分子筛Pickering界面催化体系的构建及其催化烯烃水合和环氧化性能的研究

The low reaction efficiency is mainly caused by the immiscible substrates and reaction coupling transfer in oil/water bi-phasic reaction. To increase the efficiency, traditional approaches are to introduce a phase transfer agent or organic co-solvents, however they usually lead to increase cost on production or difficulty on separation with product and recovery. Recently, Pickering interfacial catalysis brings a new opportunity for oil/water bi-phasic reaction. The principle is that amphiphilic solid particles emulsify oil/water leading to largely increase of the contact area of substrates, meanwhile catalytic reaction takes place in the numerous microscopic interfaces of emulsion droplets. . In this project, aiming for hydration of olefin and epoxidation of olefin, we will design and synthesize a series of novel amphiphilic nanozeolite with acidity or hetero atoms, build Pickering interfacial catalysis, study Pickering emulsification of amphiphilic solids and their catalytic properties , establish relationship among the nature of material, Pickering emulsifying capacity and catalytic activity, investigate microscopic reaction mechanism and the macro-control mechanism. Meantime, we will explore the separation method of bifunctional solids and their recycle. Compared with conventional approaches, this study will probably be able to improve the efficiency of hydration and epoxidation of alkene, and lower the cost. The depth study of formation conditions of Pickering interfacial catalysis will probably provide a new way for the development of green biphasic catalytic processes.

反应底物不互溶和反应传递耦合是制约油水两相催化反应效率低下的关键因素。传统解决办法是引入相转移剂或有机共溶剂，这些方法或者成本高或者后续分离困难。而Pickering界面催化为解决这一困境提供了新的思路。它的原理是通过两亲性的固体催化颗粒乳化油水反应系统从而大幅增加反应底物接触面积，同时在形成的无数微观界面上催化反应。. 本课题针对烯烃水合及环氧化两类典型反应，拟设计合成出一系列两亲性酸性与含杂原子的新型纳米分子筛，构建Pickering界面催化体系，考察固体颗粒Pickering 乳化及催化性能，从而建立材料性质、Pickering乳化能力和催化活性三者之间的关系，研究反应微观机理与宏观调控机制。同时，我们将探讨双功能固体颗粒分离与回收利用。该研究有望提高目标反应效率，降低反应成本。Pickering界面催化形成条件的深入研究能够为开发新型绿色两相催化反应过程提供新途径。

本项目针对化学过程常见的油水两相催化体系传质难反应效率低的问题，构建Pickering界面催化体系，通过研究催化材料的设计、催化性能和Pickering乳化之间三者关系，为解决上述两相催化提供可行性新方案。系统设计出系列两亲性的纤维硅包裹的TS-1纳米颗粒，通过表面硅烷化调节材料在水油达到合适的亲水亲油性，该类材料应用于苯羟基化反应制备苯酚和烯烃的环氧化两类两相反应中。催化结果显示，材料所构建的Pickering界面催化活性优于同一反应条件下的界面催化体系，而其催化活性与材料的Pickering乳化能力有着直接的联系。本项目中对两相催化反应所提出的Pickering界面催化为两相催化提供了新思路和解决方案，具有潜在的工业价值。