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采用 Ti/SnO2-Sb/PbO2 电极在水溶液中对 4-氯-3-甲基苯酚进行阳极氧化的机理。

Mechanism of the anodic oxidation of 4-chloro-3-methyl phenol in aqueous solution using Ti/SnO2-Sb/PbO2 electrodes.

机构信息

College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032, People's Republic of China.

出版信息

J Hazard Mater. 2010 Mar 15;175(1-3):614-21. doi: 10.1016/j.jhazmat.2009.10.051. Epub 2009 Oct 22.

Abstract

Electrochemical oxidation of 4-chloro-3-methyl phenol (CMP) was examined using Ti/SnO(2)-Sb/PbO(2) anodes. The physicochemical properties of the electrodes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The degradation was studied by monitoring the total organic carbon (TOC) removal of CMP, and variation of the concentration of intermediates by high-performance liquid chromatography (HPLC), ion chromatography (IC) and gas chromatography/mass spectrometry (GC/MS). The mineralization of CMP is confirmed to be controlled by mass transfer or by both chemical reaction and mass transfer. Hydroxyl radicals (OH) and active chlorine on the electrode surface had a dominant role in the electro-oxidation process. The chloride element in CMP was immediately driven away from parent substance by OH attack, and then accelerated the ring cleavage of methyl-p-benzoquinone, which was formed during the anodic oxidation of CMP. Ultimately, the chlorine of CMP was mainly transformed to hypochlorite and chloride ion in aqueous solution. Additionally, formic acid and acetic acid were relatively stable products that were not electro-oxidized efficiently in our experiments. The degradation pathway of CMP is proposed on the basis of these results.

摘要

采用 Ti/SnO(2)-Sb/PbO(2) 电极对 4-氯-3-甲基苯酚(CMP)进行电化学氧化研究。通过 X 射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试对电极的物理化学性质进行了表征。通过监测 CMP 的总有机碳(TOC)去除率以及高效液相色谱(HPLC)、离子色谱(IC)和气相色谱/质谱(GC/MS)中中间产物浓度的变化来研究降解情况。CMP 的矿化被证实是由传质或化学反应和传质共同控制的。羟基自由基(OH)和电极表面的活性氯在电氧化过程中起主导作用。CMP 中的氯元素立即被 OH 攻击从母体物质中驱离,然后加速 CMP 阳极氧化过程中形成的甲基对苯醌的环裂解。最终,CMP 中的氯主要转化为次氯酸盐和氯离子在水溶液中。此外,在我们的实验中,甲酸和乙酸是相对稳定的产物,不能有效地进行电氧化。根据这些结果提出了 CMP 的降解途径。

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