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三氯生的光解及二氧化钛光催化的动力学与机理

Kinetics and mechanism of photolysis and TiO2 photocatalysis of triclosan.

作者信息

Son Hyun-Seok, Ko Gwangpyo, Zoh Kyung-Duk

机构信息

Institute of Health & Environment, Seoul National University, Seoul 110-799, Republic of Korea.

出版信息

J Hazard Mater. 2009 Jul 30;166(2-3):954-60. doi: 10.1016/j.jhazmat.2008.11.107. Epub 2008 Dec 6.

Abstract

The degradations of triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol), a potent broad-spectrum antimicrobial agent, were compared in TiO2-only in the dark condition, photolysis, and TiO2 photocatalysis with a UV-A lamp. TiO2 photocatalysis more effectively degraded and mineralized triclosan compared to TiO2-only and photolysis conditions. While triclosan removed only 30% by TiO2-only condition within 20 min, the triclosan degradation in photolysis and photocatalysis at the same time was 75 and 82%, respectively, and TOC removal was significantly higher in photocatalysis than in photolysis. The data of kinetics showed that triclosan adsorption onto TiO2 was fitted to Langmuir isotherm, and TiO2 photocatalysis was fitted to Langmuir-Hinshelwood model (b=27.99 mM(-1), K(triclosan)=9.49 mM(-1)). The neutral range of pH was favorable to photocatalysis due to the charge effect between TiO2 and triclosan. The addition of 2-propanol, a radical scavenger, significantly reduced the degradation of triclosan both in photolysis and photocatalysis. Dioxin-type intermediates such as dibenzo-dichloro-p-dioxin (DCDD), dibenzo-p-dioxin were produced in photolysis with and without 2-propanol, and also in photocatalysis with 2-propanol, but these intermediates were not detected in photocatalysis without 2-propanol. This result indicates that the photocatalytic degradation of triclosan is mainly achieved by radicals, and these radicals can further degrade dioxin-type intermediates once they are produced in photocatalysis.

摘要

在黑暗条件下仅使用二氧化钛、光解以及使用紫外A灯进行二氧化钛光催化这三种情况下,对高效广谱抗菌剂三氯生(5-氯-2-(2,4-二氯苯氧基)-苯酚)的降解情况进行了比较。与仅使用二氧化钛和光解条件相比,二氧化钛光催化能更有效地降解和矿化三氯生。在仅使用二氧化钛的条件下,20分钟内三氯生的去除率仅为30%,而在光解和光催化条件下,同一时间内三氯生的降解率分别为75%和82%,且光催化过程中总有机碳的去除率显著高于光解。动力学数据表明,三氯生在二氧化钛上的吸附符合朗缪尔等温线,二氧化钛光催化符合朗缪尔-欣谢尔伍德模型(b = 27.99 mM⁻¹,K(三氯生)= 9.49 mM⁻¹)。由于二氧化钛和三氯生之间的电荷效应,pH的中性范围有利于光催化。自由基清除剂2-丙醇的添加显著降低了光解和光催化过程中三氯生的降解。在有和没有2-丙醇的光解过程中以及有2-丙醇的光催化过程中都会产生二噁英类中间体,如二苯并二氯对二噁英(DCDD)、二苯并对二噁英,但在没有2-丙醇的光催化过程中未检测到这些中间体。这一结果表明,三氯生的光催化降解主要通过自由基实现,并且一旦这些自由基在光催化过程中产生,它们可以进一步降解二噁英类中间体。

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