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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (18): 2191-2195. 上一篇    下一篇

研究简报

高温水中多产物反应模型的构建及机理研究

王志忠，王媛媛，常永娟，戴立益*   

  1. (华东师范大学化学系 上海市绿色化学与化工过程绿色化重点实验室 上海 200062)
  • 投稿日期:2011-01-26 修回日期:2011-03-16 发布日期:2011-05-06
  • 通讯作者: 戴立益 E-mail:lydai@chem.ecnu.edu.cn

Multiproduct Reactions in High Temperature Water: Model Building and Mechanism Investigation

WANG Zhi-Zhong, WANG Yuan-Yuan, CHANG Yong-Juan, DAI Li-Yi   

  1. (Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, Shanghai 200062)
  • Received:2011-01-26 Revised:2011-03-16 Published:2011-05-06

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建立了高温水中的反应模型并采用密度泛函理论(DFT)对香叶醇在高温水中的反应路径进行了研究. 通过前线轨道分析确定了反应的可能性. 高温水中香叶醇的反应路径与常温水中不同, 从常态下的酸催化反应路径转变为高温水状态下的酸碱共催化路径, 计算所得反应能垒为205.8 kJ/mol. 分别计算分析了高温水环境和周围水分子对反应能垒的影响, 结果表明, 高温水对反应物零点能的影响最大为0.966 kJ/mol, 水分子个数的影响最大可达94.7 kJ/mol. 官能团周围水分子个数变化对反应所产生的的影响大于高温水环境的影响.

关键词: 高温水, 香叶醇, 密度泛函理论, 模型, 机理

Multiproduct reactions of geraniol with H3O＋and (H2O)6 model in high temperature water (HTW) have been investigated by the use of density functional theory calculations. A model considering both HTW ambient and water molecular is built to investigate the reaction and the results show that the reaction is total acid-base catalyzed in high temperature. The two influence factors have been investigated separately. The energy barrier of this reaction is 205.8 kJ/mol. The results show that the local water number has more effect than overall environment.

Key words: high temperature water, geraniol, density functional theory, model, mechanism