CN107698775B - Multi-rare earth-organic framework material for white light emission and preparation method thereof - Google Patents

Multi-rare earth-organic framework material for white light emission and preparation method thereof Download PDF

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CN107698775B
CN107698775B CN201710908569.1A CN201710908569A CN107698775B CN 107698775 B CN107698775 B CN 107698775B CN 201710908569 A CN201710908569 A CN 201710908569A CN 107698775 B CN107698775 B CN 107698775B
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rare earth
white light
framework material
light emission
organic framework
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CN107698775A (en
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张佩聪
周敬修
邱克辉
杜海英
黄艺
倪师军
李峻峰
张文涛
高庆
王甜
巨力
黄滔滔
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Chengdu Univeristy of Technology
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The invention relates to a multi-rare earth-organic framework material and a preparation method thereof, belonging to the technical field of luminescent materials. The invention relates to a multi-rare earth-organic framework material for white light emission, which takes 2, 6-pyridinedicarboxylic acid as an organic ligand, takes metal zinc as a matrix, and is doped with europium and terbium. The invention creatively uses the metal zinc as the matrix and the europium terbium is codoped in the white light emission MOFs material which takes the 2, 6 dipicolinic acid as the organic ligand to prepare the multi-rare earth-organic framework material for white light emission, and the luminescent intensity is enhanced and the stability is better. The invention also successfully adopts a one-step synthesis method to prepare the multi-rare earth-organic framework material, compared with the existing multi-rare earth-organic framework material, the invention has simpler synthesis steps and higher efficiency, the preparation process equipment of the material is also simple, and the synthesis cost of the material is greatly reduced.

Description

Multi-rare earth-organic framework material for white light emission and preparation method thereof
Technical Field
The invention relates to a multi-rare earth-organic framework material and a preparation method thereof, belonging to the technical field of luminescent materials.
Background
The application of luminescent materials in many fields such as fluorescent lamps, plasma panel displays, optical switches, light emitting diodes and the like makes the luminescent materials become a research hotspot at the international leading edge in recent decades, the design and development of luminescent materials with long service life, low energy consumption and high efficiency are the targets pursued by numerous physical and chemists, the white light L ED becomes a new generation of energy-saving light source due to the advantages of small volume, low heat productivity, low power consumption, long service life and the like, the traditional L ED white light fluorescent powder is formed by combining multiple colors of fluorescent powder and does not have single fluorescent powder, the traditional fluorescent powder has the defects of low color rendering index, low color temperature, low luminous efficiency and the like, further improvement is needed, the single fluorescent powder can be prepared and realized by utilizing the multi-metal organic frame material, the white light with high color rendering index, qualified color temperature value and improved luminous efficiency is irradiated under the excitation of ultraviolet light, and the design and the preparation of the materials are significant.
A Metal-organic frameworks (MOFs for short) is used as a novel organic-inorganic hybrid material, which is a crystal material with a periodic one-dimensional, two-dimensional or three-dimensional network structure, and is self-assembled by using Metal ions or Metal clusters as nodes and organic ligands as connecting units and utilizing the coordination between the Metal ions and the organic ligands. A polymetal-organic framework material is used as one of the metal-organic framework materials. It has abundant luminescent sites like the latter, and multiple rare earth metal ions and organic ligands in the structure can be used as luminescent units. Secondly, there are abundant energy transfer processes in the rare earth-organic framework material, such as energy transfer from rare earth metal to organic ligand (matrix-ligand transfer), energy transfer from rare earth metal to organic ligand (ligand-matrix transfer), and energy transfer between rare earth metal and metal (matrix-metal energy transfer), and these energy transfer processes between rare earth metal ion and organic ligand can induce luminescence.
All light emitted is induced to mix to give a mixed color, e.g. yellow, purple, white. The white light is generally formed by mixing blue light, green light and red light, and since rare earth metal ions, organic ligands, substrates and the like have influence on the luminescence performance, a plurality of luminescence sites are provided, and a plurality of kinds of luminescence are provided, the metal-organic framework material for obtaining the white light is difficult, and the ligands, the substrates and the rare earth metals are required to be integrated and closely matched to emit the white light. Dyes can also be introduced to obtain white light-emitting metal-organic framework materials, but no white light-emitting material with zinc as a matrix and 2, 6-pyridinedicarboxylic acid as an organic ligand exists in the prior art.
“Eu3+-doped Tb3+A metal-organic framework material emitting white light is disclosed, which is a two-dimensional structure and the preparation method thereof is divided into three steps, the first step is synthesized [ EuOH (H4634-)2O)6][Zn2Eu4(4-Htbca)2-(4-tbca)8(H2O)12]}n.6nH2O (1-Eu), and the second step of synthesizing [ TbOH (H)2O)6][Zn2Tb4(4-Htbca)2-(4-tbca)8(H2O)12]}n.6nH2O (2-Tb), and a third step of mixing the materials prepared in the first step and the second step to obtain a white light-emitting mixed material, wherein the process steps are complex and the cost is high.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a white light emitting material which takes zinc as a matrix and 2, 6 pyridine dicarboxylic acid as an organic ligand.
In order to solve the first technical problem, the multi-rare earth-organic framework material for white light emission of the invention takes 2, 6-pyridinedicarboxylic acid as an organic ligand, metal zinc as a matrix, and europium and terbium are co-doped.
Preferably, the molar ratio of the 2, 6-dipicolinic acid to the europium to the terbium is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02.
Further, the preparation method of the rare-earth organic framework material for white light emission comprises the following steps:
a. dissolving 2, 6-pyridinedicarboxylic acid, zinc salt, europium salt and terbium salt in a mixed solvent, uniformly mixing, and carrying out a closed reaction at a constant temperature of 90-100 ℃ for 3-4 days to obtain a crude product;
b. purifying the crude product to obtain a multi-rare earth organic framework material for white light emission;
wherein the molar ratio of the 2, 6 dipicolinic acid to the zinc salt to the europium salt to the terbium salt is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02; the mixed solvent is a mixed solution of an organic solvent and water according to a volume ratio of 1-2: 1, the organic solvent is ethanol or DMF, and the organic solvent is preferably ethanol.
Further, the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, preferably zinc nitrate hexahydrate; the europium salt is europium nitrate hexahydrate; the terbium salt is terbium nitrate hexahydrate.
Preferably, the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072-0.12 mol/L.
Preferably, the purification method comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF, and the organic solvent is preferably ethanol; the multiple times are preferably 3-5 times.
The second technical problem to be solved by the invention is to provide a preparation method of the multi-rare earth-organic framework material for white light emission.
To solve the second technical problem of the present invention, the method for preparing the multiple rare earth-organic framework material for white light emission of the present invention comprises the steps of:
a. dissolving 2, 6-pyridinedicarboxylic acid, zinc salt, europium salt and terbium salt in a mixed solvent, uniformly mixing, and carrying out a closed reaction at a constant temperature of 90-100 ℃ for 3-4 days to obtain a crude product;
b. purifying the crude product to obtain a multi-rare earth organic framework material for white light emission;
wherein the molar ratio of the 2, 6 dipicolinic acid to the zinc salt to the europium salt to the terbium salt is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02; the mixed solvent is a mixed solution of an organic solvent and water according to a volume ratio of 1-2: 1, the organic solvent is ethanol or DMF, and the organic solvent is preferably ethanol.
Further, the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, preferably zinc nitrate hexahydrate; the europium salt is europium nitrate hexahydrate; the terbium salt is terbium nitrate hexahydrate.
Preferably, the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072-0.12 mol/L.
Preferably, the purification method comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF, and the organic solvent is preferably ethanol; the multiple times are preferably 3-5 times.
Has the advantages that:
1. the invention creatively uses metal zinc as a matrix and europium terbium to be codoped in the white light emitting MOFs material which takes 2, 6 dipicolinic acid as an organic ligand to prepare the white light emitting multi-rare earth-organic framework material.
2. The multi-rare earth-organic framework material prepared by the invention is a three-dimensional capsule-shaped structure consisting of a plurality of metal ions and organic frame ligands, so that the probability of non-radiative transition is greatly reduced, the common luminous intensity of the plurality of rare earth ions is enhanced, and the stability is better.
3. The multi-rare earth-organic framework structure used by the invention has the advantage of designability, effectively improves the luminous efficiency of multi-rare earth, and increases the utilization efficiency of energy. And the color rendering index and the luminous efficiency can be adjusted and optimized by changing the co-doping proportion of the multiple rare earths.
4. The invention also successfully adopts a one-step synthesis method to prepare the multi-rare earth-organic framework material, compared with the existing multi-rare earth-organic framework material, the invention has simpler synthesis steps and higher efficiency, the preparation process equipment of the material is also simple, and the synthesis cost of the material is greatly reduced.
Drawings
FIG. 1 shows Eu according to the present invention3+ 0.08Tb3+ 0.02Emission spectrum of @ ZnPDA.
FIG. 2 shows Eu according to the present invention3+ 0.08Tb3+ 0.02The chromaticity coordinate graph of @ ZnPDA.
FIG. 3 shows Eu according to the present invention3+ 0.08Tb3+ 0.02RXRD plot of @ ZnPDA.
FIG. 4 Eu according to the present invention3+ 0.08Tb3+ 0.02SEM picture of @ ZnPDA.
FIG. 5 shows Eu according to the present invention3+ 0.08Tb3+ 0.02IR plot of @ ZndPDA.
FIG. 6 shows Eu according to the present invention3+ 0.08Tb3+ 0.02TG pattern of @ ZnPDA.
Detailed Description
In order to solve the first technical problem, the multi-rare earth-organic framework material for white light emission of the invention uses 2, 6-pyridinedicarboxylic acid as an organic ligand, metal zinc as a matrix, and europium and terbium are codoped.
Preferably, the molar ratio of the 2, 6-dipicolinic acid to the europium to the terbium is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02.
Further, the preparation method of the rare-earth organic framework material for white light emission comprises the following steps:
a. dissolving 2, 6-pyridinedicarboxylic acid, zinc salt, europium salt and terbium salt in a mixed solvent, uniformly mixing, and carrying out a closed reaction at a constant temperature of 90-100 ℃ for 3-4 days to obtain a crude product;
b. purifying the crude product to obtain a multi-rare earth organic framework material for white light emission;
wherein the molar ratio of the 2, 6 dipicolinic acid to the zinc salt to the europium salt to the terbium salt is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02; the mixed solvent is a mixed solution of an organic solvent and water according to a volume ratio of 1-2: 1, the organic solvent is ethanol or DMF, and the organic solvent is preferably nontoxic, green and environment-friendly ethanol.
Wherein, the constant temperature closed reaction prevents the evaporation of the ethanol and the distilled water and simultaneously avoids the external influence.
Further, the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, and the zinc nitrate can play a role of a crystal modifier, so that a stable structure is obtained, and zinc substitution is facilitated, so that the zinc nitrate hexahydrate is preferably selected; the europium salt is europium nitrate hexahydrate; the terbium salt is terbium nitrate hexahydrate.
Preferably, the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072-0.12 mol/L.
Preferably, the purification method comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the repeated cleaning is carried out by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, the organic solvent is ethanol or DMF, and the ethanol is nontoxic and environment-friendly, so that the organic solvent is preferably ethanol; the plurality of times is 2 or more times, preferably 3 to 5 times.
To solve the second technical problem of the present invention, the method for preparing the multiple rare earth-organic framework material for white light emission of the present invention comprises the steps of:
a. dissolving 2, 6-pyridinedicarboxylic acid, zinc salt, europium salt and terbium salt in a mixed solvent, uniformly mixing, and carrying out a closed reaction at a constant temperature of 90-100 ℃ for 3-4 days to obtain a crude product;
b. purifying the crude product to obtain a multi-rare earth organic framework material for white light emission;
wherein the molar ratio of the 2, 6 dipicolinic acid to the zinc salt to the europium salt to the terbium salt is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02; the mixed solvent is a mixed solution of an organic solvent and water according to a volume ratio of 1-2: 1, the organic solvent is ethanol or DMF, and the organic solvent is preferably nontoxic, green and environment-friendly ethanol.
Further, the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, preferably zinc nitrate hexahydrate; the europium salt is europium nitrate hexahydrate; the terbium salt is terbium nitrate hexahydrate.
Preferably, the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072-0.12 mol/L.
Preferably, the purification method comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the repeated cleaning is carried out by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, the organic solvent is ethanol or DMF, and the ethanol is nontoxic and environment-friendly, so that the organic solvent is preferably ethanol; the plurality of times is more than 2 times, and the plurality of times is preferably 3 to 5 times.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Dissolving 1.8mmol of 2, 6-pyridinedicarboxylic acid ligand, 0.540mmol of zinc nitrate hexahydrate, 0.048mmol of europium nitrate hexahydrate and 0.012mmol of terbium nitrate hexahydrate in a mixed solvent of 10ml of ethanol and 10ml of water, uniformly stirring by using a glass rod, putting into a closed reaction kettle, and reacting at a constant temperature of 90-100 ℃ for 3 days. After the reaction, the sample is subjected to centrifugal treatment, the sample is washed for 3 times by using a mixed solvent with the volume ratio of absolute ethyl alcohol to water being 1:1, and the sample is dried to obtain the zinc-based multi-rare earth-organic framework material, wherein the emission spectrum of the zinc-based multi-rare earth-organic framework material is shown as figures 1, 2, 3, 4 and 5 respectively in a chromaticity coordinate diagram, an RXRD diagram, an SEM diagram, an IR diagram and a TG diagram.
When the excitation wavelength is 325nm, the fluorescent powder with the maximum peaks of the emission spectra respectively positioned at 410nm, 550nm and 617nm emits white light with color coordinates of (0.3311,0.3251), and the emission intensity is 5000cd when the fluorescent powder is tested under 500v voltage and the slit and the narrow width are both 5 nm.
Example 2
1.8mmol of 2, 6 dipicolinic acid ligand, 0.540mmol of zinc salt zinc nitrate hexahydrate, 0.046mmol of europium salt europium nitrate hexahydrate and 0.014mmol of terbium salt terbium nitrate hexahydrate are dissolved in a mixed solvent of 10ml of ethanol and 10ml of water, stirred uniformly by a glass rod, and then placed in a closed reaction kettle for constant-temperature reaction at 90-100 ℃ for 3 days. And after the reaction, carrying out centrifugal treatment on the sample, washing the sample for 3 times by using a mixed solvent of absolute ethyl alcohol and water in a volume ratio of 1:1, and drying to obtain the zinc-based multi-rare earth-organic framework material.
When the excitation wavelength is 325nm, the fluorescent powder with the maximum peaks of the emission spectra respectively positioned at 410nm, 550nm and 617nm emits white light, and the color coordinates are (0.3155, 0.3101).
Example 3
Dissolving 1.8mmol of 2, 6 dipicolinic acid ligand, 0.540mmol of zinc salt zinc nitrate hexahydrate, 0.044mmol of europium nitrate hexahydrate and 0.016mmol of terbium nitrate hexahydrate in a mixed solvent of 10ml of ethanol and 10ml of water, uniformly stirring by using a glass rod, placing into a closed reaction kettle, and carrying out constant temperature reaction at 90-100 ℃ for 3 days. And after the reaction, carrying out centrifugal treatment on the sample, washing the sample for 3 times by using a mixed solvent of absolute ethyl alcohol and water in a volume ratio of 1:1, and drying to obtain the zinc-based multi-rare earth-organic framework material.
When the excitation wavelength is 325nm, the fluorescent powder with the maximum peaks of the emission spectra respectively positioned at 410nm, 550nm and 617nm emits white light, and the color coordinates are (0.3031, 0.3306).
Example 4
Dissolving 1.8mmol of 2, 6 dipicolinic acid ligand, 0.540mmol of zinc salt zinc nitrate hexahydrate, 0.042mmol of europium salt europium nitrate hexahydrate and 0.018mmol of terbium salt terbium nitrate hexahydrate in a mixed solvent of 10ml of ethanol and 10ml of water, uniformly stirring by using a glass rod, then placing into a sealed reaction kettle, and carrying out constant-temperature reaction at 90-100 ℃ for 3 days. And after the reaction, carrying out centrifugal treatment on the sample, washing the sample for 3 times by using a mixed solvent of absolute ethyl alcohol and water in a volume ratio of 1:1, and drying to obtain the zinc-based multi-rare earth-organic framework material.
When the excitation wavelength is 325nm, the fluorescent powder with the maximum peaks of the emission spectra respectively positioned at 410nm, 550nm and 617nm emits white light with color coordinates of (0.3115, 0.3234).
Example 5
Dissolving 1.8mmol of 2, 6 dipicolinic acid ligand, 0.540mmol of zinc salt zinc nitrate hexahydrate, 0.040mmol of europium salt europium nitrate hexahydrate and 0.020mmol of terbium salt terbium nitrate hexahydrate in a mixed solvent of 10ml of ethanol and 10ml of water, uniformly stirring by using a glass rod, then placing into a sealed reaction kettle, and carrying out constant-temperature reaction at 90-100 ℃ for 3 days. And after the reaction, carrying out centrifugal treatment on the sample, washing the sample for 3 times by using a mixed solvent with the volume ratio of the organic solvent to the water being 1:1, and drying to obtain the zinc-based multi-rare earth-organic framework material.
When the excitation wavelength is 325nm, the fluorescent powder with the maximum peaks of the emission spectra respectively positioned at 410nm, 550nm and 617nm emits white light, and the color coordinates are (0.3179, 0.33246).
As can be seen from examples 1-5 and FIGS. 1 and 2, when the excitation wavelength of the phosphor of the present invention is 325nm, the maximum peaks of the emission spectra are respectively located at 410nm, 550nm and 617nm, the emission is white, the color coordinates (0.3031-0.3311, 0.3101-0.33246) are narrow, and the range is very close to the CIE chromaticity coordinates (0.333 ) of international pure white light.
It can be seen from FIG. 3 that Eu and Tb are distributed uniformly and have purity close to pure phase.
As can be seen from FIG. 4, the multi-rare earth-organic framework material prepared by the invention is a three-dimensional capsule-shaped structure consisting of a plurality of metal ions and organic frame ligands, so that the probability of non-radiative transition can be greatly reduced, and the common luminous intensity of a plurality of rare earth ions is enhanced.
From FIG. 5, Zn can be seen0.90Eu0.08Tb0.02(PDA)3·(H2O)5Infrared spectrum analysis chart. At 3442cm-1Shows a stretching vibration peak of H-O, 1612cm-1The deformation vibration absorption peak of H-O-H appears at the position of 1000--1The stretching vibration peak of the C-O bond appeared nearby is 420-763cm-1The C-H vibration absorption peak containing benzene ring appears.
It can be seen from FIG. 6 that an exothermic peak at about 200 ℃ may be caused by the thermal decomposition of water molecules, and an exothermic peak at 485 ℃ may be caused by the reaction of the organic ligand with the matrix. The residual mass of the intense exothermic peak at around 547 deg.C was 34.74%, and the sintering temperature of the sample was probably around 896.5 deg.C.

Claims (21)

1. A multiple rare earth-organic framework material for white light emission, characterized by: the multi-rare-earth organic framework material for white light emission takes 2, 6-dipicolinic acid as an organic ligand, metal zinc as a matrix, and europium and terbium are codoped;
the preparation method of the multi-rare earth organic framework material for white light emission comprises the following steps:
a. dissolving 2, 6-dipicolinic acid, zinc salt, europium salt and terbium salt in a mixed solvent, uniformly mixing, and carrying out a closed reaction at a constant temperature of 90-100 ℃ for 3-4 days to obtain a crude product;
b. purifying the crude product to obtain a multi-rare earth organic framework material for white light emission;
wherein the molar ratio of the 2, 6-dipicolinic acid to the zinc salt to the europium salt to the terbium salt is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02; the mixed solvent is a mixed solution of an organic solvent and water according to a volume ratio of 1-2: 1, and the organic solvent is ethanol or DMF.
2. The multiple rare earth-organic framework material for white light emission according to claim 1, wherein the organic solvent is ethanol.
3. The multiple rare earth-organic framework material for white light emission according to claim 1 or 2, characterized in that: the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate; the europium salt is europium nitrate hexahydrate; the terbium salt is terbium nitrate hexahydrate.
4. The poly-rare earth-organic framework material for white light emission of claim 3, wherein: the zinc salt is zinc nitrate hexahydrate.
5. The poly rare earth-organic framework material for white light emission according to claim 1, wherein the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072 to 0.12 mol/L.
6. The poly rare earth-organic framework material for white light emission according to claim 3, wherein the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072 to 0.12 mol/L.
7. The multiple rare earth-organic framework material for white light emission according to claim 1 or 2, wherein the method of purification comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF.
8. The multiple rare earth-organic framework material for white light emission of claim 3, wherein the method of purification comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF.
9. The poly-rare earth-organic framework material for white light emission of claim 5, wherein the method of purification comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF.
10. The multiple rare earth-organic framework material for white light emission according to claim 7, wherein the organic solvent is ethanol.
11. The multiple rare earth-organic framework material for white light emission according to claim 7, wherein the multiple times is 3 to 5 times.
12. The method of preparing a multiple rare earth-organic framework material for white light emission according to any one of claims 1 to 11, wherein the method comprises the steps of:
a. dissolving 2, 6-dipicolinic acid, zinc salt, europium salt and terbium salt in a mixed solvent, uniformly mixing, and carrying out a closed reaction at a constant temperature of 90-100 ℃ for 3-4 days to obtain a crude product;
b. purifying the crude product to obtain a multi-rare earth organic framework material for white light emission;
wherein the molar ratio of the 2, 6-dipicolinic acid to the zinc salt to the europium salt to the terbium salt is as follows: 1.8: 0.54-0.55: 0.04-0.05: 0.01-0.02; the mixed solvent is a mixed solution of an organic solvent and water according to a volume ratio of 1-2: 1, and the organic solvent is ethanol or DMF.
13. The method of preparing a multiple rare earth-organic framework material for white light emission of claim 12, wherein the organic solvent is ethanol.
14. The method of preparing a multiple rare earth-organic framework material for white light emission according to claim 12, wherein: the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate; the europium salt is europium nitrate hexahydrate; the terbium salt is terbium nitrate hexahydrate.
15. The method of preparing a multiple rare earth-organic framework material for white light emission according to claim 14, wherein: the zinc salt is zinc nitrate hexahydrate.
16. The method for preparing the multi-rare earth-organic framework material for white light emission according to claim 12, wherein the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the mixed solvent is 0.072-0.12 mol/L.
17. The method according to any one of claims 13 to 15, wherein the molar volume ratio of the 2, 6-pyridinedicarboxylic acid to the solvent mixture is 0.072 to 0.12 mol/L.
18. The method of preparing a multiple rare earth-organic framework material for white light emission of claim 12, wherein the method of purification comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF.
19. The method of any one of claims 13-16, wherein the purifying comprises: sequentially centrifuging, washing and drying the crude product obtained by the reaction;
the multiple washing is performed by adopting a mixture of an organic solvent and water in a volume ratio of 1-2: 1, wherein the organic solvent is ethanol or DMF.
20. The method of claim 18, wherein the organic solvent is ethanol.
21. The method of claim 18, wherein the plurality of times is 3 to 5 times.
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