富氮配体基PMOFs材料的设计合成及其对溶液中离子“裸眼”检测性能的研究

As a challenging scientific task, the preparation and development of new sensing devices with high stabilities and “naked-eye” recognition to different ions by colorimetric sensors in solution has important academic significance and practical value to environmental protection and life-sciences research. Porous Metal-Organic Frameworks (PMOFs) material, a new category of ion probes, has aroused considerable attention. In this project, we will design or select N-rich organic ligands as building blocks, which feature different sizes and preference to controllable assembly of PMOFs materials with novel structures and tunable sizes and shapes of channel by incorporating Cu2+, Zn2+, Eu3+ or Tb3+ metal ion. We will try to reveal the law of synthesis, structural control and ion detection performance to these materials. Meanwhile, in-depth exploration will be conducted by ion-exchanged approach, including the “naked-eye” detection ability of these materials to different ions in solution (such as halogen anions, MnO4¯、ClO4¯ etc. oxo-anions, salicylate etc. organic anions or Fe2+、Fe3+、Mn2+ etc. heavy metal ions), the potential properties induced by guest ions, and the interaction mechanism between the guest ion and the host framework. We wish what we do in this project will provide material foundation and prototype devices for the rational design of new PMOFs materials with ion detection ability.

制备和开发新的具有良好稳定性，在溶液中能够通过颜色变化来识别不同尺寸离子的传感器件对环境保护和生命科学具有重要的学术意义和实用价值，同时也是极具挑战性的科学任务。作为一种新型的离子探针，多孔金属-有机框架（PMOFs）材料已经引起了研究者极大的关注。本项目旨在设计合成或选用不同尺寸和趋向性的富氮配体作为建筑块，与Cu2+、Zn2+、Eu3+或Tb3+离子进行组装，构筑结构新颖的PMOFs材料，通过有机配体来调节其孔道的尺寸和形状，揭示这类材料的合成、结构及离子检测性能调控规律。通过离子交换途径，深入研究这类材料对溶液中不同离子（如卤素离子，MnO4¯、ClO4¯等含氧离子；水杨酸根等有机离子；Fe2+、Fe3+、Mn2+等重金属离子）的“裸眼”检测能力以及由客体离子诱导的潜在性质；探索客体离子与主体骨架间的作用机理，为设计合成新型具有离子检测功能的PMOFs材料提供物质基础和器件原型。

近年来，MOFs材料在气体吸附与分离、磁性、光催化、传感等方面已表现出潜在的应用性。在本项目的研究中，我们按照研究计划合成了6个富氮配体，并在此基础上合成了18例MOFs材料。我们初步进行了这些材料在离子传感、磁性与发光等方面的应用，揭示了结构与性能之间的关系，基本建立了基于富氮配体的MOFs材料合成体系，为进一步研发具有实用价值的功能MOFs材料奠定了基础。有关研究成果已在Cryst. Growth Des., CrystEngComm, J. Solid State Chem., J. Coord. Chem., 东北师大学报（自然科学版）等多种国内外重要刊物发表，其中SCI收录论文5篇；申请国内发明专利1项；出版专著一部，相关研究成果受到广泛关注，实现了项目预期研究目标。