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电化学高级氧化工艺在除草剂敌草隆矿化中的应用。

Application of electrochemical advanced oxidation processes to the mineralization of the herbicide diuron.

机构信息

Laboratori d'Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain; Departamento de Química, Laboratório de Eletrocatálise e Eletroquímica Ambiental, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo (FFCLRP, USP), Av. Bandeirantes 3900, 14040-901 Ribeirão Preto, SP, Brazil.

Laboratori d'Electroquímica dels 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. 2014 Aug;109:49-55. doi: 10.1016/j.chemosphere.2014.03.006. Epub 2014 Apr 10.

Abstract

Here, solutions with 0.185mM of the herbicide diuron of pH 3.0 have been treated by electrochemical advanced oxidation processes (EAOPs) like electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) or solar PEF (SPEF). Trials were performed in stirred tank reactors of 100mL and in a recirculation flow plant of 2.5L using a filter-press reactor with a Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 electrogeneration. Oxidant hydroxyl radicals were formed from water oxidation at the anode and/or in the bulk from Fenton's reaction between added Fe(2+) and generated H2O2. In both systems, the relative oxidation ability of the EAOPs increased in the sequence EO-H2O2<EF<PEF or SPEF. The two latter processes were more powerful due to the photolysis of intermediates by UV radiation. In the stirred tank reactor, the PEF treatment with BDD was the most potent method, yielding 93% mineralization after 360 min at 100 mA cm(-2). In the flow plant, the SPEF process attained a maximum mineralization of 70% at 100 mA cm(-2). Lower current densities slightly reduced the mineralization degree in SPEF, enhancing the current efficiency and dropping the energy consumption. The diuron decay always obeyed a pseudo-first-order kinetics, with a much greater apparent rate constant in EF and SPEF compared to EO-H2O2. Oxalic and oxamic acids were detected as final carboxylic acids. Ammonium and chloride ions were also released, the latter ion being partially converted into chlorate and perchlorate ions at the BDD surface.

摘要

这里,用 pH 值为 3.0 的除草剂敌草隆 0.185mM 的溶液通过电化学高级氧化工艺(EAOPs)进行处理,如电生成 H2O2 的电化学氧化(EO-H2O2)、电芬顿(EF)和 UVA 光电芬顿(PEF)或太阳能光电芬顿(SPEF)。在 100mL 的搅拌槽反应器中和 2.5L 的循环流动装置中进行了试验,使用带 Pt 或掺硼金刚石(BDD)阳极和空气扩散阴极的压滤机反应器进行 H2O2 的电生成。氧化剂羟基自由基是由阳极的水氧化和/或在 bulk 中从加入的 Fe(2+)和生成的 H2O2 之间的芬顿反应形成的。在这两种系统中,EAOPs 的相对氧化能力按 EO-H2O2<EF<PEF 或 SPEF 的顺序增加。后两种工艺更强大,因为中间产物在 UV 辐射下发生光解。在搅拌槽反应器中,BDD 的 PEF 处理是最有效的方法,在 100 mA cm(-2)下 360 分钟后达到 93%的矿化度。在流动工厂中,SPEF 过程在 100 mA cm(-2)时达到 70%的最大矿化度。较低的电流密度略微降低了 SPEF 中的矿化度,提高了电流效率并降低了能耗。敌草隆的衰减始终遵循准一级动力学,EF 和 SPEF 中的表观速率常数明显大于 EO-H2O2。检测到草酸和氨基三亚甲基膦酸作为最终羧酸。也释放了铵和氯离子,后者离子在 BDD 表面部分转化为氯酸盐和高氯酸盐离子。

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