基于杂环羧酸配体的金属有机骨架化合物的合成、表征及性质研究

Syntheses,Characterizations and Properties of Metal-Organic Frameworks Based on Heterocyclic Carboxylate Ligands

以噻吩-2,5-二羧酸(tdc)为主要配体、4,4'-联吡啶(bpy)或邻菲咯啉(phen)为辅助配体通过水热法合成了3种MOFs材料[Cd(tdc)(bpy)]n、[Zn(tdc)(bpy)]n和[Co(tdc)(phen)(OH)]n。利用X射线单晶衍射仪、红外光谱仪对3种MOFs材料进行了结构表征与分析,同时利用荧光光谱仪、热重分析仪测定了MOFs材料的荧光性质和热稳定性,并将Co-MOFs修饰到玻碳电极(GCE)表面,通过电化学工作站测定其电化学行为。结果表明,3种MOFs材料比配体有更好的荧光强度和热稳定性,制备的Co-MOFs/GCE比裸GCE对铁氰化钾溶液和含1. 0mmol/L Na NO2的pH=5 PBS溶液表现出更强的循环伏安响应,有望作为修饰剂应用于GCE修饰中。

Three kinds of MOFs,namely [Cd（tdc）（bpy） ]n,[Zn（tdc）（bpy） ]nand [Co（tdc）（phen）（OH） ]n,were synthesized using thiophene-2,5-dicarboxylic acid（tdc） as the main ligand and 4,4-dipyridyl（bpy）or phenanthroline（phen） as the second ligand by hydrothermal method. Their structures were characterized and analyzed by X-ray single crystal diffractometer and infrared spectrometer. At the same time,the fluorescence properties and thermal stabilities of these three MOFs were measured by fluorescence spectrometer and thermogravimetric analyzer. Co-MOFs was modified to the surface of glassy carbon electrode（GCE）,and its electrochemical behavior were studies through cyclic voltammetry（CV）. The results indicated that these three kinds of MOFs have stronger fluorescence intensity and better thermal stability than ligands. The prepared Co-MOFs modified GCE showed stronger CV response than the bare GCE for potassium cyanide solution and pH 5 PBS solution containing 1. 0 mmol/L Na NO2. It is expected to be used as a modifier in modified GCE.