CN106832311A - The multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof - Google Patents
The multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000002178 crystalline material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 124
- 229910001868 water Inorganic materials 0.000 claims description 120
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 125000003636 chemical group Chemical group 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 description 23
- 238000007710 freezing Methods 0.000 description 8
- 230000008014 freezing Effects 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000000799 fluorescence microscopy Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001857 fluorescence decay curve Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005170 crystalloluminescence Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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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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Abstract
The invention discloses the multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof, wherein, the multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials are one-component, and chemical composition is respectively：{[Eu4(4,4 ' oxydibenzoic acid)6(H2O)9]·(H2O)}∞、{[Tb4(4,4 ' oxydibenzoic acid)6(H2O)9]·(H2O) } ∞, and the multicolor luminous crystalline materials of Eu MOF can realize white light emission.The present invention is advantageous in that：(1) the multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystals material not only have good heat endurance and photostability, but also are a kind of excellent new and effective luminescent crystal materials with luminous efficiency higher；(2) it is prepared under the conditions of low-temperature hydrothermal, process is simple, condition requirement is more relaxed, and cost is relatively low, reproducible, and environment is not polluted, and can be produced in enormous quantities.
Description
Technical field
Luminescent crystal material the present invention relates to organic inorganic hybridization and preparation method thereof, and in particular to be made up of one-component
The multicolor luminous crystalline materials of Eu-MOF (achievable white light emission) and (can by the Tb-MOF green light crystal materials that one-component is constituted
Realize green emission), and the preparation method of the two, belong to technical field of chemistry.
Background technology
With the exhaustion of fossil energy, the step of energy crisis increasingly closes on.While regenerative resource is developed,
The utilization rate for improving the energy equally causes the highest attention of countries in the world.
At present, illuminate and show that consumed electric energy account for more than the 50% of global generating total amount.In order to effectively improve energy
The utilization ratio of amount, with energy conversion efficiency higher and can be prevented effectively from higher-energy present in conventional luminescent material and damage
The high efficient luminous material of consumption receives scientific circles and business circles and more and more widely pays close attention to.
Luminescent material will realize quantum yield higher, then, its energy that will be absorbed for allowing for maximum possible turns
Photon is turned to, rather than heat energy is converted into by non-radiative relaxation.However, reduce material non-radiative relaxation need material have compared with
Small phonon energy, preferable crystallinity and larger light transmission rate etc..It is worth noting that optical crystal material have compared with
Good crystallization property and larger light transmission rate and less phonon energy (<1000cm-1) can avoid amorphous material
The non-radiative relaxation effect of presence.Therefore, optical crystal material generally has luminous efficiency higher.
The optical crystal material of inorganic-organic hybrid have in addition to luminous efficiency higher, also structured diversity and
Adjustability, this makes them to have the multicolor luminous characteristic for exciting dependence.Additionally, they also have preferable photochemical stability
And high thermal stability such that it is able to stabilization is kept in temperature wider, humidity, pressure limit.Therefore, even if special at some
Under conditions of different or extreme, they are also widely applied to the multicolor luminous component for showing or illuminating or biological thin
On the fluorescence imaging of born of the same parents.This has promoted a research of the optical crystal material of inorganic-organic hybrid just as high efficient luminous material
Focus.
In recent years, due to metal center and the diversity of organoligand coordination, MOFs is that luminescent device and optics show and carries
For a good platform.Lanthanide series metal organic framework materials (LnMOFs) have luminous efficiency high, narrow bandwidth and luminescent lifetime
Long the advantages of, it is set to can be applied to the fields such as display and white-light illuminating.Glow and sent out realizing white light with the crystalline material of green glow
Penetrate and have very important significance, because the mixed proportion that we can launch component by adjusting red, green, blue three primary colors makes
Material is in white light emission (WLE).Additionally, compared with the material of three component white light emissions, (SC-WLE) of single-component white light transmitting
Crystalline material has color homogeneous, is easily processed and low cost and other advantages, however, single-component white light material is very rare.Due to
Most crystallo-luminescence materials are all prepared by high temperature czochralski method or molten-salt growth method, so its preparation condition requirement ratio
It is harsher and relatively costly, certain pollution is also caused to environment.
Therefore, stabilization and efficient nothing are prepared using relatively simple preparation method and relatively mild experiment condition
Machine organic crystal luminescent material receives the extensive concern of people.
The content of the invention
First purpose of the invention is to provide a kind of with good thermal stability and photostability, by single group packet
Into, be capable of achieving the multicolor luminous crystalline materials of Eu-MOF of white light emission, and its preparation method under the conditions of low-temperature hydrothermal.
Second object of the present invention is to provide a kind of with good thermal stability and photostability, by single group packet
Into, be capable of achieving the Tb-MOF green light crystal materials of green emission, and its preparation method under the conditions of low-temperature hydrothermal.
In order to realize above-mentioned first aim, the present invention is adopted the following technical scheme that：
A kind of multicolor luminous crystalline materials of Eu-MOF, it is characterised in that the foregoing multicolor luminous crystalline materials of Eu-MOF are single
Component, chemical composition is：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The multicolor luminous crystalline materials of foregoing Eu-MOF, it is characterised in that be prepared by the following method：
Step1：At room temperature, by Eu (NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added to the height equipped with deionized water
In pressure kettle, stirring obtains well mixed solution, then adjusts pH value to 7.5-11 with ammoniacal liquor or NaOH solution；
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C；
Step3：Solution after above-mentioned heat treatment is cooled to room temperature；
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product.
The multicolor luminous crystalline materials of foregoing Eu-MOF, it is characterised in that in Step3, solution is with 2 DEG C of h-1Or 3
℃·h-1Or 6 DEG C of h-1Speed cooling.
In order to realize above-mentioned second target, the present invention is adopted the following technical scheme that：
A kind of Tb-MOF green light crystals material, it is characterised in that foregoing Tb-MOF green light crystals material is one-component, chemistry
Constitute and be：{[Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
Foregoing Tb-MOF green light crystal materials, it is characterised in that be prepared by the following method：
Step1：At room temperature, by Tb (NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added to the height equipped with deionized water
In pressure kettle, stirring obtains well mixed solution, then adjusts pH value to 7.5-11 with ammoniacal liquor or NaOH solution；
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C；
Step3：Solution after above-mentioned heat treatment is cooled to room temperature；
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product.
Foregoing Tb-MOF green light crystal materials, it is characterised in that in Step3, solution is with 2 DEG C of h-1Or 3 DEG C of h-1
Or 6 DEG C of h-1Speed cooling.
The present invention is advantageous in that：
(1) it is prepared under the conditions of low-temperature hydrothermal, process is simple, condition requirement is more relaxed, and cost is relatively low, repeatability
It is good, and environment is not polluted, can be produced in enormous quantities；
(2) the multicolor luminous crystalline materials of Eu-MOF for preparing can realize white light emission, and the Tb-MOF for preparing is brilliant
Body material can realize green emission, both at one-component, not only with good heat endurance and photostability, but also have
There is luminous efficiency higher, be a kind of excellent new and effective luminescent crystal material.
Brief description of the drawings
Fig. 1 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Eu in crystal3+With part 4,4 '-hexichol
The coordination environment perspective view of ether dioctyl phthalate；
Fig. 2 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The FTIR of crystal；
Fig. 3 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The FTIR of crystal；
Fig. 4 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal X-ray powder diffraction spectrum and
The spectrogram for obtaining is fitted by mono-crystalline structures；
Fig. 5 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal X-ray powder diffraction spectrum and
The spectrogram for obtaining is fitted by mono-crystalline structures；
Fig. 6 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The normalized emission spectrum of crystal；
Fig. 7 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O) } ∞ crystal is under 290nm excitation wavelengths
Emission spectra；
Fig. 8 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal and { [Tb4(4,4 '-diphenyl ether two
Formic acid)6(H2O)9]·(H2O the) } fluorescence decay curve of ∞ crystal；
Fig. 9 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The thermal multigraph of crystal；
Figure 10 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The thermal multigraph of crystal.
Specific embodiment
Make specific introduction to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1
Step1：At room temperature, 29.8mg Eu (NO are weighed3)3·6H2O and 30.0mg4,4 '-oxydibenzoic acid, by Eu
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 5ml deionized waters, and stirring is obtained
Well mixed solution, then adjusts pH value to 7.5 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), then
Continue to stir 5h, obtain well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 3 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 82.6%.
Bright feux rouges is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change, with good photostability.
As can be seen here, product { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O) } ∞ (Eu-MOF crystalline materials)
Have in extreme temperature conditions on the fluorescence imaging for being applied to the multicolor luminous component or biological cell for showing or illuminating
Potential.
Embodiment 2
Step1：At room temperature, 29.8mg Tb (NO are weighed3)3·6H2O and 30.0mg4,4 '-oxydibenzoic acid, by Tb
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 5ml deionized waters, and stirring is obtained
Well mixed solution, then adjusts pH value to 8 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), followed by
Continuous stirring 5h, obtains well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 3 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 82.5%.
Bright green glow is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
As can be seen here, product { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O) } ∞ (Tb-MOF crystalline materials)
Have in extreme temperature conditions on the fluorescence imaging for being applied to the multicolor luminous component or biological cell for showing or illuminating
Potential.
Embodiment 3
Step1：At room temperature, 59.6mg Eu (NO are weighed3)3·6H2O and 60.0mg4,4 '-oxydibenzoic acid, by Eu
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 10ml deionized waters, and stirring is obtained
Well mixed solution, then adjusts pH value to 8.5 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), then
Continue to stir 5h, obtain well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 6 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 69.2%.
Bright feux rouges is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
Embodiment 4
Step1：At room temperature, 59.6mg Tb (NO are weighed3)3·6H2O and 60.0mg4,4 '-oxydibenzoic acid, by Tb
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 10ml deionized waters, and stirring is obtained
Well mixed solution, then adjusts pH value to 9 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), followed by
Continuous stirring 5h, obtains well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 6 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 69.3%.
Bright green glow is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
Embodiment 5
Step1：At room temperature, 45.1mg Eu (NO are weighed3)3·6H2O and 45.0mg4,4 '-oxydibenzoic acid, by Eu
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 12.5ml deionized waters, is stirred
To well mixed solution, pH value then is adjusted to 9.5 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions),
It is further continued for stirring 5h, obtains well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 2 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 52.9%.
Bright feux rouges is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
Embodiment 6
Step1：At room temperature, 45.1mg Tb (NO are weighed3)3·6H2O and 45.0mg4,4 '-oxydibenzoic acid, by Tb
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 12.5ml deionized waters, is stirred
To well mixed solution, pH value then is adjusted to 10 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), then
Continue to stir 5h, obtain well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 2 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 52.9%.
Bright green glow is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
Embodiment 7
Step1：At room temperature, 90.8mg Eu (NO are weighed3)3·6H2O and 90.0mg4,4 '-oxydibenzoic acid, by Eu
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 15ml deionized waters, and stirring is obtained
Well mixed solution, then adjusts pH value to 10.5 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), then
Continue to stir 5h, obtain well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 3 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield that amount according to 4,4 ' for using-oxydibenzoic acid is calculated product is 34.6%.
Bright feux rouges is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
Embodiment 8
Step1：At room temperature, 90.8mg Tb (NO are weighed3)3·6H2O and 90.0mg4,4 '-oxydibenzoic acid, by Tb
(NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added in the autoclave of the 25ml equipped with 15ml deionized waters, and stirring is obtained
Well mixed solution, then adjusts pH value to 11 with 1ml25% ammoniacal liquor (or 1ml 0.01mol/L NaOH solutions), followed by
Continuous stirring 5h, obtains well mixed solution.
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C.
Step3：By the solution after above-mentioned heat treatment with 3 DEG C of h-1Rate of temperature fall cooling, until being cooled to room temperature.
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal for obtaining is
Product { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
The yield of the product that the amount according to 4,4 ' for using-oxydibenzoic acid is calculated is 34.7%.
Bright green glow is can see with the portable fluorescent lamp product of 4W.When by crystal prototype refrigerator freezing area (-
18 DEG C) place ten hours after, or after (100 DEG C) of high temperature furnace places a few hours, its luminous performance does not observe any change
Change.
From the result of embodiment 1 to embodiment 8：
(1)Eu(NO3)3·6H2The consumption of O and 4,4 '-oxydibenzoic acid and the pH value of solution can influence product
{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O the) } yield of ∞, but the luminosity of product can't be influenceed；
(2)Tb(NO3)3·6H2The consumption of O and 4,4 '-oxydibenzoic acid and the pH value of solution can influence product
{[Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O the) } yield of ∞, but the luminosity of product can't be influenceed.
The products collection efficiency that embodiment 1 and embodiment 2 are obtained is higher, and we have carried out some phases by sample of this two groups of products
Close test.
1st, crystal structure
Fig. 1 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Eu in crystal3+With part 4,4 '-hexichol
The coordination environment perspective view of ether dioctyl phthalate.
From Fig. 1 we：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞It is crystalline material, the crystalline substance
4,4 '-oxydibenzoic acid part of three crystallography independences in body material shows three different coordination configurations.
2nd, FTIR
Fig. 2 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The FTIR of crystal.
Fig. 3 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The FTIR of crystal.
From Fig. 2 and Fig. 3 we：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal and { [Tb4
(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞All there is 4,4 '-oxydibenzoic acid organic group in the structure of crystal
Group.
3rd, X-ray single crystal diffraction
Fig. 4 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal X-ray powder diffraction spectrum and
The spectrogram for obtaining is fitted by mono-crystalline structures.
Fig. 5 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal X-ray powder diffraction spectrum and
The spectrogram for obtaining is fitted by mono-crystalline structures.
From Fig. 4 and Fig. 5 we：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal and { [Tb4
(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal is all mono-crystalline structures, and is all the crystal material of highly crystalline
Material.
4th, emission spectra
Fig. 6 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The normalized emission spectrum of crystal.
Fig. 7 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O) } ∞ crystal is under 290nm excitation wavelengths
Emission spectra.
From Fig. 6 we：Under different excitation wavelengths, by adjusting Eu3+On to part the transmitting of energy transfer with
Eu3+The strength ratio of ion red emission, is capable of achieving the white light emission of Eu-MOF one-components.
From Fig. 7 we：Under excitation wavelength 290nm irradiations, { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·
(H2O)}∞Show very strong green emission.
6th, fluorescence decay
Fig. 8 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal and { [Tb4(4,4 '-diphenyl ether two
Formic acid)6(H2O)9]·(H2O)}∞The fluorescence decay curve of crystal.
From Fig. 8 we：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal and { [Tb4(4,
4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal has fluorescence lifetime long, is good fluorescent material.
7th, thermogravimetric change
Fig. 9 is { [Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The thermal multigraph of crystal.
Figure 10 is { [Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞The thermal multigraph of crystal.
From Fig. 9 and Figure 10 we：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal and
{[Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞Crystal keeps stabilization in the range of 30-100 DEG C of temperature, has
Good heat endurance, the two has the value applied in wide temperature range.
As can be seen here, the multicolor luminous crystalline materials of Eu-MOF for being prepared using the method for the present invention (are capable of achieving white light
Transmitting) and Tb-MOF green light crystals material (achievable green emission) can apply in commercial fluorescent material, anti-fake mark material, electricity
Stablize multicolor luminous component neck under photoluminescence diode, biological labled material, photoswitch and optical memory material, extreme condition
Domain.
It should be noted that above-described embodiment the invention is not limited in any way, all use equivalents or equivalent change
The technical scheme that the mode changed is obtained, all falls within protection scope of the present invention.
Claims (6)
1. multicolor luminous crystalline materials of a kind of Eu-MOF, it is characterised in that the multicolor luminous crystalline materials of Eu-MOF are single group
Part, chemical composition is：{[Eu4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
2. multicolor luminous crystalline materials of Eu-MOF according to claim 1, it is characterised in that be prepared by the following method and
Come：
Step1：At room temperature, by Eu (NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added to the autoclave equipped with deionized water
In, stirring obtains well mixed solution, then adjusts pH value to 7.5-11 with ammoniacal liquor or NaOH solution；
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C；
Step3：Solution after above-mentioned heat treatment is cooled to room temperature；
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal as product for obtaining.
3. multicolor luminous crystalline materials of Eu-MOF according to claim 2, it is characterised in that in Step3, solution is with 2
℃·h-1Or 3 DEG C of h-1Or 6 DEG C of h-1Speed cooling.
4. a kind of Tb-MOF green light crystals material, it is characterised in that the Tb-MOF green light crystals material is one-component, chemical group
Turn into：{[Tb4(4,4 '-oxydibenzoic acid)6(H2O)9]·(H2O)}∞。
5. Tb-MOF green light crystals material according to claim 4, it is characterised in that be prepared by the following method：
Step1：At room temperature, by Tb (NO3)3·6H2O and 4,4 '-oxydibenzoic acid is added to the autoclave equipped with deionized water
In, stirring obtains well mixed solution, then adjusts pH value to 7.5-11 with ammoniacal liquor or NaOH solution；
Step2：Above-mentioned well mixed solution is incubated 72h at 180 DEG C；
Step3：Solution after above-mentioned heat treatment is cooled to room temperature；
Step4：Mother liquor is removed, the solid that will be obtained is washed with water repeatedly, the water white transparency flat crystal as product for obtaining.
6. Tb-MOF green light crystals material according to claim 5, it is characterised in that in Step3, solution is with 2 DEG C of h-1Or 3 DEG C of h-1Or 6 DEG C of h-1Speed cooling.
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