新型-SO3H功能化离子液体微观结构及增效机制研究

项目名称： 新型-SO3H功能化离子液体微观结构及增效机制研究

项目编号： No.21203218

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 物理化学

项目作者： 王芳

作者单位： 中国科学院兰州化学物理研究所

项目金额： 23万元

中文摘要： -SO3H 功能化离子液体因结合了液体酸和离子液体的优点，有望替代传统的液体无机酸和固体酸成为环境友好的反应介质和催化剂，近年来备受关注。与较多的实验研究相比，人们利用理论计算研究-SO3H功能化离子液体的报道较少。本项目拟首先运用量子化学计算和分子动力学模拟，对磺酸功能化离子液体的微观结构进行系统的研究，探讨阴阳离子的相互作用方式，并结合实验手段，研究阴阳离子种类、侧链长度、溶剂化效应等对其结构和物化性质（如酸性）的影响，获取相关的热力学数据和动力学信息。继而采用量化计算和原位谱学表征技术，对此类酸性离子液体催化醇醛缩合和Beckmann重排的反应开展机理研究，探讨催化剂结构、催化剂体系组成与催化性能间的关系，考察催化反应的历程，确定反应进行的有利通道，掌握控制反应的关键因素，获取酸性离子液体高催化活性和高选择性的内在原因，从微观角度加深人们对-SO3H功能化离子液体的认识。

中文关键词： -SO3H；离子液体；微观结构；反应机理；密度泛函

英文摘要： Due to simultaneously possess proton acidity of liquid acid and characteristic properties of ionic liquid, -SO3H functionalized ionic liquids (-SO3H FILs) have the potential to replace traditional liquid inorganic acids and solid acids, and offer the possibility to be environmental-friendly solvents and catalysts. Compared with the extensive experimental studies for -SO3H FILs, the theoretical studies is relatively limited. In present program, the structures,dynamics, nature of the interaction between cation and anion for -SO3H FILs will be systematicly studied at first employing density functional theory study (DFT) and molecular dynamics simulation (MD). Along with experiment, the influence for the structure and physical-chemical properties originated from the kinds of ctions and anions, side chains and solvents will also be investigated. Then the mechanistic details for aldol condensation and Beckmann rearrangement promoted by ILs with and without -SO3H functional group will be explored by DFT calculation and in-situ spectral characterization. We are interested to discuss the relationship between catalysts structure, components and catalytic activity, investigate the possible pathways, determine the favorable channels, search the keys controlling the reaction, and understand the origination for the high activ

英文关键词： -SO3H；ionic liquids；microstructure；mechanism；DFT