CN107698775A - More rare earth organic framework materials for white light emission and preparation method thereof - Google Patents
More rare earth organic framework materials for white light emission and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of more rare earth organic framework materials and preparation method thereof, belong to luminescent material technical field.More rare earth organic framework materials for white light emission of the present invention, with 2,6 pyridinedicarboxylic acids for organic ligand, metallic zinc is matrix, and europium, terbium are co-doped with.Initiative of the invention uses metallic zinc as matrix in 2,6 pyridinedicarboxylic acids for the white light emission MOFs materials of organic ligand, and europium terbium is co-doped with to prepare more rare earth organic framework materials of white light emission, luminous intensity enhancing, and stability is more preferable.The present invention also successfully prepares more rare earth organic framework materials using the method for one-step synthesis, and compared to the simpler high efficiency of synthesis step of existing more rare earth organic framework materials, the process equipment of the preparation of material is also simple, and the synthesis cost of material substantially reduces.
Description
Technical field
The present invention relates to a kind of more rare earth-organic framework materials and preparation method thereof, belong to luminescent material technical field.
Background technology
The application in many fields such as luminescent material is in fluorescent lamp, plasma flat-plate is shown, photoswitch, light emitting diode makes it
As the study hotspot in international forward position in recent ten years.Design and exploitation are with long-life, low energy consumption, efficient luminescent material
It is numerous physics and target that chemist is pursued.The advantages that small volume, caloric value are low, power consumption is small, long lifespan causes white light
LED becomes the energy-conserving light source of a new generation.Traditional LED white emitting fluorescent powders are that multiple color phosphor combination forms, not
Single fluorescent material.Also, conventional fluorescent powder has the shortcomings that colour rendering index is low, colour temperature is low, luminous efficiency is low etc., it is necessary to enter one
The improvement of step.It can be prepared using more metal-organic framework materials and realize single fluorescent material, irradiated under ultraviolet excitation
Colour rendering index is high, color temperature value meets the requirements, the white light of luminous efficiency lifting, thus the design and preparation of its material be have it is important
Meaning.
Metal-organic framework materials (Metal-organic frameworks, abbreviation MOFs) are as a kind of new organic
Inorganic hybrid material, it be one kind using metal ion or metal cluster as node, organic ligand as connection unit, using metal from
Son and the coordination asked of organic ligand, periodicity that self assembly is built into is one-dimensional, two-dimentional or three-dimensional net structure crystal
Material.The one kind of more organic framework materials of metal one as the organic framework materials of metal one.It has rich first as the latter
Rich luminescence sites, more rare earth ions, organic ligand in its structure can serve as luminescence unit.Secondly, rare earth-have
Also there is abundant energy transfer process in machine frame frame material, if rare earth metal is to the energy transfer (matel- of organic ligand
Ligand charge transfer), rare earth metal is to energy transfer (the ligand-matel charge between organic ligand
Transfer energy transmission (matel-metal energy transfer)) and between rare earth metal etc., these rare earth metals
Energy transfer process can induced luminescence between ion and organic ligand.
All light sent are induced to be mixed to get a kind of secondary colour, such as yellow, purple, white.White light is generally blue, it is green and
Feux rouges mixes, and because rare earth ion, organic ligand, matrix etc. have an impact to luminescent properties, luminescence sites are a lot,
Luminous species is also a lot, therefore the metal-organic framework materials that obtain white light are difficult, it is necessary to part, matrix, rare earth metal
It is integrated, close fit emits white light.The metal-organic framework materials that dyestuff can also be introduced to be emitted white light, but prior art
In also not using zinc as matrix, 2,6 pyridinedicarboxylic acids be organic ligand white light emitting material.
“Eu3+-doped Tb3+metal–organic frameworks emitting tunable three
Primary colors towards white light ", Zhi-Fa Liu, Mei-Feng Wu, Shuai-Hua Wang.et
Al.J.Mater.Chem.C, 2013, Isosorbide-5-Nitrae 634-4639. discloses a kind of metal-organic framework materials to emit white light, the material
For two-dimensional structure, and its preparation method is divided into three steps, first step synthesis [EuOH (H2O)6][Zn2Eu4(4-Htbca)2-(4-
tbca)8(H2O)12]}n.6nH2O (1-Eu), second step synthesis [TbOH (H2O)6][Zn2Tb4(4-Htbca)2-(4-tbca)8
(H2O)12]}n.6nH2O (2-Tb), the 3rd step, the material that the first step and second step are prepared is mixed to get emit white light it is mixed
Condensation material, processing step is complicated, and cost is high.
The content of the invention
The invention solves first technical problem be to provide one kind using zinc as matrix, 2,6 pyridinedicarboxylic acids is organic
The white light emitting material of part.
To solve above-mentioned first technical problem, more rare earth-organic framework materials for white light emission of the invention, with
2,6 pyridinedicarboxylic acids are organic ligand, and metallic zinc is matrix, and europium, terbium are co-doped with.
Preferably, described 2,6 pyridinedicarboxylic acids:Zinc:Europium:The mol ratio of terbium is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02.
Further, the preparation method of more rare earth organic framework materials for white light emission comprises the following steps：
A. 2,6 pyridinedicarboxylic acids, zinc salt, europium salt and terbium salt are dissolved in the mixed solvent, at 90~100 DEG C after mixing
Constant-temperature enclosed reaction 3~4 days, obtains crude product；
B. by the crude product purified more rare earth organic framework materials produced for white light emission；
Wherein, described 2,6 pyridinedicarboxylic acids:Zinc salt:Europium salt:The mol ratio of terbium salt is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02；It is 1~2 that the mixed solvent, which is organic solvent with water according to volume ratio,:1 mixed solution, it is described to have
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 six water nitric acid
Zinc；The europium salt is six water europium nitrates；The terbium salt is six water terbium nitrates.
Preferably, described 2, the molal volume ratio of 6 pyridinedicarboxylic acids and mixed solvent is：0.072~0.12mol/L.
Preferably, the method for the purifying includes：The crude product that reaction obtains is centrifuged successively, be cleaned multiple times, dried
It is dry；
Wherein, described be cleaned multiple times uses organic solvent with water volume ratio for 1~2:1 mixture, the organic solvent
For ethanol or DMF, the organic solvent is preferably ethanol；Described is preferably repeatedly 3~5 times.
The invention solves second technical problem be to provide above-mentioned more rare earths-organic frame material for white light emission
The preparation method of material.
To solve second technical problem of the present invention, more rare earths-organic frame material for white light emission of the invention
The preparation method of material comprises the following steps：
A. 2,6 pyridinedicarboxylic acids, zinc salt, europium salt and terbium salt are dissolved in the mixed solvent, at 90~100 DEG C after mixing
Constant-temperature enclosed reaction 3~4 days, obtains crude product；
B. by the crude product purified more rare earth organic framework materials produced for white light emission；
Wherein, described 2,6 pyridinedicarboxylic acids:Zinc salt:Europium salt:The mol ratio of terbium salt is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02；It is 1~2 that the mixed solvent, which is organic solvent with water according to volume ratio,:1 mixed solution, it is described to have
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 six water nitric acid
Zinc；The europium salt is six water europium nitrates；The terbium salt is six water terbium nitrates.
Preferably, described 2, the molal volume ratio of 6 pyridinedicarboxylic acids and mixed solvent is：0.072~0.12mol/L.
Preferably, the method for the purifying includes：The crude product that reaction obtains is centrifuged successively, be cleaned multiple times, dried
It is dry；
Wherein, described be cleaned multiple times uses organic solvent with water volume ratio for 1~2:1 mixture, the organic solvent
For ethanol or DMF, the organic solvent is preferably ethanol；Described is preferably repeatedly 3~5 times.
Beneficial effect：
What the 1st, the present invention was initiative uses gold in 2,6 pyridinedicarboxylic acids for the white light emission MOFs materials of organic ligand
Belong to zinc as matrix, europium terbium is co-doped with to prepare more rare earth-organic framework materials of white light emission.
2nd, more rare earth-organic framework materials that the present invention is prepared are various metals ion and are made up of machine frame part
Three-dimensional capsule-like structure, greatly reduce the probability of nonradiative transition so that a variety of common luminous intensity enhancings of rare earth ion,
And stability is more preferable.
3rd, more rare earth-organic frameworks that the present invention uses, have the advantages of designability, and effectively increase more
The luminous efficiency of rare earth, add the utilization ratio of energy.And ratio can be co-doped with to realize that colour developing refers to by changing more rare earths
Number, the regulation and optimization of luminous efficiency.
4th, the present invention also successfully prepares more rare earth-organic framework materials using the method for one-step synthesis, compared to existing
The simpler high efficiency of synthesis step of more rare earth-organic framework materials, the process equipment of the preparation of material is also simple, the conjunction of material
Substantially reduced into cost.
Brief description of the drawings
Fig. 1 is the Eu of the present invention3+ 0.08Tb3+ 0.02@ZnPDA emission spectrum.
Fig. 2 is the Eu of the present invention3+ 0.08Tb3+ 0.02@ZnPDA chromaticity coordinate figure.
Fig. 3 is the Eu of the present invention3+ 0.08Tb3+ 0.02@ZnPDA RXRD figures.
The Eu of Fig. 4 present invention3+ 0.08Tb3+ 0.02@ZnPDA SEM figures.
Fig. 5 is the Eu of the present invention3+ 0.08Tb3+ 0.02@ZndPDA IR figures.
Fig. 6 is the Eu of the present invention3+ 0.08Tb3+ 0.02@ZnPDA TG figures.
Embodiment
To solve this above-mentioned first technical problem, more rare earth-organic framework materials for white light emission of the invention,
With 2,6 pyridinedicarboxylic acids for organic ligand, metallic zinc is matrix, and europium, terbium are co-doped with.
Preferably, described 2,6 pyridinedicarboxylic acids:Zinc:Europium:The mol ratio of terbium is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02.
Further, the preparation method of more rare earth organic framework materials for white light emission comprises the following steps：
A. 2,6 pyridinedicarboxylic acids, zinc salt, europium salt and terbium salt are dissolved in the mixed solvent, at 90~100 DEG C after mixing
Constant-temperature enclosed reaction 3~4 days, obtains crude product；
B. by the crude product purified more rare earth organic framework materials produced for white light emission；
Wherein, described 2,6 pyridinedicarboxylic acids:Zinc salt:Europium salt:The mol ratio of terbium salt is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02；It is 1~2 that the mixed solvent, which is organic solvent with water according to volume ratio,:1 mixed solution, it is described to have
Solvent is ethanol or DMF, and the organic solvent is preferably nontoxic, green ethanol.
Wherein, constant-temperature enclosed reaction prevents the evaporation of ethanol and distilled water while it also avoid external influence.
Further, the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, and zinc nitrate can rise
To the effect of crystal modifier, be advantageous to the structure stablized, while be also beneficial to the substitution of zinc, therefore preferred zinc nitrate hexahydrate；
The europium salt is six water europium nitrates；The terbium salt is six water terbium nitrates.
Preferably, described 2, the molal volume ratio of 6 pyridinedicarboxylic acids and mixed solvent is：0.072~0.12mol/L.
Preferably, the method for the purifying includes：The crude product that reaction obtains is centrifuged successively, be cleaned multiple times, dried
It is dry；
Wherein, described be cleaned multiple times uses organic solvent with water volume ratio for 1~2:1 mixture, the organic solvent
For ethanol or DMF, ethanol is nontoxic, green, therefore the organic solvent preferably uses ethanol；It is described repeatedly refer to 2 times with
On, preferably 3~5 times.
To solve second technical problem of the present invention, more rare earths-organic frame material for white light emission of the invention
The preparation method of material comprises the following steps：
A. 2,6 pyridinedicarboxylic acids, zinc salt, europium salt and terbium salt are dissolved in the mixed solvent, at 90~100 DEG C after mixing
Constant-temperature enclosed reaction 3~4 days, obtains crude product；
B. by the crude product purified more rare earth organic framework materials produced for white light emission；
Wherein, described 2,6 pyridinedicarboxylic acids:Zinc salt:Europium salt:The mol ratio of terbium salt is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02；It is 1~2 that the mixed solvent, which is organic solvent with water according to volume ratio,:1 mixed solution, it is described to have
Solvent is ethanol or DMF, and the organic solvent is preferably nontoxic, green ethanol.
Further, the zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, preferably six water nitric acid
Zinc；The europium salt is six water europium nitrates；The terbium salt is six water terbium nitrates.
Preferably, described 2, the molal volume ratio of 6 pyridinedicarboxylic acids and mixed solvent is：0.072~0.12mol/L.
Preferably, the method for the purifying includes：The crude product that reaction obtains is centrifuged successively, be cleaned multiple times, dried
It is dry；
Wherein, described be cleaned multiple times uses organic solvent with water volume ratio for 1~2:1 mixture, the organic solvent
For ethanol or DMF, ethanol is nontoxic, green, therefore the organic solvent preferably uses ethanol；It is described repeatedly refer to 2 times with
On, described is preferably repeatedly 3~5 times.
The embodiment of the present invention is further described with reference to embodiment, therefore not limited the present invention
System is among described scope of embodiments.
Embodiment 1
By the 2 of 1.8mmol, 6 pyridinedicarboxylic acid parts, 0.540mmol zinc nitrate hexahydrate, 0.048mmol six water nitre
Six water terbium nitrates of sour europium and 0.012mmol are dissolved in the in the mixed solvent of 10ml ethanol and 10ml water, are stirred with glass bar
It is put into after uniformly in closed reactor, in 90~100 DEG C of isothermal reactions 3 days.Centrifugal treating is carried out to sample after reaction, is used in combination
Absolute ethyl alcohol is 1 with water volume ratio:1 mixed solvent cleans 3 samples, and more rare earths-have using zinc as matrix are obtained after drying
Machine frame frame material, its emission spectrum such as figure, chromaticity coordinate figure, RXRD figure, SEM figures, IR figures, TG figures are respectively such as Fig. 1,2,3,4,5
It is shown.
When excitation wavelength is 325nm, the maximum peak of emission spectrum is located at 410nm, 550nm and 617nm fluorescent material respectively
Light as white, its chromaticity coordinates is (0.3311,0.3251), and in 500v voltages, slit, narrow width are to be tested under 5nm, is lighted
Intensity is 5000cd.
Embodiment 2
By the 2 of 1.8mmol, 6 pyridinedicarboxylic acid parts, 0.540mmol zinc salt zinc nitrate hexahydrate, 0.046mmol europium
The water europium nitrate of salt six and 0.014mmol the water terbium nitrate of terbium salt six are dissolved in the in the mixed solvent of 10ml ethanol and 10ml water,
It is put into after being stirred with glass bar in closed reactor, in 90-100 DEG C of isothermal reaction 3 days.Sample is carried out after reaction from
Heart processing, and be 1 with absolute ethyl alcohol and water volume ratio:1 mixed solvent cleans 3 samples, is obtained after drying using zinc as matrix
More rare earth-organic framework materials.
When excitation wavelength is 325nm, the maximum peak of emission spectrum is located at 410nm, 550nm and 617nm fluorescent material respectively
To light as white, its chromaticity coordinates be (0.3155,0.3101).
Embodiment 3
By the 2 of 1.8mmol, 6 pyridinedicarboxylic acid parts, 0.540mmol zinc salt zinc nitrate hexahydrate, 0.044mmol europium
The water europium nitrate of salt six and 0.016mmol the water terbium nitrate of terbium salt six are dissolved in the in the mixed solvent of 10ml ethanol and 10ml water,
It is put into after being stirred with glass bar in closed reactor, in 90-100 DEG C of isothermal reaction 3 days.Sample is carried out after reaction from
Heart processing, and be 1 with absolute ethyl alcohol and water volume ratio:1 mixed solvent cleans 3 samples, is obtained after drying using zinc as matrix
More rare earth-organic framework materials.
When excitation wavelength is 325nm, the maximum peak of emission spectrum is located at 410nm, 550nm and 617nm fluorescent material respectively
To light as white, its chromaticity coordinates be (0.3031,0.3306).
Embodiment 4
By the 2 of 1.8mmol, 6 pyridinedicarboxylic acid parts, 0.540mmol zinc salt zinc nitrate hexahydrate, 0.042mmol europium
The water europium nitrate of salt six and 0.018mmol the water terbium nitrate of terbium salt six are dissolved in the in the mixed solvent of 10ml ethanol and 10ml water,
It is put into after being stirred with glass bar in closed reactor, in 90-100 DEG C of isothermal reaction 3 days.Sample is carried out after reaction from
Heart processing, and be 1 with absolute ethyl alcohol and water volume ratio:1 mixed solvent cleans 3 samples, is obtained after drying using zinc as matrix
More rare earth-organic framework materials.
When excitation wavelength is 325nm, the maximum peak of emission spectrum is located at 410nm, 550nm and 617nm fluorescent material respectively
To light as white, its chromaticity coordinates be (0.3115,0.3234).
Embodiment 5
By the 2 of 1.8mmol, 6 pyridinedicarboxylic acid parts, 0.540mmol zinc salt zinc nitrate hexahydrate, 0.040mmol europium
The water europium nitrate of salt six and 0.020mmol the water terbium nitrate of terbium salt six are dissolved in the in the mixed solvent of 10ml ethanol and 10ml water,
It is put into after being stirred with glass bar in closed reactor, in 90-100 DEG C of isothermal reaction 3 days.Sample is carried out after reaction from
Heart processing, and be 1 with organic solvent and water volume ratio:1 mixed solvent cleans 3 samples, is obtained after drying using zinc as matrix
More rare earth-organic framework materials.
When excitation wavelength is 325nm, the maximum peak of emission spectrum is located at 410nm, 550nm and 617nm fluorescent material respectively
To light as white, its chromaticity coordinates be (0.3179,0.33246).
When the fluorescent material excitation wavelength of the present invention is 325nm it can be seen from embodiment 1-5 and Fig. 1 and 2, emission spectrum
Maximum peak be respectively located at 410nm, 550nm and 617nm, light as white, chromaticity coordinates (0.3031~0.3311,0.3101
~0.33246), narrow range, very close international pure white smooth cie color coordinate (0.333,0.333).
Eu, Tb distribution are very uniform as seen from Figure 3, and purity is close to pure phase.
As seen from Figure 4, more rare earth-organic framework materials for being prepared of the present invention for various metals ion with it is organic
The three-dimensional capsule-like structure of frame part composition, therefore can greatly reduce the probability of nonradiative transition so that a variety of rare earth ions
Common luminous intensity enhancing.
Zn as seen from Figure 50.90Eu0.08Tb0.02(PDA)3·(H2O)5Infrared spectrum analysis figure.In 3442cm-1Place goes out
H-O stretching vibration peak, 1612cm are showed-1There is H-O-H deformation vibration the absworption peak in place, in 1000-1300cm-1Locate attached
The stretching vibration peak of the C-O keys closely occurred is in 420-763cm-1There are the C-H vibration absorption peaks containing phenyl ring in place.
It is probably appearance at 485 DEG C caused by hydrone thermal decomposition that 200 DEG C or so, which have an exothermic peak, as seen from Figure 6
Exothermic peak is probably organic ligand react with matrix caused by.Nearby there is violent exothermic peak residual mass at 547 DEG C
For 34.74%, the sintering temperature of sample may be near 896.5 DEG C.
Claims (10)
1. more rare earth-organic framework materials for white light emission, it is characterised in that：More rare earths for white light emission have
For machine frame frame material with 2,6 pyridinedicarboxylic acids for organic ligand, metallic zinc is matrix, and europium, terbium are co-doped with.
2. more rare earth-organic framework materials according to claim 1 for white light emission, it is characterised in that described 2,6
Pyridinedicarboxylic acid:Zinc:Europium:The mol ratio of terbium is：1.8:0.54~0.55:0.04~0.05:0.01~0.02.
3. more rare earth-organic framework materials according to claim 1 or 2 for white light emission, it is characterised in that described
Preparation method for more rare earth organic framework materials of white light emission comprises the following steps：
A. 2,6 pyridinedicarboxylic acids, zinc salt, europium salt and terbium salt are dissolved in the mixed solvent, in 90~100 DEG C of constant temperature after mixing
Confined reaction 3~4 days, obtains crude product；
B. by the crude product purified more rare earth organic framework materials produced for white light emission；
Wherein, described 2,6 pyridinedicarboxylic acids:Zinc salt:Europium salt:The mol ratio of terbium salt is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02；It is 1~2 that the mixed solvent, which is organic solvent with water according to volume ratio,:1 mixed solution, it is described to have
Solvent is ethanol or DMF, and the organic solvent is preferably ethanol.
4. more rare earth-organic framework materials according to claim 3 for white light emission, it is characterised in that：The zinc
Salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, preferably zinc nitrate hexahydrate；The europium salt is six water nitric acid
Europium；The terbium salt is six water terbium nitrates.
5. more rare earth-organic framework materials for white light emission according to claim 3 or 4, it is characterised in that：It is described
The molal volume of 2,6 pyridinedicarboxylic acids and mixed solvent ratio is：0.072~0.12mol/L.
6. more rare earth-organic framework materials for white light emission according to any one of claim 3-5, its feature exist
In the method for the purifying includes：The crude product that reaction obtains is centrifuged successively, be cleaned multiple times, dried；
Wherein, described be cleaned multiple times uses organic solvent with water volume ratio for 1~2:1 mixture, the organic solvent are second
Alcohol or DMF, the organic solvent are preferably ethanol；Described is preferably repeatedly 3~5 times.
7. the preparation method of more rare earth-organic framework materials for white light emission described in claim 1-6, its feature exist
In the preparation method comprises the following steps：
A. 2,6 pyridinedicarboxylic acids, zinc salt, europium salt and terbium salt are dissolved in the mixed solvent, in 90~100 DEG C of constant temperature after mixing
Confined reaction 3~4 days, obtains crude product；
B. by the crude product purified more rare earth organic framework materials produced for white light emission；
Wherein, described 2,6 pyridinedicarboxylic acids:Zinc salt:Europium salt:The mol ratio of terbium salt is：1.8:0.54~0.55:0.04~
0.05:0.01~0.02；It is 1~2 that the mixed solvent, which is organic solvent with water according to volume ratio,:1 mixed solution, it is described to have
Solvent is ethanol or DMF, and the organic solvent is preferably ethanol.
8. the preparation method of more rare earth-organic framework materials according to claim 7 for white light emission, its feature exist
In：The zinc salt is at least one of zinc chloride, zinc acetate or zinc nitrate hexahydrate, preferably zinc nitrate hexahydrate；The europium salt is
Six water europium nitrates；The terbium salt is six water terbium nitrates.
9. the preparation method of more rare earth-organic framework materials for white light emission according to claim 7 or 8, it is special
Sign is：Described 2, the molal volume ratio of 6 pyridinedicarboxylic acids and mixed solvent is：0.072~0.12mol/L.
10. the preparation side of more rare earth-organic framework materials for white light emission according to any one of claim 7-9
Method, it is characterised in that the method for the purifying includes：The crude product that reaction obtains is centrifuged successively, be cleaned multiple times, dried
；
Wherein, described be cleaned multiple times uses organic solvent with water volume ratio for 1~2:1 mixture, the organic solvent are second
Alcohol or DMF, the organic solvent are preferably ethanol；Described is preferably repeatedly 3~5 times.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112592487A (en) * | 2020-12-11 | 2021-04-02 | 成都理工大学 | Adenine and citric acid with Zn2+Constructed MOFs material and preparation method thereof |
| CN113549224A (en) * | 2021-08-15 | 2021-10-26 | 福州大学 | Metal covalent organic framework material with intrinsic white light emission |
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| CN110951083A (en) * | 2018-09-26 | 2020-04-03 | 天津工业大学 | Double-rare-earth metal organic framework material based on white light emission and preparation method thereof |
| CN109608650B (en) * | 2018-12-10 | 2021-11-30 | 怀化学院 | MOF composite material and preparation method and application thereof |
| CN109608650A (en) * | 2018-12-10 | 2019-04-12 | 怀化学院 | MOF composite material and preparation method and application |
| CN109796477A (en) * | 2019-01-28 | 2019-05-24 | 武汉理工大学 | A kind of preparation method of rare earth ion doped metal-organic framework fluorescent material |
| CN109796477B (en) * | 2019-01-28 | 2020-12-22 | 武汉理工大学 | Preparation method of rare earth ion doped metal-organic framework fluorescent material |
| CN111961215A (en) * | 2020-08-11 | 2020-11-20 | 盐城工学院 | Light-emitting metal-organic framework material based on PBP and dicarboxylic acid ligand and preparation method and application thereof |
| CN111961215B (en) * | 2020-08-11 | 2022-04-05 | 盐城工学院 | Light-emitting metal-organic framework material based on PBP and dicarboxylic acid ligand and preparation method and application thereof |
| CN111909084A (en) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | Eu/Tb (BPDC) (NO) for detecting DPA3) Preparation method of (1) |
| CN112592487A (en) * | 2020-12-11 | 2021-04-02 | 成都理工大学 | Adenine and citric acid with Zn2+Constructed MOFs material and preparation method thereof |
| CN113549224A (en) * | 2021-08-15 | 2021-10-26 | 福州大学 | Metal covalent organic framework material with intrinsic white light emission |
| CN113896900A (en) * | 2021-10-19 | 2022-01-07 | 黑龙江希光科技有限公司 | Lanthanide series metal organic framework Ln-MOF material and preparation method thereof |
| CN115181288A (en) * | 2022-08-05 | 2022-10-14 | 澳门大学 | Anionic metal-organic framework material, preparation method thereof and crystalline heavy metal ion probe material |
| CN115181288B (en) * | 2022-08-05 | 2023-10-20 | 澳门大学 | Anionic metal-organic framework material, preparation method thereof and crystalline heavy metal ion probe material |
| CN115404072A (en) * | 2022-08-17 | 2022-11-29 | 浙江理工大学 | Single-phase white light emitting material based on lanthanide metal-organic framework and preparation method thereof |
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