发光金属有机骨架的合成及光学性能研究

发布时间：2018-07-18 11:34

【摘要】：发光金属有机骨架是一类孔隙率高、比表面积大、孔结构可控、化学性质稳定和制备过程简单的新型多孔晶态发光材料。该类材料在荧光传感检测污染物方面具有检测速度快、灵敏度高、选择性好、稳定可靠等优点,成为新一代的理想发光材料。此外,拥有不同功能基团的发光金属有机骨架可以作为一个保护性的支架,避免在主-客体体系中稀土离子的水合淬灭。(1)本论文以4,4'-二苯乙烯基二羧酸(L1)和2,5-二-(3,5-二羧基苯基)噻吩二甲酰胺(L2)作为有机配体与具有d10结构的过渡金属锌和镉离子构筑了三个发光金属有机骨架材料Zn3 L1）3(DMF)2(MOF1)、Zn3(L1)3(DMA)2(H20)3(MOF2)和[Cd2(H2L)2(H20)5]·5H20·2DMF(MOF3)。通过红外光谱(FT-IR)、粉末X-射线衍射(PXRD)、热重(TG)和元素分析(EA)等手段对发光金属有机骨架材料进行了表征和分析,并利用荧光光谱(PL)研究了其光学性质。(2)研究了发光金属有机骨架MOF1和MOF2对硝基芳香化合物和金属离子的荧光传感性能。研究结果表明,硝基芳香化合物使MOF1和MOF2的荧光强度都发生了不同程度地淬灭。其中,对硝基苯胺的荧光淬灭效果最明显。金属离子使MOF1和MOF2的荧光强度也发生了不同程度的淬灭或增强。在所选择的13种金属离子中,Fe3+使MOF1和MOF2发生了明显的荧光淬灭,而A13+使MOF1的荧光强度发生了明显的增强。另外,研究发现MOF1和MOF2具有良好的循环稳定性和抗干扰性。因此,MOF1和MOF2在选择性荧光检测硝基芳香化合物和金属离子方面具有潜在的应用价值。(3)研究了发光金属有机骨架MOF3对硝基芳香化合物和金属离子的荧光传感检测性能以及敏化稀土离子发光的作用。研究发现,MOF3对Fe3+离子和对硝基苯胺的荧光传感具有高选择性、高灵敏性、抗干扰性和循环稳定性。对于水溶液中稀土离子的敏化研究发现,MOF3对水溶液中的Eu3+离子具有良好的敏化效果,深入研究发现随着敏化浓度和时间的增加敏化效果越好,并且在紫外灯下呈现出肉眼可见的由蓝到红的颜色变化实现了可以调节的荧光发射。
[Abstract]:Luminescent metal organic skeleton is a new kind of porous crystalline luminescent material with high porosity, large specific surface area, controllable pore structure, stable chemical properties and simple preparation process. This kind of material has the advantages of high detection speed, high sensitivity, good selectivity, stability and reliability in the detection of pollutants by fluorescence sensing. It has become a new generation of ideal luminescent materials. In addition, luminescent organometallic skeletons with different functional groups can be used as protective scaffolds. Avoid hydration quenching of rare earth ions in the host-guest system. (1) in this thesis, the organic ligands (L _ 2) and the transition metal zinc (Zn) with d10 structure were used as organic ligands and 2o _ 5- (3o _ 5-dicarboxyphenyl) thiophene dicarboxylic acid (L1) and 2o _ 5- (3o _ 5-dicarboxyphenyl) thiophene dicarboxylic acid (L2) as organic ligands. Three luminescent metal organic skeleton materials Zn3L1) 3 (DMF) 2 (MOF1) Zn3 (L1) 3 (DMA) 2 (H20) 3 (MOF2) and [CD2 (H2L) 2 (H20) 5] 5H202DMF (MOF3) were constructed by cadmium ion. The luminescent metal-organic skeleton materials were characterized by FT-IR, X-ray diffraction (PXRD), thermogravimetry (TG) and elemental analysis (EA). The optical properties were studied by fluorescence spectroscopy (PL). (2) the fluorescence sensing properties of MOF1 and MOF2 p-nitroaromatic compounds and metal ions were studied. The results showed that the fluorescence intensity of MOF1 and MOF2 were quenched to varying degrees by nitroaromatic compounds. The fluorescence quenching effect of p-nitroaniline was the most obvious. The fluorescence intensity of MOF1 and MOF2 was quenched or enhanced in varying degrees by metal ions. Among the 13 metal ions selected, Fe _ 3 can cause the fluorescence quenching of MOF _ 1 and MOF _ 2, while A _ 13 enhances the fluorescence intensity of MOF _ 1. In addition, it is found that MOF 1 and MOF 2 have good cycle stability and anti-interference. Therefore, MOF1 and MOF2 have potential application value in selective fluorescence detection of nitroaromatic compounds and metal ions. (3) the fluorescence sensing properties of luminescent metal organic framework MOF3 for nitroaromatic compounds and metal ions have been studied. Energy and sensitized effect of rare earth ion luminescence. It is found that MOF3 has high selectivity, high sensitivity, anti-interference and cyclic stability for the fluorescence sensing of Fe _ 3 and p-nitroaniline. For the sensitization of rare earth ions in aqueous solution, it is found that MOF3 has a good sensitization effect on EU3 ions in aqueous solution. The further study shows that the better the sensitization effect is with the increase of sensitizing concentration and time. And under the ultraviolet lamp, visible to the naked eye from blue to red color change to achieve adjustable fluorescence emission.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.4;O657.3

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