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在酸性 pH 值下苯甲酸的自增强臭氧化。

Self-enhanced ozonation of benzoic acid at acidic pHs.

机构信息

State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China.

State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China; School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310012, China.

出版信息

Water Res. 2015 Apr 15;73:9-16. doi: 10.1016/j.watres.2015.01.010. Epub 2015 Jan 16.

Abstract

Ozonation of recalcitrant contaminants under acidic conditions is inefficient due to the lack of initiator (e.g., OH(-)) for ozone to produce hydroxyl radicals (HO). In this study, we reported that benzoic acid (BA), which is inert to ozone attack, underwent efficient degradation by ozone at acidic pH (2.3). The kinetics of BA degradation and ozone decomposition were both enhanced by increasing BA concentrations. Essentially, it is a HO-mediated reaction. Based on the exclusion of possible contributions of H2O2 and phenol-like intermediates for HO production, the reaction mechanism involved the formation of ozone ion ( [Formula: see text] ), which is an effective precursor of HO, was thus proposed. The hydroxycyclohexadienyl-type radicals generated during the attack of BA by HO may lead to the formation of [Formula: see text] . Meanwhile, [Formula: see text] could also be possibly formed from the reaction between ozone and organic (e.g., ROO∙) or inorganic peroxyl radicals (e.g., HO2). In addition, the hydroxylated products like phenol-like intermediates also played a positive role in HO production. Consequently, HO was produced efficiently under acidic conditions, resulting in rapid degradation of BA. This study provides a new approach for ozone activation even at acidic pHs, and broadens the knowledge of ozonation in removal of micropollutants from water.

摘要

在酸性条件下,由于缺乏引发剂(例如 OH(-))来产生羟基自由基(HO),因此难以对顽固污染物进行臭氧化处理。在本研究中,我们发现苯甲酸(BA)在酸性 pH(2.3)条件下可被臭氧有效降解,而 BA 对臭氧攻击是惰性的。BA 浓度的增加会同时增强 BA 降解和臭氧分解的动力学。从本质上讲,这是一种 HO 介导的反应。基于排除 H2O2 和类酚中间体对 HO 生成的可能贡献,提出了涉及臭氧离子( [Formula: see text] )形成的反应机制,该离子是 HO 的有效前体。HO 攻击 BA 过程中生成的羟基环己二烯基型自由基可能导致 [Formula: see text] 的形成。同时,[Formula: see text]也可能是臭氧与有机(例如 ROO∙)或无机过氧自由基(例如 HO2)之间的反应产物。此外,羟基化产物(如类酚中间体)也在 HO 生成中发挥了积极作用。因此,即使在酸性条件下,HO 也能有效地生成,导致 BA 迅速降解。该研究为在酸性 pH 下甚至为臭氧活化提供了一种新方法,并拓宽了水中微污染物去除的臭氧化知识。

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