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小分子插层诱导溴掺杂的氧氯化铋缺陷生成以增强其对四环素的光催化降解和解毒性能。

Small-molecule intercalation induces defective generation of bromine-doped bismuth oxychloride to enhance photocatalytic degradation and detoxification of tetracycline.

机构信息

Key Laboratory of Integrated Regulation and Resources Development of Shallow Lakes of Ministry of Education, Hohai University, Nanjing 210098, China; College of Environment, Hohai University, Nanjing 210098, China.

Key Laboratory of Integrated Regulation and Resources Development of Shallow Lakes of Ministry of Education, Hohai University, Nanjing 210098, China; College of Environment, Hohai University, Nanjing 210098, China.

出版信息

J Colloid Interface Sci. 2025 Jan;677(Pt A):994-1004. doi: 10.1016/j.jcis.2024.08.025. Epub 2024 Aug 8.

DOI:10.1016/j.jcis.2024.08.025
PMID:39128293
Abstract

Photocatalysts are one of the effective methods to degrade antibiotic contamination, but the efficiency is low and the toxicity is not well recognized. Deep lattice doping to induce defect generation is an effective way to improve the performance of photocatalysts. Here, defect-rich bromine-doped BiOCl-XBr photocatalysts were constructed with the help of small molecules inserted into the interlayer. The photocatalytic degradation performance of BiOCl-XBr was significantly enhanced, and its degradation rate was up to about 12 times that of BiOCl monomer. The main reasons for the stronger photocatalytic performance of BiOCl-XBr include Br doping to enhance visible light absorption, surface defects, and Bi valence changes to improve charge transport. The degradation of tetracycline (TC) produced more toxic intermediates, and the biotoxicity experiments also confirmed that the toxicity showed a trend of increasing and then decreasing, indicating that the more toxic intermediates were also mineralized during the degradation process. However, the mortality and hatching rate of zebrafish in the exposed group after degradation recovered but changed their activity pattern under light and dark conditions. This further warns us to focus on the toxicity changes after antibiotic degradation. Finally, based on the free radical analysis, the mechanism of photocatalytic degradation and detoxification of TC by BiOCl-XBr was proposed.

摘要

光催化剂是降解抗生素污染的有效方法之一,但效率低,毒性尚未得到充分认识。深晶格掺杂诱导缺陷产生是提高光催化剂性能的有效方法。在这里,借助小分子插入层间,构建了富缺陷的溴掺杂 BiOCl-XBr 光催化剂。BiOCl-XBr 的光催化降解性能显著提高,其降解速率达到 BiOCl 单体的约 12 倍。BiOCl-XBr 具有更强光催化性能的主要原因包括 Br 掺杂以增强可见光吸收、表面缺陷和 Bi 价态变化以改善电荷输运。四环素 (TC) 的降解产生了更多毒性中间体,生物毒性实验也证实,毒性在降解过程中呈现出先增加后减少的趋势,表明更多毒性中间体也被矿化。然而,降解后暴露组斑马鱼的死亡率和孵化率恢复,但它们在光照和黑暗条件下的活动模式发生了变化。这进一步警告我们要关注抗生素降解后毒性的变化。最后,基于自由基分析,提出了 BiOCl-XBr 光催化降解和解毒 TC 的机制。

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