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电化学氧化法在中性水溶液介质中通过阳极氧化焚烧双氯芬酸,使用 Pt 和掺硼金刚石阳极。

Electrochemical incineration of diclofenac in neutral aqueous medium by anodic oxidation using Pt and boron-doped diamond anodes.

机构信息

Laboratori d'Electroquímica de Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.

出版信息

Chemosphere. 2010 Apr;79(6):605-12. doi: 10.1016/j.chemosphere.2010.03.004. Epub 2010 Mar 21.

DOI:10.1016/j.chemosphere.2010.03.004
PMID:20307900
Abstract

The degradation of diclofenac, a common non-steroidal anti-inflammatory drug, in aqueous medium has been studied by anodic oxidation (AO) using an undivided cell with a Pt or boron-doped diamond (BDD) anode. Operating without pH regulation, AO with Pt acidifies the solution with precipitation of its protonated form, whereas using BDD, the solution becomes alkaline and only attains partial mineralization. Total incineration of low contents of the drug is feasible by AO with BDD in a neutral buffer medium of pH 6.5. Comparative treatment with Pt gives poor decontamination. The diclofenac decay always follows a pseudo first-order reaction. The increase in current for AO with BDD accelerates the degradative process, but decreases its efficiency. 2-Hydroxyphenylacetic acid, 2,5-dihydroxyphenylacetic acid, 2,6-dichloroaniline and 2,6-dichlorohydroquinone have been identified as aromatic intermediates. For AO with Pt, high amounts of malic, succinic, tartaric and oxalic acids are accumulated in the bulk and the N-derivatives produced are rapidly destroyed with loss of NH4+. When BDD is employed, some carboxylic acids are also accumulated in small extent, with a larger persistence of oxalic and oxamic acids. The process involves the formation of different N-derivatives that slowly release NH4+ and NO3(-) ions. Chloride ion is lost in all cases.

摘要

在无 pH 值调节条件下,使用 Pt 作为阳极进行阳极氧化(AO)会使溶液酸化,并促使其质子化形式沉淀,而使用掺硼金刚石(BDD)作为阳极则会使溶液呈碱性,且仅实现部分矿化。在中性缓冲介质(pH 值为 6.5)中,使用 BDD 进行 AO 可实现低含量药物的完全焚烧。相比之下,使用 Pt 进行 AO 的处理效果较差,无法有效净化。

降解反应始终遵循一级动力学。BDD 进行 AO 时电流的增加会加速降解过程,但降低其效率。已鉴定出 2-羟基苯乙酸、2,5-二羟基苯乙酸、2,6-二氯苯胺和 2,6-二氯对苯二酚等芳香族中间体。对于使用 Pt 的 AO,大量的苹果酸、琥珀酸、酒石酸和草酸在主体中积累,生成的 N-衍生物迅速被破坏,同时失去 NH4+。当使用 BDD 时,也会在较小程度上积累一些羧酸,并且草酸和草酰胺的持久性更大。该过程涉及形成不同的 N-衍生物,这些衍生物会缓慢释放 NH4+和 NO3(-)离子。在所有情况下,氯离子都会丢失。

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