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硼掺杂生物炭作为高效无金属过一硫酸盐活化剂的研究进展:-O-B-O-结构的重要作用。

Insight into boron-doped biochar as efficient metal-free catalyst for peroxymonosulfate activation: Important role of -O-B-O- moieties.

机构信息

College of Architecture Engineering, Beijing University of Technology, 100 Pingleyuan, Chaoyang District, Beijing 100124, China.

College of Architecture Engineering, Beijing University of Technology, 100 Pingleyuan, Chaoyang District, Beijing 100124, China.

出版信息

J Hazard Mater. 2023 Mar 5;445:130479. doi: 10.1016/j.jhazmat.2022.130479. Epub 2022 Nov 25.

Abstract

In recent years, metal-free catalysts for persulfate-mediated oxidation processes have been widely applied to remove contaminants in the aquatic environment. Herein, a simple pyrolysis approach was used to synthesize the boron doped biochars (B@TBCs) derived from boric acid mixed with tea seed shells powders. The obtained B@TBCs exhibited fantastic capability to boost PMS (0.5 mM) activation for 90%∼ removal of oxytetracycline (OTC) within 20 min. Through the correlation analysis and DFT calculations, it was concluded that the apparent rate constant of pollutants removal was greatly related to the -O-B-O- groups on the biochars, which could improve the electron-donating capacity of the biochar. In addition, the degradation process of OTC was pH-dependent because of the changed roles of ROSs under different pH. Finally, according to the DFT calculation, LC-MS and toxicological analysis, the degradation pathways of pollutants and the toxicity changes during the degradation process were obtained. These findings consolidated the theoretical basis for further boosting the catalytic activity of B-doped biochars and expanded the imagination for the modification of other metal-free biochar catalysts for PMS activation.

摘要

近年来,无金属催化剂在过硫酸盐介导的氧化过程中得到了广泛应用,用于去除水环境污染中的污染物。在此,采用一种简单的热解方法合成了由硼酸与茶籽壳粉末混合得到的硼掺杂生物炭(B@TBCs)。所得到的 B@TBCs 表现出了极好的性能,能够在 20 分钟内促进 PMS(0.5 mM)的活化,将土霉素(OTC)的去除率提高到 90%。通过相关性分析和 DFT 计算,得出污染物去除的表观速率常数与生物炭上的-O-B-O-基团密切相关,这可以提高生物炭的供电子能力。此外,由于不同 pH 下 ROSs 的作用发生变化,OTC 的降解过程呈现 pH 依赖性。最后,根据 DFT 计算、LC-MS 和毒理学分析,得到了污染物的降解途径和降解过程中毒性变化。这些发现为进一步提高 B 掺杂生物炭的催化活性提供了理论基础,并为 PMS 活化的其他无金属生物炭催化剂的修饰提供了新的思路。

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