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使用商业 DSA®-Cl 在甲醇介质中电氧化莠去津产生的自由基的检测:理解该过程的关键。

Detection of radicals produced during electro-oxidation of atrazine using commercial DSA®-Cl in methanol media: Keys to understand the process.

机构信息

São Carlos Institute of Chemistry, University of São Paulo, P.O. Box 780, CEP 13560-970. São Carlos, SP, Brazil.

São Carlos Institute of Chemistry, University of São Paulo, P.O. Box 780, CEP 13560-970. São Carlos, SP, Brazil.

出版信息

Chemosphere. 2022 Nov;307(Pt 4):136157. doi: 10.1016/j.chemosphere.2022.136157. Epub 2022 Aug 24.

Abstract

This work reports the radicals detected and identified during the degradation of atrazine in methanol medium in the presence and absence of different proportions of water (0%, 5%, and 10%). The determination of these radicals is an important step to understand the electrolysis processes in methanol medium and contribute to clarify the degradation mechanism. Furthermore, the parameters for the successful removal of the contaminant were optimized and the results showed that the application of the technique led to the removal of nearly 99.8% of atrazine after 1 h of electrolysis. The oxidation kinetics was found to be very fast and most of the atrazine molecule in the medium was degraded in the first hour of electrolysis. The results obtained from a thorough analysis conducted with a view to evaluating the effects of different current densities and initial pH values on atrazine degradation showed that the application of higher current densities resulted in lower energy consumption, as this led to faster removal of atrazine. Additionally, the initial pH of the solution was found to favor the formation of different species of active chlorine. The radicals formed during the electro-oxidation process were detected by electron paramagnetic resonance spectroscopy and include hydroxyl, methoxy and hydroxymethyl. The use of methanol for the degradation of pollutants is a highly promising technique and this work shows that the identification of the different radicals formed in the process can be the key to understanding the degradation mechanism.

摘要

这项工作报道了在甲醇介质中存在和不存在不同比例水(0%、5%和 10%)的情况下莠去津降解过程中检测到的自由基。确定这些自由基是理解甲醇介质中电解过程的重要步骤,并有助于阐明降解机制。此外,优化了成功去除污染物的参数,结果表明,该技术的应用导致在 1 小时的电解后,莠去津的去除率接近 99.8%。发现氧化动力学非常快,介质中的大部分莠去津分子在电解的第一个小时内被降解。通过彻底分析获得的结果,评估了不同电流密度和初始 pH 值对莠去津降解的影响,结果表明,应用更高的电流密度导致更低的能耗,因为这导致莠去津更快地去除。此外,发现溶液的初始 pH 值有利于形成不同种类的活性氯。通过电子顺磁共振波谱法检测到电氧化过程中形成的自由基,包括羟基、甲氧基和羟甲基。甲醇用于降解污染物是一种很有前途的技术,本工作表明,识别过程中形成的不同自由基可能是理解降解机制的关键。

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