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农药灭多威的光催化降解:反应途径的确定及中间产物的鉴定

Photocatalytic degradation of pesticide methomyl: determination of the reaction pathway and identification of intermediate products.

作者信息

Tamimi M, Qourzal S, Assabbane A, Chovelon J-M, Ferronato C, Ait-Ichou Y

机构信息

Laboratoire de Chimie-Physique, Equipe de Photocatalyse et Environnement, Département de Chimie, Faculté des Sciences, Université Ibn Zohr, B.P. 8106 Cité Dakhla, Agadir, Maroc.

出版信息

Photochem Photobiol Sci. 2006 May;5(5):477-82. doi: 10.1039/b517105a. Epub 2006 Mar 20.

Abstract

The degradation of pesticide methomyl in aqueous solution by UV-irradiation in the presence of TiO2 "Degussa P-25" has been studied. It was found that mineralisation to carbon dioxide, water, sulfate and ammonia took place during the process. The rate of photodecomposition of methomyl was measured using high performance liquid chromatography (HPLC), while its mineralization was followed using ion chromatography (IC), and total organic carbon (TOC) analysis. The identification of reaction intermediate products was carried out using coupled techniques HPLC-MS (electrospray ionization in positive mode) and a degradation pathway was proposed. Under our conditions, complete disappearance of 1.23 x 10(-4) mol l(-1) of pure pesticide occurred within 45 min of illumination and 80% TOC removal occurred in less than 4 h. Three main intermediates were identified resulting from (i) the rupture of the ester bond (or the N-O bond), (ii) the hydroxylation of methyl group borne by the nitrogen atom and (iii) the product resulting from the decarboxylation of the oxidized hydroxylated methyl group (photo-Kolbe reaction). In order to be sure that the photocatalytic results were consistent, hydrolysis and photolysis tests were performed. Photocatalysis proved to be an excellent new advanced oxidation technology (AOT) to eliminate methomyl present in water.

摘要

研究了在二氧化钛“德固赛P - 25”存在下,通过紫外线照射降解水溶液中的农药灭多威。结果发现,在此过程中灭多威矿化为二氧化碳、水、硫酸盐和氨。使用高效液相色谱法(HPLC)测定灭多威的光分解速率,同时使用离子色谱法(IC)和总有机碳(TOC)分析跟踪其矿化过程。利用HPLC - MS联用技术(正模式电喷雾电离)对反应中间产物进行鉴定,并提出了降解途径。在我们的实验条件下,1.23×10⁻⁴ mol·L⁻¹的纯农药在光照45分钟内完全消失,在不到4小时内TOC去除率达到80%。鉴定出三种主要中间体,分别来自(i)酯键(或N - O键)断裂,(ii)氮原子所带甲基的羟基化,以及(iii)氧化羟基化甲基脱羧产物(光柯尔伯反应)。为确保光催化结果的一致性,进行了水解和光解试验。事实证明,光催化是一种消除水中灭多威的优秀新型高级氧化技术(AOT)。

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