CN110951083A - Double rare earth metal organic framework based on white light emission and preparation method thereof - Google Patents
Double rare earth metal organic framework based on white light emission and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 title abstract description 42
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 19
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 17
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 16
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 13
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001217 Terbium Chemical class 0.000 claims 3
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 18
- -1 rare earth ions Chemical class 0.000 description 14
- 238000012546 transfer Methods 0.000 description 11
- 239000003086 colorant Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- UTCARTSNNKGRTD-UHFFFAOYSA-N terbium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O UTCARTSNNKGRTD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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Abstract
The invention relates to a preparation method of white light-emitting organic-inorganic hybrid double rare earth metal organic framework and brief description of a preparation method thereof. Experimental research results show that the metal organic framework emitting white light is synthesized by using a blue-emitting 2, 5-thiophene dicarboxylic acid organic ligand and red-emitting and green-emitting rare earth metals of europium and terbium according to a three-primary-color principle. The method is to change the molar ratio of the rare earth metal europium to the terbium to search the MOFs emitted by white light under the same excitation wavelength, and then to search the MOFs emitting the white light by using different fluorescence excitation wavelengths under the rare earth metal europium and the terbium with the same ratio.
Description
Technical Field
The invention belongs to the field of material science and technology, and particularly relates to a preparation method for constructing a double rare earth metal organic framework with white light emission by using 2, 5-thiophenedicarboxylic acid (L) as an organic ligand and double rare earth metals of europium and terbium.
Background
Since the first recording of fluorescence by scientists at the end of the 16 th century, luminescent materials have been widely used in various fields of human life such as illumination, display, imaging, sensing, biomarkers, and medical diagnostics. The design and development of luminescent materials with good luminescent efficiency, long lifetime, low energy consumption and high stability have received a lot of attention from physical and chemical chemists. The white light LED becomes a new generation of energy-saving light source due to the advantages of energy conservation, environmental protection, low energy consumption, long service life, high color rendering property, high light energy concentration and the like. At present, the LED white light fluorescent powder is mainly formed by combining fluorescent powder with various colors, most of the fluorescent powder is made of inorganic luminescent materials, and besides some inorganic materials, organic compounds/polymers, metal compounds and the like are also available. However, the multi-color phosphors composed of a single inorganic light emitting material and a single organic light emitting material have disadvantages of low color rendering index, poor light stability, low light emitting efficiency, etc., thereby hindering the normal commercialization development thereof. Thus, scientists have conceived overcoming long-standing deficiencies in the performance of single phosphors or organic phosphors by hybridizing inorganic and organic components.
The rare earth luminescent metal-organic frameworks (LnMOFs) have potential exploration value in the aspect of white light materials due to the special structure, the unique energy transfer process and the excellent luminescent property of the rare earth luminescent metal-organic frameworks. In the single rare earth metal organic framework material, the rare earth ions can be used as a display emitting primary colors, and the organic ligand can be used as a cross-linking agent and a sensitizer or even a light emitter for the rare earth ions. However, the emission of the single rare earth luminescent MOFs can only cover a part of the visible spectrum, and in order to overcome the limitation factor, the characteristics of different monochromatic luminescence of different rare earth ions can be combined to obtain the dual-core rare earth MOFs material with more variable luminescent colors and better controllability. For double-rare-earth MOFs, the relative luminous intensity between rare-earth ions and ligands is determined by energy transfer, and different energy transfer efficiencies in the double-rare-earth MOFs can be caused by different chemical factors (rare-earth ion types and concentrations, ligand structures, coordination states and object types) and different physical parameters (excitation wavelength and temperature), so that the luminous color of the MOFs material is changed. The double rare earth MOFs has a plurality of luminescence advantages (1) luminescence sites are more abundant, and rare earth metal ions, organic ligands, guest molecules and the like can be used as the luminescence sites of the material; (2) the light-emitting range is wide, and all the wave bands from ultraviolet to near infrared (300-; (3) the energy transfer is more varied: there is Ligand-to-Metal charge transfer (Ligand-to-Metal charge transfer), Metal-to-Ligand energy transfer (Metal-to-Metal charge transfer) and rare earth Metal ion energy transfer (Metal-to-Metal charge transfer). The energy transfer process of Ln-MOFs is changed by changing the types of rare earth ions and organic ligands, and the regulation and control of the luminescent property of the complex can be realized. The double rare earth MOFs have abundant coordinated luminescence properties, so that the double rare earth MOFs have great application values in the aspects of white light materials and temperature sensing.
The invention selects organic ligand 2, 5-thiophene dicarboxylic acid (L) with blue light emission and Eu and Tb metal ions with red light and green light emission, successfully synthesizes double rare earth metal organic framework materials with white light emission according to the three primary colors principle, and the materials have characteristic fluorescence emission and can be used for White Light Emitting Diodes (WLEDS), fluorescent probes, molecular recognition, fluorescent sensing and the like.
Disclosure of Invention
The invention aims to provide a complex of double rare earth metals europium and terbium by taking 2, 5-thiophenedicarboxylic acid (L) as an organic ligand and a preparation method thereof. The metal organic complex has stable white light emission, and the complex has wide application prospect as a novel white light emission material.
The invention provides a preparation method of a double rare earth metal organic framework material with white light emission, which comprises the following steps:
the organic ligand and the metal ion of the invention are 2, 5-thiophenedicarboxylic acid (L) and rare earth metal ions of europium and terbium respectively, and Eu (NO) is added3)2·6H2O(0.0012g，0.003mmol)、Tb(NO3)2·6H2O (0.1800g, 0.397mmol), 2, 5-thiophenedicarboxylic acid (L) (0.0688g, 0.4mmol) and methanol (10ml) are mixed and then placed in a sealed stainless steel reaction kettle with a polytetrafluoroethylene lining, stirred to be uniform and then placed in a constant-temperature oven, heated for three days at 120 ℃, then cooled to room temperature, and filtered to obtain colorless transparent crystals. Wherein the ratio of europium to terbium is 1: 149 and the ratio of rare earth metal ions to 2, 5-thiophenedicarboxylic acid (L) ligand is 1: 1.
The method for synthesizing the double rare earth metal organic framework for white light emission comprises the following steps: based on the three primary colors principle of white light and the international pure white light CIE chromaticity coordinates (0.3333 ), we select an organic ligand 2, 5-thiophenedicarboxylic acid (L) with blue light emission and continuously adjust the molar ratio of rare earth metal ions Eu and Tb with red light and green light emission to synthesize MOFs, and make a CIE diagram corresponding to the MOFs, thereby obtaining the rare earth metal organic skeleton required by us for white light emission. The specific operation steps are as follows:
Operation step 2, different fluorescence excitation wavelengths are selected for the MOFs synthesized by the rare earth metal ions europium and terbium with the same molar ratio:
we select three proportions (Eu) in a series of double rare earth MOFsxTb1-xL) (where n (Eu: Tb) is 1: 119, 1: 149, 1: 199) was plotted on a CIE diagram with excitation wavelengths in the range of 320-380nm to find metal-organic frameworks which are closer to the CIE coordinates (0.3333 ) of white light.
The invention is not a metal organic framework which is obtained by combining simple rare earth metal and organic ligand and emits white light, but creatively adopts a novel idea, so that the invention has the advantages of high luminous intensity, pure white color, low energy excitation, high luminous efficiency, easy dissolution in organic solvent and the like.
The invention has the following remarkable advantages: (1) the synthetic materials are terbium nitrate hexahydrate, europium nitrate hexahydrate and 2, 5-thiophenedicarboxylic acid (L), and the materials are easy to obtain, and impurities are not generated in the reaction, and the impurities are completely converted into the metal organic framework which emits white light. (2) The organic solvent is a nontoxic, green and environment-friendly methanol solution. (3) The product obtained by the reaction is easy to clean, and pure crystals can be obtained by repeating the methanol solution for 2-3 times. (4) All property tests used solvents were selected to be non-toxic ethanol solutions.
Drawings
FIG. 1 is a CIE diagram of different proportions of MOFs at the same excitation wavelength.
FIG. 2 is a CIE diagram of MOFs at the same scale at different excitation wavelengths.
Detailed Description
Example 1, the method for synthesizing a double rare earth metal organic framework comprises the following steps:
eu (NO)3)2·6H2O(0.0012g，0.003mmol)、Tb(NO3)2·6H2O (0.1800g, 0.397mmol), 2, 5-thiophenedicarboxylic acid (L) (0.0688g, 0.4mmol) and methanol (10ml) are mixed and then placed in a sealed stainless steel reaction kettle with a polytetrafluoroethylene lining, stirred to be uniform and then placed in a constant-temperature oven, heated for three days at 120 ℃, then cooled to room temperature, and filtered to obtain colorless transparent crystals.
Example 2 a method of modulating white light emission from a dual rare earth metal organic framework comprises:
the crystals obtained in example 1 were ground to a powder and tested for fluorescence in a spectrofluorometer F-380 by selecting the MOFs with the same excitation wavelength and different molar ratios of the rare earth metal ions europium and terbium and calculating the corresponding CIE coordinates by CIE software. A series of double rare earth MOFs (Eu)xTb1-x-L) wherein n (Eu: Tb) ═ 1: 9, 5: 5, 1: 19, 1: 99, 1: 119, 1: 149, 1: 199-MOF have coordinates (0.6026, 0.3236), (0.5870, 0.3164), (0.5998, 0.3246), (0.5770, 0.3232), (0.5736, 0.3450), (0.5617, 0.3448), (0.5254, 0.3601), respectively, at a fluorescence excitation wavelength of 320nm, and its CIE chromatogram is shown in fig. 1. The selection of 1: 119-MOF, 1: 149-MOF and 1: 199-MOF resulted in the measurement of corresponding CIE data in the range of 320-380nm, which have CIE coordinates (0.3456, 0.2363), (0.3652, 0.3457), (0.2863, 0.3317), (0.3137, 0.2184), (0.3333, 0.3394), (0.2664, 0.3238), (0.2946, 0.2770), (0.3219, 0.3883), (0.2761, 0.3498) at different excitation wavelengths of 340nm, 350nm and 360nm, and the corresponding CIE diagram is shown in FIG. 2. The CIE coordinates of 1: 149-MOF at 350nm (0.3333, 0.3394) are obtained as closest to those of white light (0.3333 ), and it is considered that M which gives white light emission is soughtOFs, also provides reference for finding metal organic frameworks that emit white light.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116239783A (en) * | 2023-01-16 | 2023-06-09 | 福州大学 | Double-emission rare earth metal organic framework material for detecting heavy metal lead ions and sulfonamides |
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| CN101101291A (en) * | 2007-07-16 | 2008-01-09 | 南开大学 | Three-dimensional nanoporous Eu coordination polymer type zinc ion fluorescent probe and its preparation method and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116239783A (en) * | 2023-01-16 | 2023-06-09 | 福州大学 | Double-emission rare earth metal organic framework material for detecting heavy metal lead ions and sulfonamides |
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