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α-(Fe,Cu)OOH/RGO 纳米复合材料在可见光照射下用于异相光芬顿-like 降解环丙沙星。

α-(Fe, Cu)OOH/RGO nanocomposites for heterogeneous photo-Fenton-like degradation of ciprofloxacin under visible light irradiation.

机构信息

College of Civil Engineering, Fuzhou University, Fuzhou, 350108, Fujian, China.

出版信息

Environ Sci Pollut Res Int. 2022 Nov;29(52):78874-78886. doi: 10.1007/s11356-022-21245-3. Epub 2022 Jun 14.

Abstract

Ciprofloxacin (CIP) is a third-generation fluoroquinolones (FQs) antibiotic, and the occurrence of CIP in the water environment has raised growing concerns owning to its environmental toxicity. In this paper, a novel α-(Fe, Cu)OOH/RGO nanocomposite was synthesized via a one-step reflux method for CIP degradation through a photo-Fenton-like process. When the RGO content was 1 wt%, CIP degradation ratio by the α-(Fe, Cu)OOH/RGO nanocomposite reached 100% under visible light irradiation within 120 min, and total organic carbon (TOC) removal ratio reached 60% within 180 min. The result of molecular fluorescence spectra highlighted that the loading of RGO on the α-(Fe, Cu)OOH significantly increased the content of hydroxyl radicals (·OH) in the heterogeneous photo-Fenton-like system and simultaneously inhibited the recombination of photogenerated electron and hole, which played critical roles in the enhancement of CIP degradation. In addition, 11 main intermediates were identified as the degradation products of CIP in the α-(Fe, Cu)OOH/RGO/HO/visible light reaction systems using liquid chromatograph-mass spectrometer (LC-MS) analyses. The results demonstrated that three degradation pathways for CIP removal by α-(Fe, Cu)OOH/RGO nanocomposite occurred, including (i) oxidation on the piperazine ring and dealkylation, (ii) defluorination and decarboxylation, and (iii) hydroxylation on the quinolone ring. This work would provide a novel insight of CIP degradation pathways in photo-Fenton-like processes.

摘要

环丙沙星(CIP)是第三代氟喹诺酮类(FQs)抗生素,由于其环境毒性,水环境中 CIP 的出现引起了越来越多的关注。在本文中,通过一步回流法合成了一种新型的α-(Fe,Cu)OOH/RGO 纳米复合材料,用于通过类芬顿光降解法降解 CIP。当 RGO 含量为 1wt%时,α-(Fe,Cu)OOH/RGO 纳米复合材料在可见光照射下 120min 内 CIP 的降解率达到 100%,总有机碳(TOC)去除率在 180min 内达到 60%。分子荧光光谱的结果表明,RGO 在α-(Fe,Cu)OOH 上的负载显著增加了非均相类芬顿体系中羟基自由基(·OH)的含量,同时抑制了光生电子和空穴的复合,这在 CIP 降解的增强中起着关键作用。此外,使用液相色谱-质谱(LC-MS)分析在α-(Fe,Cu)OOH/RGO/HO/可见光反应体系中鉴定出 CIP 的 11 种主要中间产物。结果表明,α-(Fe,Cu)OOH/RGO 纳米复合材料去除 CIP 有 3 种降解途径,包括(i)哌嗪环的氧化和脱烷基化,(ii)脱氟和脱羧基化,和(iii)喹诺酮环的羟化。这项工作将为类芬顿过程中 CIP 的降解途径提供新的见解。

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