A DFT Study Toward the Reaction Mechanisms of TNT With Hydroxyl Radicals for Advanced Oxidation Processes

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• 作者：Xi He ; Qun Zeng ; Yang Zhou ; Qingxuan Zeng ; Xianfeng Wei ; Chaoyang Zhang
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：May 26, 2016
• 年：2016
• 卷：120
• 期：20
• 页码：3747-3753
• 全文大小：477K
• 年卷期：0
• ISSN：1520-5215

文摘

The degradation pathway of environmental contaminant 2,4,6-trinitrotoluene (TNT) was investigated computationally at the SMD(Pauling)/M06-2X/6-311+G(d,p) level of theory. The dominant decomposition pathway of TNT → 4,6-dinitro-o-cresol → 4,6-dinitro-2-hydroxybenzylalcohol → 4,6-dinitro-2-hydroxybenzaldehyde was provided, and the corresponding predicted products and their distributions are in a good agreement with available experimental data on TNT degradation by Fenton reaction. It was shown that the mechanism of addition–elimination is crucial for this stage of the reaction. The reaction of H atom abstraction is a minor competing pathway. The details on transition states, intermediate radicals, and free energy surfaces for all proposed reactions are given and make up for a lack of experimental knowledge.