CN103740358B - Rare earth organic-inorganic hybrid luminescent material and preparation method thereof - Google Patents
Rare earth organic-inorganic hybrid luminescent material and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 63
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 rare earth ion Chemical class 0.000 claims abstract description 23
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000005711 Benzoic acid Substances 0.000 claims description 9
- 235000010233 benzoic acid Nutrition 0.000 claims description 9
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- 230000002431 foraging effect Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- 229910052719 titanium Inorganic materials 0.000 abstract description 9
- 239000010936 titanium Substances 0.000 abstract description 9
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- 238000003980 solgel method Methods 0.000 abstract description 5
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- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- WPCJCSMZBVKHRJ-UHFFFAOYSA-K C(C)O.[Cl-].[Eu+3].[Cl-].[Cl-] Chemical compound C(C)O.[Cl-].[Eu+3].[Cl-].[Cl-] WPCJCSMZBVKHRJ-UHFFFAOYSA-K 0.000 description 1
- BPHNQHWJEXYRNC-UHFFFAOYSA-K C(C)O.[Cl-].[Tb+3].[Cl-].[Cl-] Chemical compound C(C)O.[Cl-].[Tb+3].[Cl-].[Cl-] BPHNQHWJEXYRNC-UHFFFAOYSA-K 0.000 description 1
- PYGKPPDIQDANRM-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Tb+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Tb+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] PYGKPPDIQDANRM-UHFFFAOYSA-N 0.000 description 1
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- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明涉及一种稀土有机和无机杂化发光材料及其制备方法，所述的稀土有机和无机杂化发光材料，是带有羧酸基团并带有与稀土离子配位的吡啶基团化合物。具体说本发明是将一类带有羧酸基团并带有与稀土离子配位的吡啶基团的化合物与钛酸四异丙酯或异丙醇铝反应，通过价键的作用将稀土有机配合物嫁接到的钛和铝复合网络基质中，从而实现了稀土有机配合物与钛和铝复合网络基质之间在分子的水平上的复合，制备出了稀土有机和无机发光杂化材料，所制备的材料具有良好的光和热稳定性。在制备工艺上，溶胶—凝胶法实验条件温和，这就为材料的制备和加工提供了便利，降低了生产成本，可操作性强，重现性好，且所得产品质量稳定。
The invention relates to a rare earth organic and inorganic hybrid luminescent material and a preparation method thereof. The rare earth organic and inorganic hybrid luminescent material is a compound with a carboxylic acid group and a pyridine group coordinated with a rare earth ion . Specifically, the present invention reacts a class of compounds with a carboxylic acid group and a pyridine group coordinated with a rare earth ion with tetraisopropyl titanate or aluminum isopropoxide, and the rare earth is organically The complexes are grafted into the titanium and aluminum composite network matrix, thereby realizing the recombination at the molecular level between the rare earth organic complex and the titanium and aluminum composite network matrix, and preparing a rare earth organic and inorganic light-emitting hybrid material. The prepared material has good light and thermal stability. In the preparation process, the sol-gel method has mild experimental conditions, which provides convenience for the preparation and processing of materials, reduces production costs, has strong operability, good reproducibility, and stable product quality.
Description
技术领域：Technical field:
本发明涉及一种有机和无机杂化光学材料，具体涉及一种基于钛和铝复合网络的稀土吡啶功能化稀土有机和无机杂化发光材料及其制备方法。The invention relates to an organic and inorganic hybrid optical material, in particular to a rare earth pyridine functionalized rare earth organic and inorganic hybrid luminescent material based on a composite network of titanium and aluminum and a preparation method thereof.
背景技术：Background technique:
目前随着现代科学技术的发展，单一性质的稀土发光材料已不能充分满足人们生产生活的需要，近年来稀土发光材料的发展趋势是通过物理或化学的方法将一种或多种功能材料引入到稀土发光材料体系中得到性能互补、功能优异的杂化材料。At present, with the development of modern science and technology, rare earth luminescent materials with a single property can no longer fully meet the needs of people's production and life. In recent years, the development trend of rare earth luminescent materials is to introduce one or more functional materials into Hybrid materials with complementary properties and excellent functions are obtained in the rare earth luminescent material system.
稀土离子具有独特的电子层结构，因而表现出许多优良的光学性能，例如发射谱带窄、激发态寿命长等。然而，稀土离子的f-f跃迁属于禁阻跃迁，在可见与紫外光区只表现出很弱的吸收，所以单一稀土离子的发光较弱。由于有机配体在紫外区常常有较大的吸收，人们便将稀土离子与有机配体络合得到稀土有机配合物。研究发现引入适当的有机配体与稀土离子配位，通过分子内的能量传递，敏化中心离子发光，可以有效的增强稀土离子的荧光性质，因此稀土有机配合物具有优异的发光性能——具有色纯度高、荧光寿命较长、量子产率高、谱线丰富等优点，这种材料在显示、光波导放大、固体激光器、生物标记以及防伪等领域有着广泛的用途。但稀土有机配合物的热稳定性差以及不易加工等缺点却限制了它们的进一步应用。为了拓展稀土有机配合物的使用范围人们利用溶胶-凝胶的方法把一些具备良好的光、热和化学稳定性无机材料与稀土有机配合物结合起来形成性能优异的稀土有机/无机杂化发光材料，这成为稀土发光材料领域中的研究热点。Rare earth ions have a unique electronic shell structure, so they exhibit many excellent optical properties, such as narrow emission bands and long lifetimes of excited states. However, the f-f transition of rare earth ions is a forbidden transition, which only shows weak absorption in the visible and ultraviolet regions, so the luminescence of a single rare earth ion is weak. Since organic ligands often have greater absorption in the ultraviolet region, people complex rare earth ions with organic ligands to obtain rare earth organic complexes. The study found that the introduction of appropriate organic ligands to coordinate with rare earth ions, through intramolecular energy transfer, sensitized central ion luminescence, can effectively enhance the fluorescence properties of rare earth ions, so rare earth organic complexes have excellent luminescent properties - with With the advantages of high color purity, long fluorescence lifetime, high quantum yield, and rich spectral lines, this material has a wide range of applications in the fields of display, optical waveguide amplification, solid-state lasers, biomarkers, and anti-counterfeiting. However, the disadvantages of rare earth organic complexes, such as poor thermal stability and difficult processing, limit their further applications. In order to expand the application range of rare earth organic complexes, people use the sol-gel method to combine some inorganic materials with good light, heat and chemical stability with rare earth organic complexes to form rare earth organic/inorganic hybrid luminescent materials with excellent performance. , which has become a research hotspot in the field of rare earth luminescent materials.
目前，利用溶胶-凝胶的方法制备这些有机/无机杂化材料主要有物理掺杂法和化学掺杂法。At present, the preparation of these organic/inorganic hybrid materials by sol-gel methods mainly includes physical doping and chemical doping.
物理掺杂方法是利用溶胶-凝胶的方法将无机、有机两组分通过弱作用力(如氢键、范德华力、静电等)相互作用，简单地将稀土有机配合物包埋于无机介质中制备的有机/无机杂化材料。由于有机相/无机相之间较弱的作用力,不可避免地会存在有机/无机相分离严重的情况，导致杂化材料中掺杂稀土量浓度偏低。The physical doping method is to use the sol-gel method to interact the inorganic and organic components through weak forces (such as hydrogen bonds, van der Waals forces, electrostatics, etc.), and simply embed the rare earth organic complexes in the inorganic medium. Preparation of organic/inorganic hybrid materials. Due to the weak force between the organic phase/inorganic phase, there will inevitably be severe separation of the organic/inorganic phase, resulting in a low concentration of doped rare earths in the hybrid material.
化学掺杂方法是利用含高化学活性组分的稀土配合物作为前驱体，在液相下将这些原料均匀混合并进行水解、缩合等化学反应，在溶液中形成稳定的溶胶体系，溶胶经陈化后胶粒间缓慢聚合，形成三维空间网络结构或纤维状结构的凝胶，凝胶网络间充满了失去流动性的溶剂，溶剂蒸发后就得到干凝胶从而制备有机/无机杂化材料。由于这种杂化材料在有机相/无机相之间存在着较强的共价键，实现了材料之间的在分子水平或纳米尺寸上的复合，使功能活性组份的掺杂量相对较高。另外这种方法可在低温下制备纯度高、粒径分布均匀的杂化材料。The chemical doping method is to use rare earth complexes containing highly chemically active components as precursors, uniformly mix these raw materials in the liquid phase and perform chemical reactions such as hydrolysis and condensation to form a stable sol system in the solution. After melting, the colloidal particles are slowly aggregated to form a gel with a three-dimensional space network structure or a fibrous structure. The gel network is filled with a solvent that loses fluidity. After the solvent evaporates, a xerogel is obtained to prepare an organic/inorganic hybrid material. Due to the strong covalent bond between the organic phase and the inorganic phase of this hybrid material, the recombination between the materials at the molecular level or at the nanometer scale is realized, and the doping amount of the functional active component is relatively small. high. In addition, this method can prepare hybrid materials with high purity and uniform particle size distribution at low temperature.
利用化学掺杂方法通过构筑稀土有机/无机杂化材料，这样既能体现无机基质材料拥有的良好的光、热和化学稳定性，又能凸显稀土有机配合物的良好的光学性能，无机组分和有机组分的合理优化，将会极大限度的改善稀土配合物的发光性能以及光、热和化学稳定性。最终开发出具有高量子效率、稳定性好的优良稀土有机/无机杂化材料。The chemical doping method is used to construct rare earth organic/inorganic hybrid materials, which can not only reflect the good light, heat and chemical stability of inorganic matrix materials, but also highlight the good optical properties of rare earth organic complexes. And the reasonable optimization of organic components will greatly improve the luminescent properties and light, thermal and chemical stability of rare earth complexes. Finally, an excellent rare earth organic/inorganic hybrid material with high quantum efficiency and good stability was developed.
目前的研究发现这类杂化材料仍有一些需要解决的问题，即如果简单地利用无机、有机两组分之间的作用力(如氢键、范德华力、静电等)相互作用将稀土有机配合物包埋于无机介质中制备的有机/无机杂化材料会不可避免地存在有机/无机相分离严重的情况，导致杂化材料中掺杂稀土量浓度偏低影响杂化材料的发光性能。所以如何避免地存在有机/无机相分离，提高稀土离子的掺杂量是研究这类材料的关键。Current research has found that there are still some problems to be solved for this kind of hybrid materials, that is, if the interaction between the inorganic and organic components (such as hydrogen bonds, van der Waals forces, electrostatic, etc.) Organic/inorganic hybrid materials prepared by entrapment in inorganic media will inevitably have severe organic/inorganic phase separation, resulting in a low concentration of doped rare earths in the hybrid material and affecting the luminescence performance of the hybrid material. Therefore, how to avoid organic/inorganic phase separation and increase the doping amount of rare earth ions is the key to study this kind of materials.
基于此，研究人员试图利用化学的方法将有机和无机相通过共价键链接起来，实现材料之间的在分子水平或纳米尺寸上的复合，增加功能活性组份的掺杂量，提高材料的发光性能。一般地，研究人员利用含高化学活性组分的稀土配合物作为前驱体，通过水解、缩合等化学反应，形成稳定的溶胶体系，经陈化形成三维空间网络结构或纤维状结构的凝胶，蒸发凝胶中的溶剂就得到了有机/无机杂化材料。利用这种方法制备的材料，既拥有无机基质材料的良好的光、热和化学稳定性，又具备稀土有机配合物的良好的光学性能。无机组分和有机组分的合理优化，将会极大限度的改善稀土配合物的发光性能以及光、热和化学稳定性。最终开发出具有高量子效率、稳定性好的优良稀土有机/无机杂化材料。另外这种方法可在低温下制备纯度高、粒径分布均匀的杂化材料。Based on this, researchers try to use chemical methods to link the organic and inorganic phases through covalent bonds, realize the compounding between materials at the molecular level or at the nanometer scale, increase the doping amount of functional active components, and improve the Luminous properties. Generally, researchers use rare earth complexes containing highly chemically active components as precursors to form stable sol systems through chemical reactions such as hydrolysis and condensation, and form gels with three-dimensional spatial network structures or fibrous structures after aging. The organic/inorganic hybrid material is obtained by evaporating the solvent in the gel. The material prepared by this method not only has the good light, heat and chemical stability of the inorganic matrix material, but also has the good optical performance of the rare earth organic complex. Reasonable optimization of inorganic components and organic components will greatly improve the luminescent properties and light, thermal and chemical stability of rare earth complexes. Finally, an excellent rare earth organic/inorganic hybrid material with high quantum efficiency and good stability was developed. In addition, this method can prepare hybrid materials with high purity and uniform particle size distribution at low temperature.
发明内容：Invention content:
本发明的目的就在于针对上述现有技术的不足，提供一种稀土有机和无机杂化发光材料；The object of the present invention is to provide a kind of rare earth organic and inorganic hybrid luminescent material aiming at the deficiencies of the above-mentioned prior art;
本发明的另一目的是提供一种稀土有机和无机杂化发光材料的制备方法。Another object of the present invention is to provide a method for preparing rare earth organic and inorganic hybrid luminescent materials.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种稀土有机和无机杂化发光材料，带有羧酸基团并带有与稀土离子配位的吡啶基团化合物的结构式为：A rare earth organic and inorganic hybrid luminescent material, the structural formula of the compound with a carboxylic acid group and a pyridine group coordinated with a rare earth ion is:
一种稀土有机和无机杂化发光材料的制备方法，包括以下步骤：A method for preparing a rare earth organic and inorganic hybrid luminescent material, comprising the following steps:
a、在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol带有羧酸基团并带有与稀土离子配位的吡啶基团的化合物；a. In a 100ml three-neck flask equipped with a stirrer and a nitrogen port, add 1mmol of a compound with a carboxylic acid group and a pyridine group coordinated with a rare earth ion;
b、再加入该化合物质量15～20倍的溶剂；b. Then add a solvent that is 15 to 20 times the mass of the compound;
c、通入氮气并升温到溶剂的回流温度，加入1mol偶联剂形成溶胶充分反应2～3小时后，c. Feed in nitrogen and heat up to the reflux temperature of the solvent, add 1mol coupling agent to form a sol and fully react for 2 to 3 hours,
d、滴加稀土离子的乙醇溶液2ml（稀土的量为0.5mol），使其发生配位反应得到稀土配合物；d. Add 2ml of ethanol solution of rare earth ions dropwise (the amount of rare earth is 0.5mol) to make it undergo a coordination reaction to obtain a rare earth complex;
e、反应1-2小时后，加入0.01mmol去离子水得到固体凝胶；e. After reacting for 1-2 hours, add 0.01 mmol deionized water to obtain a solid gel;
f、将所得的凝胶放入烘箱老化，然后用无水乙醇洗涤，干燥，即得所需杂化材料。f. Put the obtained gel into an oven for aging, then wash with absolute ethanol, and dry to obtain the desired hybrid material.
所述的稀土离子由三价铕及铽的硝酸盐或盐酸盐提供。The rare earth ions are provided by nitrate or hydrochloride of trivalent europium and terbium.
所述的偶联剂是指钛酸四异丙酯或异丙醇铝。The coupling agent refers to tetraisopropyl titanate or aluminum isopropoxide.
所述的溶剂为乙醇、正丁醇、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺。The solvent is ethanol, n-butanol, N,N-dimethylformamide or N,N-dimethylacetamide.
有益效果：本方法中将一类带有羧酸基团并带有与稀土离子配位的吡啶基团的化合物与钛酸四异丙酯或异丙醇铝反应，通过价键的作用将稀土有机配合物嫁接到的钛和铝复合网络基质中，从而实现了稀土有机配合物与钛和铝复合网络基质之间在分子的水平上的复合，制备出了稀土有机和无机发光杂化材料，所制备的材料具有良好的光、热稳定性。在制备工艺上，溶胶—凝胶法实验条件温和，这就为材料的制备和加工提供了便利，降低了生产成本，可操作性强，重现性好，且所得产品质量稳定。Beneficial effects: In this method, a compound with a carboxylic acid group and a pyridine group coordinated with a rare earth ion is reacted with tetraisopropyl titanate or aluminum isopropoxide, and the rare earth The organic complex is grafted into the titanium and aluminum composite network matrix, thereby realizing the compounding at the molecular level between the rare earth organic complex and the titanium and aluminum composite network matrix, and preparing a rare earth organic and inorganic light-emitting hybrid material. The prepared material has good light and thermal stability. In the preparation process, the sol-gel method has mild experimental conditions, which provides convenience for the preparation and processing of materials, reduces production costs, has strong operability, good reproducibility, and stable product quality.
附图说明：Description of drawings:
图1是实施例1所得一类发光材料的红外谱图Fig. 1 is the infrared spectrogram of a class of luminescent materials obtained in Example 1
图2是实施例2所得一类发光材料的发射光谱图Fig. 2 is the emission spectrogram of a class of luminescent materials obtained in Example 2
具体实施方式：Detailed ways:
下面结合实施例对本发明做进一步的详细说明：Below in conjunction with embodiment the present invention is described in further detail:
一种稀土有机和无机杂化发光材料，带有羧酸基团并带有与稀土离子配位的吡啶基团化合物的结构式为：A rare earth organic and inorganic hybrid luminescent material, the structural formula of the compound with a carboxylic acid group and a pyridine group coordinated with a rare earth ion is:
一种稀土有机和无机杂化发光材料的制备方法，包括以下步骤：A method for preparing a rare earth organic and inorganic hybrid luminescent material, comprising the following steps:
a、在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol带有羧酸基团并带有与稀土离子配位的吡啶基团的化合物；a. In a 100ml three-neck flask equipped with a stirrer and a nitrogen port, add 1mmol of a compound with a carboxylic acid group and a pyridine group coordinated with a rare earth ion;
b、再加入该化合物质量15～20倍的溶剂；b. Then add a solvent that is 15 to 20 times the mass of the compound;
c、通入氮气并升温到溶剂的回流温度，加入1mol偶联剂形成溶胶充分反应2～3小时后，c. Feed in nitrogen and heat up to the reflux temperature of the solvent, add 1mol coupling agent to form a sol and fully react for 2 to 3 hours,
d、滴加稀土离子的乙醇溶液2ml（稀土的量为0.5mol），使其发生配位反应得到稀土配合物；d. Add 2ml of ethanol solution of rare earth ions dropwise (the amount of rare earth is 0.5mol) to make it undergo a coordination reaction to obtain a rare earth complex;
e、反应1-2小时后，加入0.01mmol去离子水得到固体凝胶；e. After reacting for 1-2 hours, add 0.01 mmol deionized water to obtain a solid gel;
f、将所得的凝胶放入烘箱老化，然后用无水乙醇洗涤，干燥，即得所需杂化材料。f. Put the obtained gel into an oven for aging, then wash with absolute ethanol, and dry to obtain the desired hybrid material.
所述的稀土离子由三价铕及铽的硝酸盐或盐酸盐提供。The rare earth ions are provided by nitrate or hydrochloride of trivalent europium and terbium.
所述的偶联剂是指钛酸四异丙酯或异丙醇铝。The coupling agent refers to tetraisopropyl titanate or aluminum isopropoxide.
所述的溶剂为乙醇、正丁醇、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺。The solvent is ethanol, n-butanol, N,N-dimethylformamide or N,N-dimethylacetamide.
实施例1Example 1
在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol3,5-二（吡啶基-4-甲氧基）苯甲酸和7g乙醇。通氮气并升温到回流，加入1mol钛酸四异丙酯充分反应2小时后形成溶胶，滴加0.5mmol硝酸铕的乙醇溶液2ml剧烈搅拌反应2小时后，加入0.01mmol去离子水得到固体凝胶。将所得的固体凝胶转移至烘箱中老化处理，温度控制在65℃，老化时间为1天。最后，将所得到的材料研磨后用无水乙醇反复洗涤三次并真空干燥，便得到钛基复合网络吡啶功能化铕的发光杂化材料。In a 100ml three-necked flask equipped with a stirrer and a nitrogen port, add 1mmol of 3,5-di(pyridyl-4-methoxy)benzoic acid and 7g of ethanol. Pass nitrogen and heat up to reflux, add 1mol tetraisopropyl titanate to fully react for 2 hours to form a sol, add dropwise 2ml of ethanol solution of 0.5mmol europium nitrate and stir vigorously for 2 hours, add 0.01mmol deionized water to obtain a solid gel . The obtained solid gel was transferred to an oven for aging treatment, the temperature was controlled at 65° C., and the aging time was 1 day. Finally, after the obtained material is ground, it is repeatedly washed with absolute ethanol three times and vacuum-dried to obtain a titanium-based composite network pyridine functionalized europium luminescent hybrid material.
实施例2Example 2
在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol3,5-二（吡啶基-3-甲氧基）苯甲酸和5g正丁醇。通氮气并升温到回流，加入1mol异丙醇铝充分反应2.30小时后形成溶胶，滴加0.5mmol氯化铕的乙醇溶液2ml剧烈搅拌反应1.5小时后，加入0.01mmol去离子水得到固体凝胶。将所得的固体凝胶转移至烘箱中老化处理，温度控制在65℃，老化时间为1天。最后，将所得到的材料研磨后用无水乙醇反复洗涤三次并真空干燥，便得到铝基复合网络吡啶功能化铕的发光杂化材料。In a 100ml three-necked flask equipped with a stirrer and a nitrogen port, add 1mmol of 3,5-bis(pyridyl-3-methoxy)benzoic acid and 5g of n-butanol. Nitrogen was blown and the temperature was raised to reflux, 1mol aluminum isopropoxide was added to react fully for 2.30 hours to form a sol, 0.5mmol of europium chloride ethanol solution 2ml was added dropwise and vigorously stirred for 1.5 hours, then 0.01mmol deionized water was added to obtain a solid gel. The obtained solid gel was transferred to an oven for aging treatment, the temperature was controlled at 65° C., and the aging time was 1 day. Finally, after the obtained material is ground, it is repeatedly washed with absolute ethanol three times and vacuum-dried to obtain a luminescent hybrid material of aluminum-based composite network pyridine functionalized europium.
实施例3Example 3
在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol3,5-二（吡啶基-2-甲氧基）苯甲酸和6g N,N-二甲基甲酰胺。通氮气并升温到回流，加入1mol钛酸四异丙酯充分反应2.5小时后形成溶胶，滴加0.5mmol硝酸铽的乙醇溶液2ml剧烈搅拌反应1小时后，加入0.01mmol去离子水得到固体凝胶。将所得的固体凝胶转移至烘箱中老化处理，温度控制在65℃，老化时间为1天。最后，将所得到的材料研磨后用无水乙醇反复洗涤三次并真空干燥，便得到钛基复合网络吡啶功能化铽的发光杂化材料。In a 100ml three-necked flask equipped with a stirrer and a nitrogen port, add 1mmol of 3,5-bis(pyridyl-2-methoxy)benzoic acid and 6g of N,N-dimethylformamide. Blow nitrogen and heat up to reflux, add 1mol tetraisopropyl titanate to fully react for 2.5 hours to form a sol, dropwise add 2ml of 0.5mmol terbium nitrate ethanol solution and vigorously stir for 1 hour, add 0.01mmol deionized water to obtain a solid gel . The obtained solid gel was transferred to an oven for aging treatment, the temperature was controlled at 65° C., and the aging time was 1 day. Finally, after grinding the obtained material, it was repeatedly washed with absolute ethanol three times and dried in vacuum to obtain a titanium-based composite network pyridine functionalized terbium luminescent hybrid material.
实施例4Example 4
在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol3,4-二（吡啶基-4-甲氧基）苯甲酸和6g N,N-二甲基乙酰胺。通氮气并升温到回流，加入1mol异丙醇铝充分反应2小时后形成溶胶，滴加0.5mmol氯化铽的乙醇溶液2ml剧烈搅拌反应2小时后，加入0.01mmol去离子水得到固体凝胶。将所得的固体凝胶转移至烘箱中老化处理，温度控制在65℃，老化时间为1天。最后，将所得到的材料研磨后用无水乙醇反复洗涤三次并真空干燥，便得到铝基复合网络吡啶功能化铽的发光杂化材料。In a 100ml three-neck flask equipped with a stirrer and a nitrogen port, add 1mmol of 3,4-bis(pyridyl-4-methoxy)benzoic acid and 6g of N,N-dimethylacetamide. Nitrogen was blown and the temperature was raised to reflux. After adding 1 mol of aluminum isopropoxide and fully reacted for 2 hours, a sol was formed. After 2 ml of 0.5 mmol of terbium chloride ethanol solution was added dropwise and vigorously stirred for 2 hours, 0.01 mmol of deionized water was added to obtain a solid gel. The obtained solid gel was transferred to an oven for aging treatment, the temperature was controlled at 65° C., and the aging time was 1 day. Finally, after grinding the obtained material, it was repeatedly washed with absolute ethanol three times and dried in vacuum to obtain a luminescent hybrid material of aluminum-based composite network pyridine functionalized terbium.
实施例5Example 5
在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol3,4-二（吡啶基-3-甲氧基）苯甲酸和6g N,N-二甲基乙酰胺。通氮气并升温到回流，加入0.5mol异丙醇铝和0.5mol钛酸四异丙酯充分反应2.5小时后形成溶胶，滴加0.5mmol氯化铽的乙醇溶液2ml剧烈搅拌反应1.5小时后，加入0.01mmol去离子水得到固体凝胶。将所得的固体凝胶转移至烘箱中老化处理，温度控制在65℃，老化时间为1天。最后，将所得到的材料研磨后用无水乙醇反复洗三次并真空干燥，便得到钛/铝基复合网络吡啶功能化铽的发光杂化材料。In a 100ml three-necked flask equipped with a stirrer and a nitrogen port, add 1mmol of 3,4-bis(pyridyl-3-methoxy)benzoic acid and 6g of N,N-dimethylacetamide. Nitrogen was blown and the temperature was raised to reflux. After adding 0.5mol aluminum isopropoxide and 0.5mol tetraisopropyl titanate to fully react for 2.5 hours, a sol was formed, and 2ml of ethanol solution of 0.5mmol terbium chloride was added dropwise and stirred vigorously for 1.5 hours, then added 0.01 mmol deionized water to obtain a solid gel. The obtained solid gel was transferred to an oven for aging treatment, the temperature was controlled at 65° C., and the aging time was 1 day. Finally, after grinding the obtained material, it was repeatedly washed with absolute ethanol three times and dried in vacuum to obtain a titanium/aluminum matrix composite network pyridine functionalized terbium luminescent hybrid material.
实施例6Example 6
在装有搅拌器、氮气通口的100ml三口瓶中，加入1mmol3,4-二（吡啶基-2-甲氧基）苯甲酸和6g N,N-二甲基乙酰胺。通氮气并升温到回流，加入0.5mol异丙醇铝和0.5mol钛酸四异丙酯充分反应3小时后形成溶胶，滴加0.5mmol硝酸铕的乙醇溶液2ml剧烈搅拌反应2小时后，加入0.01mmol去离子水得到固体凝胶。将所得的固体凝胶转移至烘箱中老化处理，温度控制在65℃，老化时间为1天。最后，将所得到的材料研磨后用无水乙醇反复洗涤三次并真空干燥，便得到钛/铝基复合网络吡啶功能化铕的发光杂化材料。In a 100ml three-necked flask equipped with a stirrer and a nitrogen port, add 1mmol of 3,4-bis(pyridyl-2-methoxy)benzoic acid and 6g of N,N-dimethylacetamide. Blow nitrogen and heat up to reflux, add 0.5mol aluminum isopropoxide and 0.5mol tetraisopropyl titanate to fully react for 3 hours to form a sol, drop 2ml of ethanol solution of 0.5mmol europium nitrate to react vigorously for 2 hours, add 0.01 mmol deionized water to obtain a solid gel. The obtained solid gel was transferred to an oven for aging treatment, the temperature was controlled at 65° C., and the aging time was 1 day. Finally, after the obtained material is ground, it is repeatedly washed with absolute ethanol three times and vacuum-dried to obtain a titanium/aluminum-based composite network pyridine functionalized europium luminescent hybrid material.
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，对于本发明做出的改进和修改都应该在本发明的保护范围之内。The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative effort. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention should fall within the protection scope of the present invention.
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