二维离子液体基框架功能材料的构筑及其催化性能研究

The development of a new generation of green and efficient catalyst is an important research direction in the field of catalytic science and technology. Isobutane alkylation with butene (C4 alkylation) produce highly branched Isoparaffins for the the cleaning-burning oil pool. Based on comprehensive consideration reaction characteristics of C4 alkylation, a new idea has been proposed to design and synthesis of novel two-dimensional ionic liquid based functional frameworks as solid acid catalyst, which combines multi-advantages of enzyme catalysis, homogeneous catalysis, heterogeneous catalysis, in this project. Three key scientific questions need to systematically study and answer: 1) the controllable synthesis and surfactant mediated synthesis mechanism of two-dimensional ionic liquid based framework; 2) the micro-interaction between isobbuane/butene, intermediate, products and two-dimensional ionic liquid based framework and their catalytic mechanism; 3) multi-scale structure-activity relationship and regulation mechanism. Spectroscopy technology, such as (in-situ NMR/XRD/SAXS/MIR, Materials Studio, molecular dynamics simulation, etc) ,and simulation method will be established to in situ study lyotropic liquid crystals templating formation mechanism, structure characterization of wo-dimensional ionic liquid based framework materials, and alkylation reaction mechanism and kinetics. The influence rule of the type of the ionic liquid / organic / inorganic primary building block, key functional groups, and the synthesis methods on the structure (the structure, surface properties, thermal stability, acid, etc.) the catalytic properties and micro-catalytic mechanism of multifunctional two-dimensional ionic liquid based frameworks, and their regulation mechanism will be systematically and in depth studied. Finally, two or three type two-dimensional ionic liquid based frameworks with periodic high efficient micro catalytic reaction centers, which are composed of several synergetic functional groups including acidic catalytic sites, hydrophobic groups and catalytic aids, etc., will be synthesis in this project. Our research will provide theory and technical support for the development of a new generation of high performance solid acid catalyst.

开发新一代绿色高效催化剂是催化科技领域发展的重要方向。本项目以生产高品清洁汽油的C4烷基化为模型反应，提出设计合成具有生物/均相/异相催化多重优势的二维离子液体基框架固体酸催化剂的新思路。围绕“材料可控合成及结晶机制”、“烷基化微观反应机理、“组成-结构-性能多尺度构效关系”三个关键科学问题，结合谱学技术（原位NMR/XRD/SAXS/MIR等）和计算模拟，开展从离子液体构筑基元设计到二维离子材料催化应用的探索研究。建立对二维离子材料合成机制及烷基化反应机理等原位研究方法，揭示功能离子液体/无机/有机构筑基元组成、关键功能基团、合成方法等对结构物性（微孔结构、表界面性能、酸性、热稳定性等）、催化性能及机理的影响规律及调控机制，为具有周期性高效纳微催化中心（由强酸/疏水/助催化基团等协同功能基团组构成）的新型二维离子液体基框架固体酸催化剂的优化合成及C4烷基化新工艺开发提供理论和技术支持。

全球80%以上合成化学品的生产需要催化约占全球GDP的20%～30%，其中催化剂的变革与创新是提高其生产效率、经济性及生态性的关键。基此，本项目设计合成了桥联生物/均相/异相催化多重优势的层状阳离子有机框架化合物（离子COF）作为新一代绿色高效催化剂，在离子COF材料的优化合成、表征及多尺度规律关系方面取得如下重要进展：1）通过偶氮缩合、Zincke合成、羰基化及烷基化等反应，采用溶剂热、离子热自模板合成等方法构筑了金属卟啉类层状离子COF催化剂、紫精基阳离子COF催化剂、离子聚脲催化剂、超薄MOF/离子液体复合固体电解质共计四类离子材料；2）利用低场MRI、单晶/粉沫XRD（离线/原位）、低温XRD-DSC、SEM、高压原位拉曼、BET、TGA等谱学技术、试验评价结合计算模拟，实现对上述材料合成过程、晶态构象、孔道结构、比表面积及其催化性能、催化/失活机理进行了系统研究。3）通过合成策略、离子液体构筑基元结构/功能的优化设计、合成条件（顺序、溶剂、模板剂及温度、压力等）等调变，系统优化材料孔道结构、比表面积、稳定性、金属中心的路易斯酸度、阴离子亲核性以及材料的催化性能，获得材料组成-结构-性能三者多尺度的规律关系及调控机制。本项目发表期刊论文5篇，申请专利4项（获得授权1项），取得的成果为新一代离子多孔框架材料的靶向合成、绿色高效催化剂构筑与技术突破奠定基础。