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超声纳米零价铁/过氧化氢体系中 1-烷基-3-甲基咪唑溴盐的降解途径和动力学。

Degradation pathway and kinetics of 1-alkyl-3-methylimidazolium bromides oxidation in an ultrasonic nanoscale zero-valent iron/hydrogen peroxide system.

机构信息

Faculty of Forensic Medicine, Henan University of Science and Technology, Luoyang, Henan 471003, PR China.

School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, PR China.

出版信息

J Hazard Mater. 2015 Mar 2;284:241-52. doi: 10.1016/j.jhazmat.2014.10.050. Epub 2014 Nov 11.

Abstract

Fenton and Fenton-like oxidation has been already demonstrated to be efficient for the degradation of imidazolium ionic liquids (ILs), but little is known for their degradation pathway and kinetics in such systems. In this work, degradation pathway and kinetics of 1-alkyl-3-methylimidazolium bromides ([Cnmim]Br, n=2, 4, 6, 8, and 10) were investigated in an ultrasound nanoscale zero-valent iron/hydrogen peroxide (US-nZVI/H2O2) system. For this purpose, 1-butyl-3-methylimidazolium bromide ([C4mim]Br) was used as a representative ionic liquid to optimize pH value, nZVI dose, and H2O2 concentration for the degradation reaction. Then, the degradation kinetics of [Cnmim]Br was investigated under optimal conditions, and their degradation intermediates were monitored by gas chromatography-mass spectrometry (GC-MS). It was shown that the degradation of [Cnmim]Br in such a heterogeneous Fenton-like system could be described by a second order kinetic model, and a number of intermediate products were detected. Based on these intermediate products, detailed pathways were proposed for the degradation of [Cnmim]Br in the ultrasound-assisted nZVI/H2O2 system. These findings may be useful for the better understanding of degradation mechanism of the imidazolium ILs in aqueous solutions.

摘要

芬顿和类芬顿氧化已被证明可有效降解离子液体(ILs),但对于它们在这些体系中的降解途径和动力学知之甚少。在这项工作中,在超声纳米零价铁/过氧化氢(US-nZVI/H2O2)体系中研究了 1-烷基-3-甲基咪唑溴盐([Cnmim]Br,n=2、4、6、8 和 10)的降解途径和动力学。为此,选择 1-丁基-3-甲基咪唑溴盐([C4mim]Br)作为代表性离子液体,优化了降解反应的 pH 值、nZVI 剂量和 H2O2 浓度。然后,在最佳条件下研究了[Cnmim]Br 的降解动力学,并通过气相色谱-质谱(GC-MS)监测其降解中间体。结果表明,[Cnmim]Br 在这种多相类芬顿体系中的降解可以用二级动力学模型来描述,并检测到了一些中间产物。基于这些中间产物,提出了在超声辅助 nZVI/H2O2 体系中[Cnmim]Br 降解的详细途径。这些发现可能有助于更好地理解水溶液中咪唑 ILs 的降解机制。

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