晶体和孔道结构与活性位协同型多孔催化剂设计基础研究

Focusing on the key physiochemical issues in heterogeneous catalysis, this project will design and synthesize the integrated zeolite catalysts with collaborative functionalities of crystalline structures, pore size and shape and catalytic active sites as well as bifunctional and multi-functional microporous/mesoporpus composite catalysts with spatially separated active sites, and will investigate their application and fundamental catalysis in industrially important petrochemical reaction processes.Through a systematical study on the synthetic mechanism of new crystalline structures and specially shaped pores, the construction of active sites with catalytic functions, and in particular, the control of chiral porosity and mesoporosity, the epitaxial growth of unit cell and special planes as well as the precise tuning of morphology, it is aimed to clarify the scientific problems existing in the intensification between catalyst textual properties and active sites and in the integrated catalytic reactions catalyzed by organic-inorganic materials. We will study the systematic cooperation between the porosities of mesostructured, nanosized, and sub-nano dimension and the active sites of atomic level. Theoretical knowledge will be obtained for constructing tailor-made zeolite catalysts and corresponding reaction system, and for disclosing the inherent laws influencing the catalysis of novel porous materials.

本项目针对多相催化领域催化剂设计和功能调控的关键物理化学问题，以沸石分子筛为主要研究对象，设计晶体结构、孔道尺寸和构型与活性位相互协同和匹配的一体化多孔催化材料，创制空间分布上分区域组装的多种催化活性位协同作用的双（多）功能微介孔复合催化剂，研究它们在重要化学化工过程中的应用和催化本质。综合研究新晶体结构和孔道结构的形成机制、催化功能物种的组装和构筑方法，尤其是手性和介孔孔道构型的控制、晶胞和晶面取向和形貌的精确调控，结构与催化中心的协同增强机制，无机-有机耦合催化反应等关键课题中存在的科学问题。通过介观、纳米、亚纳米晶体和孔道结构与原子水平活性位的系统协同，形成定向设计分子筛催化剂的理论和催化反应体系，揭示多孔材料的质构性质影响催化性能的内在规律。

设计新结构、大孔径、扩散性能优异的分子筛，调控反应分子在催化剂表面尤其是孔道内的传质速度，进而提高催化活性和目标产物选择性是分子筛催化领域的核心课题，而在分子水平上认识孔道结构与催化活性位的协同机制，设计反应定向型催化剂，构建高效原子经济反应是极具挑战性的课题。本项目围绕晶体结构-孔道结构-催化活性位协调型分子筛催化体系的构建这一核心内容，基于有机模板剂与无机骨架结构的相互作用，实现了晶胞尺度上的晶面取向和形貌的精确调控；利用层状与硅锗分子筛的结构可塑性强的特点，自上而下精密调控了分子筛的孔道尺寸；可控地植入催化中心使其与结构的协同作用增强，形成了定向设计分子筛催化剂的新理论，构建了催化反应新体系，揭示了多孔材料的质构性质影响催化性能的内在规律，为大宗化学品清洁生产提供了高效催化材料和反应工艺，取得了产学研紧密结合的工业化应用成果。