基于芳香三羧酸的稀土—有机框架材料的合成及发光功能应用
发布时间：2018-07-20 10:22
【摘要】：金属-有机框架材料(Metal-Organic Frameworks,简称MOFs)是一种新型有机-无机杂化晶态多孔材料,具有多样的三维结构和孔道、尺寸可调、优异的热稳定性以及化学稳定性等优点,可潜在应用于能源气体存储、催化、光学、电学、磁学以及生物医学等领域。发光稀土MOFs材料作为新一代固态发光材料,其组成中的稀土离子、有机配体以及客体分子等组成了丰富的发光位点,可以实现稀土MOFs材料不同的发光性能应用。同时,结合结构上的多孔性特点,使得发光稀土MOFs材料具备了无机发光材料和有机发光材料所无法比拟的多功能性优势,因而其在白光发射材料、离子探测以及荧光温度传感等领域具有十分诱人的发光功能应用前景。采用配体H3TATAB(4,4',4”-三嗪-1,3,5-三氨基对苯甲酸)与稀土硝酸盐,通过溶剂热反应构筑了一种具有一维孔道结构的新型MOFs材料LnTATAB (Ln =Dy, Tb, Sm, Eu, Gd)。室温下,H3TATAB配体能够有效敏化Eu3+、Tb3+离子,部分敏化Dy3+,发出其特有的特征发光峰。其中,TbTATAB对水中汞离子具有优异的荧光探测性能,并且常见金属离子对于TbTATAB的发光强度的影响非常有限,因而这一材料具有很好的选择性探测能力。TbTATAB可以作为优异的用于水中汞离子浓度的探测材料。通过向材料TbTATAB发光体系中增加染料C460得到了双发光中心荧光温度探针。TbTATAB(?)C460在低温范围(50～300 K)对温度具有温度探测性能。染料发光强度、Tb3+发光强度的比值(IC460/ITb)与温度具有一定的线性关系,且相对灵敏度最高达Sr=3.33% K-1。改变装载的染料浓度后,TbTATAB(?)C460在生物温度范围(25～70℃)能够实现对温度的探测且相对灵敏度最大达到了1.83% K-1。该材料在低温范围和生物温度范围内都具有很好的温度循环性能,因而能够潜在应用于多范围的温度荧光探测。本文还制备得到了一种基于三羧酸配体H3BPT的稀土MOFs材料LnBPT, Ln=Eu, Tb, DMF=N,N'-二甲基甲酰胺。配体H3BPT能够高效地敏化铕、铽离子并发出其相应特征光。通过改变原料中铕、铽比例可以得到一系列发光颜色不同的混合稀土MOFs材料,随着Eu3+的浓度从40%减少到1%,整体的MOFs的发光颜色由红色转变为黄色。Eu0.059Tb0.941BPT中,Eu3+的发光面积的积分和Tb3+的发光面积的积分最为接近。在Eu0.059Tb0.941BPT中引入了蓝色荧光染料7-二乙氨基-4-甲基香豆素,为体系增加了蓝光发射,当装载浓度为13.3%时,在340nm激发下材料能够发出优质的白光。
[Abstract]:Metal-organic frameworks (MOFs) are novel organic-inorganic hybrid crystalline porous materials with various three-dimensional structures and pores, adjustable size, excellent thermal stability and chemical stability. Potential applications in energy gas storage, catalysis, optics, electricity, magnetism and biomedicine. Luminescent rare earth MOFs as a new generation of solid-state luminescent materials, its composition of rare earth ions, organic ligands and guest molecules constitute a wealth of luminescent sites, which can achieve different luminescent properties of rare earth MOFs applications. At the same time, combined with the porous characteristics of the structure, the luminescent rare earth MOFs materials have the advantages of inorganic luminescence materials and organic luminescent materials, so they can not be compared with organic luminescent materials, so they can be used in white light emitting materials. Ion detection and fluorescence temperature sensing have very attractive luminescent applications. A novel MOFs material LnTATAB (Ln Dy, TB, Sm, EuEU, Gd) with one-dimensional pore structure was prepared by solvothermal reaction of the ligand H3TATAB (4H3TATAB) with rare earth nitrate. At room temperature, H3TATAB ligands can effectively sensitize Eu3 + Tb3, partially sensitize Dy3, and emit its own characteristic luminescence peak. Among them, TbTATAB has excellent fluorescence detection performance for mercury ions in water, and the influence of common metal ions on the luminescence intensity of TbTATAB is very limited. Therefore, this material has a good selective detection ability. TbTATAB can be used as an excellent detection material for mercury ion concentration in water. By adding dye C460 to the material TbTATAB luminescence system, the double luminescence center fluorescence probe. TbTATAB (?) C460 has the temperature detection property at low temperature (50 ~ 300K). The ratio of dye luminescence intensity and Tb3 luminescence intensity (IC460 / ITb) has a linear relationship with temperature, and the highest relative sensitivity is as high as 3.33% K-1. TbTATAB (?) C460 can detect the temperature in the biological temperature range (2570 鈩，
本文编号：2133226
[Abstract]:Metal-organic frameworks (MOFs) are novel organic-inorganic hybrid crystalline porous materials with various three-dimensional structures and pores, adjustable size, excellent thermal stability and chemical stability. Potential applications in energy gas storage, catalysis, optics, electricity, magnetism and biomedicine. Luminescent rare earth MOFs as a new generation of solid-state luminescent materials, its composition of rare earth ions, organic ligands and guest molecules constitute a wealth of luminescent sites, which can achieve different luminescent properties of rare earth MOFs applications. At the same time, combined with the porous characteristics of the structure, the luminescent rare earth MOFs materials have the advantages of inorganic luminescence materials and organic luminescent materials, so they can not be compared with organic luminescent materials, so they can be used in white light emitting materials. Ion detection and fluorescence temperature sensing have very attractive luminescent applications. A novel MOFs material LnTATAB (Ln Dy, TB, Sm, EuEU, Gd) with one-dimensional pore structure was prepared by solvothermal reaction of the ligand H3TATAB (4H3TATAB) with rare earth nitrate. At room temperature, H3TATAB ligands can effectively sensitize Eu3 + Tb3, partially sensitize Dy3, and emit its own characteristic luminescence peak. Among them, TbTATAB has excellent fluorescence detection performance for mercury ions in water, and the influence of common metal ions on the luminescence intensity of TbTATAB is very limited. Therefore, this material has a good selective detection ability. TbTATAB can be used as an excellent detection material for mercury ion concentration in water. By adding dye C460 to the material TbTATAB luminescence system, the double luminescence center fluorescence probe. TbTATAB (?) C460 has the temperature detection property at low temperature (50 ~ 300K). The ratio of dye luminescence intensity and Tb3 luminescence intensity (IC460 / ITb) has a linear relationship with temperature, and the highest relative sensitivity is as high as 3.33% K-1. TbTATAB (?) C460 can detect the temperature in the biological temperature range (2570 鈩，
本文编号：2133226
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