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采用原位红外光谱法研究了碱性条件下对氯苯酚(PCP)在Pt电极上电化学氧化的脱氯反应机理.研究结果表明Pt电极对PCP有良好的电化学反应活性,其氧化过程首先是对氯苯酚负离子氧化生成对氯苯氧自由基,该自由基可与对氯苯酚负离子作用生成芳香醚低聚物;随着电位升高,对氯苯酚负离子经电化学氧化生成了苯二酚盐(还可能存在其氧化产物不饱和羧酸盐);当电位继续升高,苯二酚盐进一步氧化形成苯醌;最后,在Pt表面生成小分子羧酸盐,同时生成了最终产物CO2.但由于芳香醚低聚物等不溶性聚合物膜的形成并吸附在Pt电极表面,可造成Pt电极毒化,使得Pt电极在使用过程中逐渐失去活性.
The mechanism of dechlorination reaction of p-chlorophenol (PCP) on Pt electrode was investigated by in situ FT-IR spectroscopy. The results show that Pt electrode has a good electrochemical reactivity with PCP. The oxidation process of Pt It is the oxidation of p-chlorophenol anion to p-chlorophenoxy radical, which can react with p-chlorophenol anion to form aromatic ether oligomer. With the increase of potential, p-chlorophenol anion is electrochemically oxidized to form hydroquinone Salt (and possibly the oxidation product of unsaturated carboxylic acid salt); when the potential continues to rise, further oxidation of benzene bisphenols to form benzoquinone; finally, small molecule carboxylate is formed on the surface of Pt, and the final product CO2 is generated. However, due to the formation of an insoluble polymer film such as an aromatic ether oligomer and adsorption on the surface of the Pt electrode, Pt electrode can be poisoned, so that the Pt electrode gradually loses its activity during use.