TS-1分子筛催化剂活性中心溶剂效应及氯丙烯环氧化的理论研究
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- 英文论文题名：Theoretical Study of Solvent Effect and Expoxidation of Allyl Chloride on TS-1 Catalyst
- 论文作者：李蒙召 ; 王译晨 ; 周丹红
- 英文论文作者：Mengzhao Li ; Yichen Wang ; Danhong Zhou ; College of Chemistry and Chemical Engineering ; Liaoning Normal University
- 年：2016
- 作者机构：辽宁师范大学化学化工学院;
- 论文关键词：TS-1分子筛 ; 钛氧活性心结构 ; 溶剂效应 ; 氯丙烯
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十三分会：绿色化学
- 语种：中文
- 分类号：O621.251
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十三分会 ; 绿色化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：245k
- 原文格式：D
- 会议级别：全国
摘要
TS-1分子筛在H_2O_2水溶液中的一系列选择氧化反应均表现出优异的催化性能。本研究采用密度泛函理论计算的方法,以TS-1分子筛中Ti-η~2-OOH和Ti-η~1-OOH模型为活性中心结构,探讨了H_2O、CH_3OH溶剂在Ti中心以及通过氢键作用的吸附,并进一步研究了氯丙烯的环氧化机理。结果表明,在不同活性中心结构上,氯丙烯环氧化反应的活化能垒依照下列顺序升高:Ti-η~2-OOH-CH_3OH环氧化反应的活化能垒最低。对于五元环Ti-η~1-OOH活性中心,由于受到分子筛周围骨架空间障碍的影响,不利于溶剂分子的靠近,氯丙烯环氧化反应的活化能垒也相对较高。
TS-1 molecular sieve have been attracting much attention,because it is capable of serving as highly efficient catalysts for the oxidation of various organic substrates with H_2O_2 as an oxidant under mild conditions.Density functional theory has been used to study the effects of solvent coordination on the structure and formation of the titanium hydroperoxo species believed to be the active intermediate of epoxidation reactions in TS-1/H_2O_2 catalytic systems and allyl chloride.It indicated that the most likely reaction activation energy is Ti-η~2-OOH species with adsorption of CH_3OH by hydrogen bonding.For the Ti-η~1-OOH activity center,due to steric hindrance is not conducive to solvent molecules close that allyl chloride epoxidation reaction activation energy barrier is high,respectively.
TS-1 molecular sieve have been attracting much attention,because it is capable of serving as highly efficient catalysts for the oxidation of various organic substrates with H_2O_2 as an oxidant under mild conditions.Density functional theory has been used to study the effects of solvent coordination on the structure and formation of the titanium hydroperoxo species believed to be the active intermediate of epoxidation reactions in TS-1/H_2O_2 catalytic systems and allyl chloride.It indicated that the most likely reaction activation energy is Ti-η~2-OOH species with adsorption of CH_3OH by hydrogen bonding.For the Ti-η~1-OOH activity center,due to steric hindrance is not conducive to solvent molecules close that allyl chloride epoxidation reaction activation energy barrier is high,respectively.
引文
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