具有荧光协同效应NMOFs/一维3C-SiC材料优化设计及对典型PAHs识别机制研究

Construct and the detection for typical PAHs of solid fluorescent molecular probes is the most hot research in environmental monitoring field. Based on the principle of MOFs crystal material as fluorescence recognition, in this project, through adjusting the reaction materials and the external conditions to control selfassembly and thermodynamics process, macro porous MOFs fluorescent materials with high order and unsaturated metal sites will be synthesized by the reaction between a long π conjugated flexible Ligands and transition metal ions/rare earth ions, NMOFs film material which can recognize and detect typical PAHs in the environment will be constructed, and the problem of the structure activity relationship between NMOFs module and fluorescence, and the low life and efficiency of MOFs excited states will be solved. To break through the key technologies of in situ preparation of NMOFs/ one-dimensional 3C-SiC molecular devices such as layer and layer deposition, the crystallo graphic orientation, the thickness control of the film and the ability of interfacial bonding between 1D 3C-SiC and NMOFs will be researched, the related scientific problems about the effects of different organic ligands on the formation of multilayer multidimensional fluorescence molecular devices on the surface of the substrate, synergistic effect / mechanism of fluorescence recognition, and the mechanism of typical PAHs on the surface of NMOFs/1D 3C-SiC molecular devices will be solved, which will provide a new way and theoretical basis for the synthesis and application of the fluorescent solid materials development.

构筑固体荧光分子探针及对典型PAHs检测是环境监测领域研究热点。基于MOFs晶态材料荧光识别原理，拟设计合成大π键三角柔性芳香有机配体，以过渡金属离子/稀土离子为构筑点，通过调节反应原料和外界条件控制自组装和热力学过程，制备高度有序、具有不饱和位点大孔MOFs荧光材料，进而合成对典型PAHs特异、高效识别的NMOFs薄膜材料，解决NMOFs不易分散、不稳定、MOFs激发态寿命和效率低等问题；突破层-层沉积等技术局限原位制备NMOFs/一维3C-SiC分子器件，研究一维3C-SiC与NMOFs之间结晶取向、膜厚度控制和界面结合能力大小，解决不同有机配体在基质表面形成多层多维荧光分子器件各种影响规律、两者之间荧光识别协同效应及反应机制，阐明NMOFs/一维3C-SiC分子器件表面识别典型PAHs机理和构效机制等相关科学问题，为荧光固体材料开发、合成和应用提供一定理论基础。

构筑固体荧光分子探针及对典型PAHs检测是环境监测领域研究热点。基于MOFs晶态材料荧光识别原理，设计合成大π键芳香有机配体，以过渡金属离子/稀土离子为构筑点，通过调节反应原料和外界条件控制自组装和热力学过程，制备高度有序、具有不饱和位点MOFs荧光材料，基于此，本项目的研究成果如下：1.以富含N含吡啶羧酸 3-(pyrid -4-yl)-5-(4-carbonylphenyl) -1,2,4- triazolyl为有机配体，通过调节有机配体和外界条件控制自组装和热力学过程，构筑对小分子乙醇等有响应的新型MOF材料，并详细研究其对乙醇、三价铁离子和pH值各种影响因素，阐明荧光协同效应和反应机理；2.以新的思路构筑MOF，设计制备Zn-LDHs，Zn-Co-LDHs，Zn-Co-Ni-LDH等系列层状材料为前驱体，并以LDH为锌源，原位构筑新型MOF/LDH复合材料，进一步详细研究自组装和热力学过程中时间、配体及浓度等对膜厚的影响规律，借助模板剂和金属离子种类调控2D到3D的形貌，荧光性能与光催化反应协同作用，阐明其对染料废水降解机理。项目的研究结果主要以学术论文和专著形式体现，培养了已毕业研究生2名，在学7名硕士研究生，完成了预定的工作计划。