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过一硫酸盐在水溶液中电化学激活高效分解全氟辛烷磺酸:效能、反应机制、活性位点和应用潜力。

Efficient decomposition of perfluorooctane sulfonate by electrochemical activation of peroxymonosulfate in aqueous solution: Efficacy, reaction mechanism, active sites, and application potential.

机构信息

Guangdong Provincial Research Center for Environment Pollution Control and Remediation Materials, College of Life Science and Technology, Jinan University, Guangzhou 510632, PR China; Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, PR China; College of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, PR China.

College of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, PR China.

出版信息

Water Res. 2022 Aug 1;221:118778. doi: 10.1016/j.watres.2022.118778. Epub 2022 Jun 18.

Abstract

The electrochemical oxidation method is a promising technology for the degradation of perfluorooctane sulfonate (PFOS). However, the elimination processes of PFOS are still unknown, including the electron transfer pathway, key reactive sites, and degradation mechanism. Here, we fabricated diatomite and cerium (Ce) co-modified SbO (D-Ce/SbO) anode to realize efficient degradation of PFOS via peroxymonosulfate (PMS) activation. The transferred electron and the generated hydroxyl radical (•OH) can high-effectively decompose PFOS. The electron can be rapidly transferred from the highest occupied molecular orbital of the PFOS to the lowest unoccupied molecular orbital of the PMS via the D-Ce/SbO driven by a potential energy difference under electrochemical process. The active site of Ce-O in the D-Ce/SbO can greatly reduce the migration distance of the electron and the •OH, and thus improving the catalytic activity for degrading various organic micropollutants with high stability. In addition, the electrochemical process shows strong resistance and tolerance to the changing pH, inorganic ions, and organic matter. This study offers insights into the electron transfer pathway and PMS activation mechanism in PFOS removal via electrochemical oxidation, paving the way for its potential application in water purification.

摘要

电化学氧化法是一种很有前途的全氟辛烷磺酸(PFOS)降解技术。然而,PFOS 的消除过程仍然未知,包括电子转移途径、关键反应位点和降解机制。在这里,我们制备了硅藻土和铈(Ce)共修饰的 SbO(D-Ce/SbO)阳极,通过过一硫酸盐(PMS)活化来实现 PFOS 的有效降解。转移电子和生成的羟基自由基(•OH)可以高效地分解 PFOS。在电化学过程中,通过 D-Ce/SbO 驱动的势能差,PFOS 的最高占据分子轨道(HOMO)中的电子可以迅速转移到 PMS 的最低未占据分子轨道(LUMO)中。D-Ce/SbO 中的 Ce-O 活性位点可以大大降低电子和•OH 的迁移距离,从而提高对各种有机微污染物的催化降解活性,具有高稳定性。此外,电化学过程对 pH 值、无机离子和有机物的变化具有很强的耐抗性和耐受性。本研究深入了解了电化学氧化法去除 PFOS 过程中的电子转移途径和 PMS 活化机制,为其在水净化中的潜在应用铺平了道路。

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