基于刚柔两亲分子组装的超疏水介孔材料及其功能研究

In contrast to homogeneous catalysis, heterogeneous metal catalysis has attracted great attention in chemistry and material science with enhanced activity because of both economic and environmental reasons. However, the heterogeneous catalysts could not be controlled until the end of the reaction for the difficult separation between the supporting materials and solvents. Moreover, the catalyst tends to aggregate during the cycles of reversible reaction to decay their catalytic ability. Previously, our group has prepared novel supramolecular nanotubules assembled by alternative stacking from nitrogen hybrids trimeric macrocycles, which was found to be able to coordinate with Pd cations. The Pd complexes were used as catalytic regulator for Pd cation and provide high catalytic activities during a number of recycles according to reversible self-assembly. In addition, the catalyst recognized the size and type of starting materials and showed unprecedented selectivity for multi-functional S-M reaction. On the basis of above results, the project will show a new synthesis method for linear conjugated polymer and controlled polymerization using supramolecular porous catalysis. We believe well distributed supramolecular porous are useful substrate for controlled polymerization, as well as the meso porous properties can serve for linear polymerization against side coupling reaction. With this in mind we want to move the catalytic site from carbon wall to porous center to synthesize a new series of supramolecular catalysts. We expect the supramolecular catalysts for linearly conjugated polymerization would provide a new insight in the synthesis of OLED materials. Furthermore, we will introduce chiral molecules into carbon wall to synthesis chiral meso-porous structures, which can serve as asymmetric aldolization. While, the chirality of ligand will be transferred into metal catalysts, which developed as asymmetric catalysts for hydrogenation and oxidation.

相对于金属均相催化剂，非均相金属催化在环境保护和经济节能方面具有较多优势，由此受到广泛关注。但是，无法控制反应的进程，而且在反复的反应过程中难以保障稳定的金属催化剂结构而使团聚衰退催化性能。本课题组在最近的研究中发现基于氮杂的芳香性两亲分子组装的管状介孔载体对钯离子具有超强的稳定性和“金属催化”特征，据此利用超分子的可控组装控制反应进程，并且提高循环催化性能；借助超分子识别和反应物的匹配性，实现了单向催化选择性。本课题拟在上述发现基础上，进一步开展分子结构设计，通过分子结构和组装的介孔结构的系统研究，将芳香性碳壁中的活化催化点逐渐转移到介孔中心，研究组装的管状载体长度对催化聚合的影响，为理想的线性共轭高分子的制备及其在发光材料器件上的应用打下良好基础。在此研究基础上，利用手性单分子修饰孔道结构，制备手性介孔，研究不对称羟醛缩合反应，将配体的手性进一步扩展到金属催化剂，探讨不对称氢化和氧化。

相对于均相金属催化剂，非均相金属催化在环境保护和经济节能方面具有较多优势，其稳定金属催化剂结构是实现高效催化的关键因素，但长期存在亟待解决的共性问题：虽然多孔载体的复合解决了金属催化剂的团聚、延长寿命，但载体结构的局限性，影响催化剂和反应物的有效碰撞；负载载体之后，与溶剂隔离形成密闭环境，无法控制反应进程；稳定的载体结构，难以实现催化选择性。对此，拓扑有机配体对溶剂的识别，获得“w-type”配位模式，构筑卷曲的管状MOFs金属催化剂，提供较大的催化比表面，提高反应物和催化剂之间的有效碰撞，促进催化转化频率（TOF）。进一步修饰配体结构，获得刺激响应性搏动的非均相载体，发展催化剂的动态调控，实现反应底物交换，提高催化转化次数（TON）。 发展超分子化学识别，利用氢离子的识别技术，制备核-壳结构的超分子质子酸催化剂，在微酸性环境中实现高效曼尼希催化反应。 拓扑嵌段共聚物的组装，获得系列非均相吸附剂，在污染物的吸附、高效去除领域得到了多种应用。发展多孔聚合物的构筑方法，基于二维超分子多孔聚合物的可控聚合，获得蜂窝状多孔薄片和球状卷曲物，揭示了一并实现较高吸附容量和吸附效率的材料构筑方法。串联可控孔结构策略和手性识别技术，发展手性载体传感器，实现对有机染料和药物等疏水性物质的快速释放。结合均相和非均相吸附特征，制备两相可控的超分子吸附剂，实现对毒素污染源的彻底治理。发展吸附剂结构对污染物形貌的选择性识别，基于超分子胶体的模板聚合，提出不同维度燃料的有效分离方法。基于项目的资助共发表Angew. Chem. Int. Ed.，Nano Lett. 等论文9篇，申请5篇专利。