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受金刚石表面缺陷介导的过氧乙酸均裂连续电子转移激活的预水化电子用于增强全氟辛酸的破坏。

Prehydrated Electrons Activated by Continuous Electron Transfer Stemmed from Peracetic Acid Homolysis Mediated by Diamond Surface Defects for Enhanced PFOA Destruction.

机构信息

School of Environment, Tsinghua University, Beijing 100084, China.

Department of Chemical and Biochemical Engineering, Western University, London, Ontario N6A 5B9, Canada.

出版信息

Environ Sci Technol. 2024 Jun 25;58(25):11152-11161. doi: 10.1021/acs.est.4c02020. Epub 2024 Jun 12.

Abstract

Research on the use of peracetic acid (PAA) activated by nonmetal solid catalysts for the removal of dissolved refractory organic compounds has gained attention recently due to its improved efficiency and suitability for advanced water treatment (AWT). Among these catalysts, nanocarbon (NC) stands out as an exceptional example. In the NC-based peroxide AWT studies, the focus on the mechanism involving multimedia coordination on the NC surface (reactive species (RS) path, electron reduction non-RS pathway, and singlet oxygen non-RS path) has been confined to the one-step electron reaction, leaving the mechanisms of multichannel or continuous electron transfer paths unexplored. Moreover, there are very few studies that have identified the nonfree radical pathway initiated by electron transfer within PAA AWT. In this study, the complete decomposition ( = 0.1995) and significant defluorination of perfluorooctanoic acid (PFOA, deF% = 72%) through PAA/NC has been confirmed. Through the use of multiple electrochemical monitors and the exploration of current diffusion effects, the process of electron reception and conduction stimulated by PAA activation was examined, leading to the discovery of the dynamic process from the PAA molecule → NC solid surface → target object. The vital role of prehydrated electrons (e) before the entry of resolvable electrons into the aqueous phase was also detailed. To the best of our knowledge, this is the first instance of identifying the nonradical mechanism of continuous electron transfer in PAA-based AWT, which deviates from the previously identified mechanisms of singlet oxygen, single-electron, or double-electron single-path transfer. The pathway, along with the strong reducibility of e initiated by this pathway, has been proven to be essential in reducing the need for catalysts and chemicals in AWT.

摘要

近年来,由于其提高的效率和适用于高级水处理(AWT),使用非金属固体催化剂激活过氧乙酸(PAA)去除溶解的难处理有机化合物的研究引起了关注。在这些催化剂中,纳米碳(NC)是一个杰出的例子。在基于 NC 的过氧化物 AWT 研究中,对涉及 NC 表面上多媒体协调的机制(反应性物质(RS)途径、电子还原非 RS 途径和单线态氧非 RS 途径)的关注仅限于一步电子反应,而多通道或连续电子转移途径的机制仍未得到探索。此外,很少有研究确定了 PAA AWT 中电子转移引发的非自由基途径。在这项研究中,通过 PAA/NC 已证实全分解(=0.1995)和显著的全氟辛酸(PFOA,deF%=72%)的脱氟。通过使用多个电化学监测器和电流扩散效应的探索,检查了 PAA 激活刺激的电子接收和传导过程,从而发现了从 PAA 分子→NC 固体表面→目标物的动态过程。还详细介绍了可分辨电子进入水相之前预水合电子(e)的重要作用。据我们所知,这是首次在基于 PAA 的 AWT 中确定连续电子转移的非自由基机制的实例,该机制偏离了先前确定的单线态氧、单电子或双电子单路径转移机制。该途径以及该途径引发的 e 的强还原性已被证明对于减少 AWT 中对催化剂和化学品的需求至关重要。

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