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氧空位增强的 BiMoO 光催化降解环丙沙星:氧空位工程、生物毒性评价及机理研究。

Oxygen vacancy boosted photocatalytic decomposition of ciprofloxacin over BiMoO: Oxygen vacancy engineering, biotoxicity evaluation and mechanism study.

机构信息

College of Science, Huazhong Agricultural University, Wuhan 430070, China; Key Laboratory of Environment Correlative Dietology, Ministry of Education, Wuhan 430070, China.

College of Science, Huazhong Agricultural University, Wuhan 430070, China.

出版信息

J Hazard Mater. 2019 Feb 15;364:691-699. doi: 10.1016/j.jhazmat.2018.10.063. Epub 2018 Oct 23.

Abstract

Herein, efficient visible light driven photocatalytic degradation of ciprofloxacin was realized over BiMoO with oxygen vacancies (OVs) which can be tunably introduced through a facile solvothermal method via the modulation of tetramethylethylenediamine (TMEDA). The optimal BiMoO with OVs possessed the highest CIP degradation rate of 1.799 mg min m, about 8.4 times than that of the pristine BiMoO. And more than half of CIP was mineralized in only 2 h. The biotoxicity of ciprofloxacin and its byproducts to E. coli K-12 and saccharomyces cerevisiae was thoroughly eliminated after 6 h's photocatalytic treatment. Characterization methods revealed the rich oxygen vacancies in BiMoO not only endowed it with broader visible light absorption and faster transfer of photogenerated carriers, but also provided abundant absorption sites of surface oxygen for efficient molecular oxygen activation. Correspondingly, plentiful active species were produced and participated in the photocatalytic process, thereby efficiently promoting the ciprofloxacin degradation. Based on the HPLC-MS analysis, a possible decomposition pathway of CIP was finally proposed with the first decomposition step of pipetazine ring oxidation and breakage. This work might open up new avenues for superior visible light driven photocatalysts design to deal with pharmaceutical compounds contamination via tunable OVs Engineering.

摘要

本文通过简便的溶剂热法,通过调节四甲基乙二胺(TMEDA),可实现具有氧空位(OVs)的 BiMoO 高效可见光驱动光催化环丙沙星降解。可调氧空位的最优 BiMoO 具有最高的 CIP 降解速率为 1.799mgminm,约为原始 BiMoO 的 8.4 倍。而且,仅在 2h 内就有超过一半的 CIP 被矿化。经过 6h 的光催化处理,环丙沙星及其副产物对大肠杆菌 K-12 和酿酒酵母的生物毒性被彻底消除。表征方法表明,BiMoO 中的丰富氧空位不仅赋予了它更宽的可见光吸收和更快的光生载流子转移,而且还提供了丰富的表面氧吸附位,从而有效地激活了分子氧。相应地,产生了大量的活性物质并参与了光催化过程,从而有效地促进了环丙沙星的降解。根据 HPLC-MS 分析,最终提出了 CIP 的可能分解途径,第一个分解步骤是哌嗪环氧化和断裂。这项工作可能为通过可调 OVs 工程设计具有优越可见光驱动能力的光催化剂以处理药物化合物污染开辟了新途径。

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