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由嵌入碳量子点(CQDs)的纳米级零价铁与黑色TiO₂组成的新型Z型异质结催化剂对抗生素的卓越光消除作用

Exceptional photo-elimination of antibiotic by a novel Z-scheme heterojunction catalyst composed of nanoscale zero valent iron embedded with carbon quantum dots (CQDs)-black TiO.

作者信息

Wu Xi, Wang Xiangyu, Lynch Iseult, Guo Zhiling, Zhang Peng, Wu Lisi, Ning Ping, Ren Nanqi

机构信息

Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China.

Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China; School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham B15 2TT, UK.

出版信息

J Hazard Mater. 2023 Oct 15;460:132323. doi: 10.1016/j.jhazmat.2023.132323. Epub 2023 Aug 16.

DOI:10.1016/j.jhazmat.2023.132323
PMID:37666174
Abstract

Passivation of nanoscale zero valent iron (nZVI, Fe) impaired its longevity while black TiO (b-TiO) suffered from restricted optical properties. Using a facile approach, a novel Z-scheme heterojunction catalyst (Fe@CQDs-TiO(b)) of nZVI decorated with carbon quantum dots (CQDs) implanted into b-TiO was designed. Characterization results revealed the optical potential of the passivation coating of nZVI. The incorporation of CQDs stimulated the creation of active •OH during the dark reaction, and led to an accelerated mobility of photo-excited carriers of b-TiO and optimized its band gap (narrowing from 2.36 eV to 2.15 eV) during the light reaction. The photo-elimination capacity of metronidazole (MNZ) on Fe@CQDs-TiO(b) (99.36%) was 2.64, 8.25 and 1.34 fold beyond that on nZVI, b-TiO and Fe@b-TiO, respectively. The assembled material offered excellent adaptability to environmental substrates, in addition to being virtually unaffected by tap (95.62%) and river water (92.62%). The mechanism of MNZ degradation was elaborated, and the combination of density functional theory (DFT) calculations and LC-MS discerned 12 intermediates and 3 routes. Toxicity assessment of these products was conducted to ensure no inadvertent negative environmental impacts arose. This work proposed an original direction and mechanism for the application of passivation layers in nZVI-based materials for environmental restoration.

摘要

纳米零价铁(nZVI,Fe)的钝化会削弱其寿命,而黑色二氧化钛(b-TiO)的光学性能则受到限制。通过一种简便的方法,设计了一种新型的Z型异质结催化剂(Fe@CQDs-TiO(b)),该催化剂由植入b-TiO的碳量子点(CQDs)修饰的nZVI组成。表征结果揭示了nZVI钝化涂层的光学电位。CQDs的掺入在暗反应过程中促进了活性•OH的产生,并导致b-TiO光激发载流子的迁移加速,并在光反应过程中优化了其带隙(从2.36 eV缩小到2.15 eV)。甲硝唑(MNZ)在Fe@CQDs-TiO(b)上的光消除能力(99.36%)分别是在nZVI、b-TiO和Fe@b-TiO上的2.64、8.25和1.34倍。除了几乎不受自来水(95.62%)和河水(92.62%)的影响外,这种组装材料对环境底物具有出色的适应性。阐述了MNZ降解的机制,密度泛函理论(DFT)计算和液相色谱-质谱联用识别出12种中间体和3条途径。对这些产物进行了毒性评估,以确保不会产生意外的负面环境影响。这项工作为钝化层在基于nZVI的环境修复材料中的应用提出了一个新的方向和机制。

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