文献类型：期刊文献

英文题名：DFT studies on the reaction mechanism and kinetics of dibutyl phthalate initiated by hydroxyl and sulfate radicals: Prediction of the most reactive sites

作者：Li, Huanxuan[1];Miao, Xiangrui[1];Zhang, Jian[1];Du, Jia[1];Xu, Shaodan[1];Tang, Junhong[1];Zhang, Yayun[2]

机构：[1]Hangzhou Dianzi Univ, Coll Mat & Environm Engn, Hangzhou 310018, Zhejiang, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2020

卷号：381

外文期刊名：CHEMICAL ENGINEERING JOURNAL

收录：;EI(收录号：20193607407261);WOS:【SCI-EXPANDED(收录号:WOS:000499066900044)】；

基金：This work was supported by National Natural Science Foundation of China (No. 51808177).

语种：英文

外文关键词：Density functional theory (DFT); Dibutyl phthalate (DBP); Hydroxyl radical ((OH)-O-center dot); Sulfate radical (SO4 center dot-); Mechanism; Kinetics

摘要：In this study, the reaction mechanism and kinetics of dibutyl phthalate (DBP) initiated by hydroxyl ((OH)-O-center dot) and sulfate radicals (SO4 center dot-) were investigated at the CAM-B3LYP/6-311+G(d,p) level through Density Functional Theory (DFT), where the preferred reaction sites of DBP were determined. The calculation results revealed that the reactions of SO4 center dot- with DBP exhibited considerably higher energy barriers than that with (OH)-O-center dot because of the steric hindrance. For (OH)-O-center dot, the addition of (OH)-O-center dot to unsaturated carbons of phenyl ring was kinetically favored with respect to the direct H abstraction from the phenyl ring. In contrast, the reactions of SO4(center dot)- triggering formal hydrogen atom transfer from the phenyl ring of DBP were more likely to occur. Interestingly, all SO4 center dot-initiated reactions were not thermodynamically favorable in the gas phase, but the additions of SO4 center dot- to C2, C3, and C4 of the phenyl ring preferred to take place in water. The C2 and C3 were the most reactive sites by SO4 center dot- and (OH)-O-center dot attacks with energy barriers of 86.5 and 20.1 kJ mol(-1), respectively in the gas phase, and the corresponding rate constants were 4.33x10(-3) and 1.86x10(9) cm(3) molecule(-1) s(-1). In addition, obtained results indicated that both free radicals preferred to attack the butyl chains rather than phenyl ring, which was in good agreement with our previous experimental data. The present work could provide supplementary information on the dual-radicals dependent PAEs degradation.