物理化学学报 >> 2017, Vol. 33 >> Issue (7): 1399-1410.doi: 10.3866/PKU.WHXB201704132

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基于ReaxFF力场的对硝基苯酚臭氧氧化分子动力学模拟

王子民1,2,郑默2,谢勇冰3,李晓霞2,4,*(),曾鸣1,曹宏斌3,*(),郭力2,4   

  1. 1 中国矿业大学(北京)化学与环境工程学院,北京100083
    2 中国科学院过程工程研究所复杂系统国家重点实验室,北京100190
    3 中国科学院过程工程研究所环境技术与工程研究部,北京100190
    4 中国科学院大学化学与化工学院,北京100049
  • 收稿日期:2017-01-26 发布日期:2017-05-31
  • 通讯作者: 李晓霞,曹宏斌 E-mail:xxia@ipe.ac.cn;hbcao@ipe.ac.cn
  • 基金资助:
    国家自然科学基金(21373227);国家杰出青年科学基金(51425405);多相复杂系统国家重点实验室基金(COM2015A004)

Molecular Dynamics Simulation of Ozonation of p-Nitrophenol at Room Temperature with ReaxFF Force Field

Zi-Min WANG1,2,Mo ZHENG2,Yong-Bing XIE3,Xiao-Xia LI2,4,*(),Ming ZENG1,Hong-Bin CAO3,*(),Li GUO2,4   

  1. 1 School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing, Beijing 100083, P. R. China
    2 State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Science, Beijing 100190, P. R. China
    3 Research Center for Process Pollution Control, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Science, Beijing 100190, P. R. China
    4 School of Chemistry and Chemical Engineering, University of Chinese Academy of Science, Beijing 100049, P. R. China
  • Received:2017-01-26 Published:2017-05-31
  • Contact: Xiao-Xia LI,Hong-Bin CAO E-mail:xxia@ipe.ac.cn;hbcao@ipe.ac.cn
  • Supported by:
    The project was supported by the National Natural Science Foundation of China(21373227);National Science Fund for Distinguished Young Scholars, China(51425405);China's State Key Laboratory of Multiphase Complex Systems, China(COM2015A004)

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摘要：

本文采用基于ReaxFF反应力场的分子动力学方法（ReaxFF MD），利用自主研发的国际首个基于GPU加速的ReaxFF MD程序系统GMD-Reax和独特的化学反应分析工具VARxMD，探索臭氧氧化对硝基苯酚的反应机理。通过模拟考察了300 K恒温条件下臭氧氧化水中对硝基苯酚的行为，获得了酚结构开环、CO2生成、主要自由基（·OH、·O2、·O）及团簇型自由基的数量演变趋势，并可定性描述六元环开环和CO2生成均遵循伪一级反应动力学规律。反应机理分析表明酚类分子在水溶液中被臭氧氧化的路径主要经过攫氢、六元环开环、碳链的氧化分解三个阶段，也揭示了自由基和团簇型自由基在臭氧降解对硝基苯酚时所发挥的重要作用。本工作是应用ReaxFF MD分子模拟方法对常温水环境下臭氧降解酚类污染物反应机理研究的一个尝试，可为深入认识该机理及相关的实验、理论研究提供一定的参考。

关键词: 对硝基苯酚, 臭氧, 反应分子动力学模拟, 自由基行为, 反应机理

Abstract:

Understanding the reaction mechanism of phenol ozonation in coking wastewater is very important for industrial applications of the ozonation process. Ozonation of p-nitrophenol in water at 300 K was simulated by ReaxFF force field molecular dynamics (ReaxFF MD) employing the GPU-enabled high-performance code of GMD-Reax and a unique code of VARxMD developed in authors' group. Evolution trends of aromatic ring opening, CO2 generation, dominant radicals (·OH, ·O2, ·O), and H2O clusters were obtained. The simulated CO2 generation and reduction of aromatic ring could be described with pseudo-first-order kinetics. Moreover, the reaction pathways for the ozonation of p-nitrophenol can be divided into three stages:hydrogen abstraction, opening of the six-membered-ring structure, and the breaking of C-C bonds. The simulations revealed the important role of radicals and water clusters in the ozonation of p-nitrophenol. This work is an attempt to investigate the ozonation mechanism of phenols in aqueous solutions at room temperature using ReaxFF MD, which should be helpful for further experimental or theoretical investigation of the mechanism.

Key words: >p-Nitrophenol, Ozonation, ReaxFF MD, Radical behavior, Reaction mechanism