摘要/Abstract

以2，2'，2''-[（1，3，5）-三嗪-2，4，6-三亚胺基]三苯甲酸（L）和ZrONO₃·2H₂O为原料，在N，N-二甲基甲酰胺（DMF）/H₂O中合成了一种新的锆基金属有机框架荧光传感器（Zr-MOF）.系统地研究了Zr-MOF对水溶中的Fe³⁺和Cr₂O₇^2-离子的荧光响应，其猝灭常数（K_SV）分别为9.54×10⁴，1.75×10⁴ L·mol^-1，检测限（LOD）分别为3.78×10^-8，9.12×10^-7 mol/L.同时也研究了Zr-MOF对DMF溶液中的丙酮、CCl₄和二甲苯的荧光识别，其猝灭常数（K_SV）分别为6534.3，4325.7，4025.1 mL^-1，检测限（LOD）分别为1.09×10^-6，2.73×10^-5和3.17×10^-5 mL.通过FTIR、¹H NMR、TAG、PXRD和元素分析等对Zr-MOF进行表征.结果表明，Zr-MOF在沸水和不同pH值溶液中，结构具有较高的稳定性，但其荧光强度在不同的pH值溶液中呈现一定的变化规律.水样和尿样检测证明，Zr-MOF可作为荧光传感器应用到实际溶液检测中.模拟实验表明，Zr-MOF对丙酮，CCl₄和二甲苯有较高的选择性和灵敏度.
关键词: Zr-MOF, 荧光传感器, Fe^3＋, Cr₂O₇^2-, 丙酮, CCl₄, 二甲苯
A new zirconium(IV) metal-organic framework (Zr-MOF) based on tricarboxylate ligands, namely ZrL▪2H₂O (L=2,2',2''-([1,3,5]-triazine-2,4,6-triimino)tribenzoic acid)) has been designed and synthesized. It can be served as a platform of multi-responsive fluorescence sensor for Fe³⁺ and Cr₂O₇^2- in water. The Stern-Volmer constants (K_SV) are 9.54×10⁴, 1.75×10⁴ L·mol^-1, and the limits of detection are 3.78×10^-8, 9.12×10^-7 mol/L, respectively. Meanwhile, it can also be used as a multi-response fluorescence probe to detect acetone, CCl₄ and xylene in N,N-dimethylformamide (DMF) solution. The Stern-Volmer constants (K_SV) are 6534.3, 4325.7, 4025.1 mL^-1, and the limits of detection are 1.09×10^-6, 2.73×10^-5, 3.17×10^-5 mL, respectively. The Zr-MOF was characterized by FTIR,¹H NMR, powder X-ray diffraction (PXRD), thermo gravimetric analysis (TGA) and elemental analysis. Interestingly, the Zr-MOF has the high water stability and pH stability, but its fluorescence intensity will show certain change law in the range of pH 0~14. Water and urine sample application test showed that Zr-MOF had high sensitive detection for Fe³⁺, and simulated organic solvents test showed that Zr-MOF has high sensitivity and selectivity to acetone, CCl₄ and xylene.
Key words: Zr-MOF, fluorescence sensor, Fe³⁺, Cr₂O₇^2-, acetone, CCl₄, xylene


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