title: Reaction mechanisms of DNT with hydroxyl radicals for advanced oxidation processes-a DFT study.
abstract: In advanced oxidation processes (AOPs), the detailed degradation mechanisms of a typical explosive of 2,4-dinitrotoluene (DNT) can be investigated by the density function theory (DFT) method at the SMD/M062X/6-311+G(d) level. Several possible degradation routes for DNT were explored in the current study. The results show that, for oxidation of the methyl group, the dominant degradation mechanism of DNT by hydroxyl radicals (•OH) is a series of sequential H-abstraction reactions, and the intermediates obtained are in good agreement with experimental findings. The highest activation energy barrier is less than 20 kcal mol-1. Other routes are dominated by an addition-elimination mechanism, which is also found in 2,4,6-trinitrotoluene, although the experiment did not find the corresponding products. In addition, we also eliminate several impossible mechanisms, such as dehydration, HNO3elimination, the simultaneous addition of two •OH radials, and so on. The information gained about these degradation pathways is helpful in elucidating the detailed reaction mechanism between nitroaromatic explosives and hydroxyl radicals for AOPs. Graphical Abstract The degradation mechanism of an important explosive, 2,6-dinitrotoluene (DNT), by the hydroxyl radical for advanced oxidation progresses.
authors.affiliation: Institute of Chemical Materials, Chinese Academy of Engineering and Physics, Mianyang, 621900, China. zhouy@caep.ac.cn.|College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, 643000, China. zhouy@caep.ac.cn.
authors.forename: Yang
authors.initials: Y
authors.lastname: Zhou
authors.affiliation: Institute of Chemical Materials, Chinese Academy of Engineering and Physics, Mianyang, 621900, China.
authors.forename: Zhilin
authors.initials: Z
authors.lastname: Yang
authors.affiliation: Institute of Chemical Materials, Chinese Academy of Engineering and Physics, Mianyang, 621900, China.|School of Material Science and Engineering, Tsinghua University, Beijing, 100084, China.
authors.forename: Hong
authors.initials: H
authors.lastname: Yang
authors.affiliation: Institute of Chemical Materials, Chinese Academy of Engineering and Physics, Mianyang, 621900, China.
authors.forename: Chaoyang
authors.initials: C
authors.lastname: Zhang
authors.affiliation: College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, 643000, China.
authors.forename: Xiaoqiang
authors.initials: X
authors.lastname: Liu
keywords: 2,4-Dinitrotoluene; DFT; Degradation mechanism