基于松香基表面活性剂的手性超微孔分子筛结构组装与形成机制研究

Chiral supermicroporous molecular sieve is a class of special porous materials with ordered helical chiral channels and pore size in the critical interval between the micropore and mesopore regions. It has broad application prospects in asymmetric synthesis and chiral separation. The synthesis of chiral supermicroporous molecular sieves is still a challenge due to the lack of suitable templates. The special chiral three-ring phenanthrene skeleton gives rosin based surfactants three characteristics, high specific rotation, strong self-assembly ability and smaller molecular size, making them excellent templates for the synthesis of chiral supermicroporous molecular sieves. Therefore, based on the previous work, the synthesis and self-assembly behavior of the chiral rosin based surfactants will be systematically investigated to clarify chiral amplification mechanism in the formation process from the chiral small molecules of rosin based surfactants to chiral supramolecular aggregates. The synthesis of chiral supermicroporous molecular sieves will be guided by the formation rules of self-assembly structures to establish directional synthesis method of chiral supermicroporous molecular sieves. We will further explore the evolution of co-structures of chiral rosin based surfactant and silicon source to elucidate the chiral transfer mechanism from organic phase to inorganic phase in the synthesis process of chiral supermicroporous molecular sieves. Finally, the racemates of chiral compounds was used as probes to evaluate the chiral separation performance of chiral supermicroporous molecular sieves. This project can provide a new way toward the highly value-added utilization of rosin resources and the synthesis of chiral materials.

手性超微孔分子筛是一类具有规整螺旋手性孔道且孔径大小处于微介孔临界区间的特殊多孔材料，在不对称合成与拆分领域具有广阔应用前景。由于适宜模板剂的匮乏，手性超微孔分子筛的合成仍是一项挑战。特殊的类三环菲手性骨架赋予松香基表面活性剂高比旋光度、强自组装能力与较小分子尺寸三大特质，使其成为合成手性超微孔分子筛模板剂优良之选。因此，本项目拟在前期研究基础上，系统开展手性松香基表面活性剂的合成与自组装行为研究，明确其由手性小分子组装形成手性超分子聚集体过程中的手性放大机制，并以此指导手性超微孔分子筛的合成，建立手性超微孔分子筛定向合成方法。深入探索手性松香基表面活性剂与硅源协同共组装结构的演化规律，阐明手性超微孔分子筛合成过程中由有机相到无机相的手性传递机制。最后以系列手性化合物的外消旋体为探针，评价手性超微孔分子筛的手性拆分性能。本项目可为松香资源的高附加值利用及手性材料的合成研究提供新的思路。

合成出系列手性松香基模板剂，包括(+)-脱氢枞基季铵盐及(+)-脱氢枞酰基氨基酸及其盐。以(+)-脱氢枞基季铵盐为模板剂合成出了具有不同结构的手性超微孔分子筛，包括螺旋纤维状、陀螺状、碗状、花生壳、飘带状等多种螺旋手性超微孔分子筛，所合成材料孔径主要集中于1.5-2.0 nm，比表面积均大于1000 m2/g。同时合成出具不同介观相结构（层状、六方、立方相）的有序超微孔分子筛。针对有序立方相(Ia3 ̅d)超微孔二氧化硅，进行铝掺杂合成H型硅铝酸盐分子筛，并被用作β-蒎烯选择性二聚反应的催化剂，其催化活性高达100%。与传统的介孔H型Al-MCM-48催化剂相比，新型超微孔催化剂具有优异的择形性能，二聚体/低聚物比为7.5～10.1，蒎烯二聚体的产率高达72.4%。以(+)-脱氢枞酰氨基酸及其盐为模板剂合成了麻绳状多螺旋手性介孔分子筛及具不同介观相结构的有序介孔分子筛。所得材料孔径集中于4-5 nm，比表面积在400-600 m2/g范围内。以所合成的介孔二氧化硅为载体，采用金属盐浸渍法再磷化形成了非晶态镍钼磷化物，发现可以催化5-羟甲基糠醛选择性生成1,4-苯二酚，且选择性在70%以上。以(+)-脱氢枞酰氨基酸在醇水体系中构建的超分子聚集体为模板剂，合成出空心直管状、空心球状及手性螺旋纤维状碳质纳米材料，所得手性螺旋纤维状碳材料对手性多巴化合物具有手性识别作用。本项目系统开展了基于松香基模板剂的功能性多孔材料合成与应用研究。创制了多种超微孔分子筛材料，丰富了超微孔材料的种群类型，特别是填补了手性超微孔分子筛研究的空白。所得材料在催化、电化学传感与手性识别等领域具有广阔的应用前景。.发表 SCI 收录期刊论文 9 篇，中科院分区 1 区 2 篇，2 区 4 篇。获得授权国家发明专利 5 项。