation, decarboxylation and fluorine substitution. This study can better open up a new way for the design of visible light driven photocatalyst and provide more ideas for the removal of CIP in water environment.
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