磁孔功能微纳配位聚合物的合成、生长机理与性能研究

Coordination polymer particles with nano/micrometer size, which combine the advantages of diversified structure and properties of coordination polymers and size, surface and quantum effects of microscopic matters, can show unique optical, magnetic, catalytic, and adsorption properties, which have attracted intense attention in the recent few years. However, researches for micro/nano coordination polymers have been mainly focused on a couple of classic metal carboxylate frameworks and medical applications. So far, the crystal growth process and mechanism, and sorption and magnetic properties of micro/nano coordination polymers have been rarely studied. This project will systematically study the design, synthesis, crystal growth mechanism, and porous/magnetic properties of novel micro/nano coordination polymers. New porous/magnetic coordination polymers will be designed, and more attention will be focused on a series of metal azolate frameworks with excellent stability and adsorption properties. Scanning electron microscopy, electron backscatter diffraction, and transmission electron microscope will be used to monitor the particle size, morphology, orientation, and elemental distribution of the micro/nano crystals, which are the key to achieve controllable synthesis and understanding of the crystal growth mechanism, as well as the structure-property relationship between crystal structures, sizes, and morphologies and their porous/magnetic properties.

颗粒尺寸在微纳米级的配位聚合物在配位聚合物结构独特、性质多样的优势上进一步引入了微观领域独有的尺寸效应、表面效应和量子效应，可表现出特别的光学、磁学、催化和吸附性能，最近几年成为研究热点。但是，微纳配位聚合物研究的化合物体系基本集中于几例经典的金属多羧酸框架，功能主要集中于医学应用。目前，关于微纳配位聚合物生长过程与机理、多孔吸附或磁学性质相关的报道还很零散。本项目拟系统开展新型微纳配位聚合物的设计、合成、生长机理与磁孔性能研究。一方面有针对性的设计合成适合于微纳形貌研究的新型磁孔配位聚合物，另一方面聚焦于具有优异稳定性和吸附功能的金属多氮唑框架类化合物。利用扫描电镜、电子背散射衍射、透射电子显微学等技术观察材料不同生长阶段的尺寸和形貌、判断晶体的生长取向并进行微区元素分析，探讨微纳配位聚合物的可控合成和生长机理，并揭示其磁孔性能与晶体结构、颗粒尺寸和形貌的构效关系。

配位聚合物的微观形态对其性能具有很大的调控作用，但目前这方面的研究还不是很多，缺乏系统性。本项目针对金属配合物的微观形貌进行了系列的调控，研究了溶剂、温度及表面活性剂等对配合物的微纳结构的影响。通过对合成条件的调控合成了系列金属—有机框架微纳材料，并对其荧光，传感，电化学等性能进行了研究。金属—有机框架材料具有多种优异的性能，但相关材料的器件化研究还很少，限制了其实际应用。项目合作发展了多种方式制备金属—多氮唑的薄膜，并制作了相应的器件，并获得了优异的氧气敏感特性。