CN109232619B - Multicolor fluorescent material based on rare earth metal organic framework, preparation method thereof and application of anti-counterfeiting ink - Google Patents
Multicolor fluorescent material based on rare earth metal organic framework, preparation method thereof and application of anti-counterfeiting ink Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 54
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 14
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 15
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910001940 europium oxide Inorganic materials 0.000 claims description 5
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 5
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- YFWIACABGHWPLP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;propane-1,2,3-triol Chemical compound OCC(O)CO.OCCOCCO YFWIACABGHWPLP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000007639 printing Methods 0.000 abstract description 9
- 229910052693 Europium Inorganic materials 0.000 abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012795 verification Methods 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/307—Monocyclic tricarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Credit Cards Or The Like (AREA)
Abstract
The invention discloses a multicolor fluorescent material based on a rare earth metal organic framework, a preparation method thereof and application of anti-counterfeiting ink. The preparation method comprises the steps of uniformly mixing a rare earth nitrate solution, 1,3, 5-benzene tricarboxylic acid, anhydrous sodium acetate, anhydrous ethanol, N-dimethylformamide and deionized water, placing the mixture in a drying oven to react at 75 ℃, taking out the mixture for centrifugation, washing and drying the mixture by using the deionized water and the anhydrous ethanol, and grinding the mixture to obtain the rare earth nitrate solution. The rare earth is yttrium, terbium and europium. The material has simple synthesis condition and high luminous brightness, can realize light color adjustment from green to red, prints the preset anti-counterfeiting pattern containing a certain specific color or mixed color by an ink-jet printer, and overcomes the problem of poor concealment in anti-counterfeiting printing because the printed pattern is hidden under sunlight. In the anti-counterfeiting verification, a 254nm ultraviolet lamp is adopted to excite the pattern, a preset specific color or a preset mixed color is displayed, and a good anti-counterfeiting effect is achieved.
Description
Technical Field
The invention belongs to the field of anti-counterfeiting ink, and particularly relates to a rare earth metal organic framework-based multicolor fluorescent material, a preparation method thereof and application of the anti-counterfeiting ink.
Background
With the rapid development of economic society, the circulation speed of social wealth is accelerated, and the activities of counterfeiting commodity currency, medicines and the like and counterfeit crimes are rampant day by day, thereby causing great property loss to the masses of people. 25-26 months of 2004, "the first global major vacation" was held at the Burussell world customs organization headquarters. Conference materials show that global counterfeit and infringement goods cost more than 6000 billion dollars, which is equivalent to 7% of the total world trade, and become the third public nuisance of the world after terrorist activities and drug selling. The counterfeit infringement activities damage the investment environment, inhibit the innovation spirit of people, cause the loss of government tax and induce social problems. Therefore, such illegal criminal activities need to be stricken strictly, and besides providing a complete set of rules and regulations in law, anti-counterfeiting technology must be developed.
The anti-counterfeiting technology specified in national standards of China is' a technology which is adopted for achieving the anti-counterfeiting purpose, can accurately identify the true and false within a certain range and is not easy to copy and duplicate. The existing common anti-counterfeiting modes are mainly physical anti-counterfeiting technologies including holographic anti-counterfeiting, radio frequency identification and the like, the technologies are difficult to copy and have good anti-counterfeiting performance, but the problems of high equipment construction and high maintenance cost exist at the same time, so that the defect is overcome due to the appearance of chemical anti-counterfeiting materials.
For enterprises, the anti-counterfeiting ink is widely used. For different functions of the anti-counterfeiting ink, the anti-counterfeiting ink with the fluorescent characteristic is most accepted by the industry. For some fluorescent anti-counterfeiting inks, such as quantum dots, although the brightness of the ink is strong, the ink can also show a certain color under sunlight, and the concealment of the ink as an anti-counterfeiting material is greatly reduced. In addition, many existing fluorescent materials used as anti-counterfeiting ink have single luminescent color under the excitation of ultraviolet, are easy to copy in long-term use and have poor anti-counterfeiting effect. Therefore, it is a continuous pursuit goal to develop an anti-counterfeiting material with strong concealment, strong response after excitation, high brightness, and variable colors of emitted light.
The unique structure of the metal organic framework endows the metal organic framework with a plurality of physical and chemical properties, so that the metal organic framework can be applied to various fields. Rare earth elements can realize light emission of various colors due to their abundant energy levels, and thus play an important role in display illumination. Rare earth elements are introduced into the metal organic framework, and the energy of the ligand is transferred to rare earth ions by utilizing the antenna effect, so that the rare earth ions can generate stronger luminescence; in addition, the light color can be adjusted by doping various rare earth elements, and the possibility that the anti-counterfeiting material is repeated can be reduced by applying the multi-color luminescent material to the printing of the anti-counterfeiting pattern.
In summary, there is a need to develop the application of the multicolor fluorescent material based on the rare earth metal organic framework in the anti-counterfeiting ink, so as to solve the defects of weak concealment and single luminescent color in the existing chemical fluorescent anti-counterfeiting material, and provide the anti-counterfeiting ink with simple synthesis process, strong luminescent brightness and adjustable light color.
Disclosure of Invention
The invention aims to provide a multicolor fluorescent material based on a rare earth metal organic framework, which solves the existing defects, and is characterized in that a preset anti-counterfeiting pattern containing a certain specific color or mixed color is printed by an ink-jet printer, the printed pattern is invisible under sunlight, a 254nm ultraviolet lamp is adopted to excite the pattern in anti-counterfeiting verification, the preset specific color or mixed color is displayed, the color is adjustable in the range from green to red, and the anti-counterfeiting effect is achieved.
The invention also aims to provide a preparation method of the multicolor fluorescent anti-counterfeiting ink based on the rare earth metal organic framework.
The above purpose of the invention is realized by the following technical scheme:
a multicolor fluorescent material based on a rare earth metal organic framework is prepared by the following steps: the preparation method comprises the steps of uniformly mixing a rare earth nitrate solution, 1,3, 5-benzene tricarboxylic acid, anhydrous sodium acetate, anhydrous ethanol, N-dimethylformamide and deionized water, placing the mixture in an oven to react at 75 ℃, taking out the mixture for centrifugation, washing the mixture with the deionized water and the anhydrous ethanol, drying the washed mixture, and grinding the washed mixture in an agate mortar to obtain the multicolor fluorescent material based on the rare earth metal organic framework.
In the multicolor fluorescent material based on the rare earth metal organic framework, the rare earth is yttrium, terbium and europium.
In the above multicolor fluorescent material based on a rare earth metal organic framework, the preparation method of the rare earth nitrate solution comprises the following steps: dissolving yttrium nitrate hexahydrate in deionized water to constant volume; taking terbium oxide powder, adding a proper amount of concentrated nitric acid, stirring until the terbium oxide powder is completely dissolved, and adding deionized water to a constant volume; taking europium oxide powder, adding a proper amount of concentrated nitric acid, stirring until the europium oxide powder is completely dissolved, and adding deionized water to a constant volume.
The anti-counterfeiting ink prepared by utilizing the multicolor fluorescent material based on the rare earth metal organic framework comprises the following components in parts by weight:
rare earth metal organic framework powder 0.1 g
20-25m L of absolute ethyl alcohol
Ethylene glycol 20-25m L
1-4m L glycerol
Diethylene glycol 1-4m L
Sodium dodecyl sulfate solution 2 m L.
The preparation method of the anti-counterfeiting ink comprises the following steps: the components are uniformly mixed, ultrasonically dispersed, centrifuged and then supernatant fluid is taken, and the anti-counterfeiting ink prepared from the multicolor fluorescent material based on the rare earth metal organic framework is obtained.
The multicolor fluorescence has adjustable color from green to red, including green, yellow, orange red and red.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a multicolor fluorescent material based on a rare earth metal organic framework, a preparation method thereof and application of anti-counterfeiting ink, wherein the material has simple synthesis conditions and high luminous brightness, can realize light color adjustment from green to red, and is used for printing a preset anti-counterfeiting pattern containing a certain specific color or mixed colors by an ink-jet printer, and the printed pattern is hidden in sunlight, so that the problem of poor concealment in anti-counterfeiting printing is solved. In the anti-counterfeiting verification, a 254nm ultraviolet lamp is adopted to excite the pattern, a preset specific color or a preset mixed color is displayed, and a good anti-counterfeiting effect is achieved.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a rare earth metal organic framework multicolor fluorescent material with adjustable color from green to red in examples 1-2, wherein the pattern labeled "s" is L a (BTC). sub.6H2Crystals of OThe simulated diffraction pattern drawn by the scientific Information File (cif), wherein the samples marked as "a-h" represent the feeding volume ratio of the yttrium nitrate solution, the terbium nitrate solution and the europium nitrate solution in examples 1-2 respectively: 8 samples of 3:7:0, 5:14:1, 2:7:1, 3:14:3, 1:7:2, 1:14:5, 0:7:3, 7:0: 3.
FIG. 2 is a scanning electron microscope image of the green light emitting rare earth metal organic framework material of examples 1-2 according to the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solution of 3:7: 0. The magnification is 3 ten thousand times, and the length of the scale is 1 μm in the figure.
FIG. 3 is an emission spectrum of the rare earth metal organic framework multicolor fluorescent material at room temperature in examples 1-2. The excitation wavelength is 300nm, and the spectral range is 450 nm-750 nm. Wherein, the samples marked as "a-h" respectively represent the samples in examples 1-2 according to the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solutions: 8 samples of 3:7:0, 5:14:1, 2:7:1, 3:14:3, 1:7:2, 1:14:5, 0:7:3, 7:0: 3.
FIG. 4 is a color coordinate diagram of the color-tunable rare-earth metal organic framework multicolor fluorescent material in embodiments 1-2. Wherein, the color coordinates marked as "a-h" respectively represent the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solution in examples 1-2: color coordinates of 8 samples of 3:7:0, 5:14:1, 2:7:1, 3:14:3, 1:7:2, 1:14:5, 0:7:3, 7:0: 3.
FIG. 5 is a graph showing the effect of the green light emitting metal organic framework fluorescent anti-counterfeiting ink of examples 1 to 4 under a 254nm ultraviolet lamp after printing a pattern on an inkjet printer according to the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solutions of 3:7: 0.
FIG. 6 is a graph showing the effect of yellow light-emitting metal-organic framework fluorescent anti-counterfeiting ink on an ink-jet printer under a 254nm ultraviolet lamp after patterns are printed on the ink-jet printer according to the embodiment 1-4, wherein the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate is 5:14: 1.
FIG. 7 is a graph showing the effect of the red light-emitting metal organic framework fluorescent anti-counterfeiting ink of examples 1 to 4 under a 254nm ultraviolet lamp after printing patterns on an inkjet printer according to the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solutions of 7:0: 3.
FIG. 8 is a graph showing the effect of the yellow light-emitting metal-organic framework fluorescent anti-counterfeiting ink of examples 1 to 4 under a fluorescent lamp after a pattern is printed on an ink-jet printer according to the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solutions of 5:14: 1.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1: preparing a rare earth nitrate solution:
1.9150g of yttrium nitrate hexahydrate is weighed, deionized water is added and stirred to dissolve, the volume is determined to be 50 m L, 1.8692 g of terbium oxide powder with the purity of 99.99% is weighed, a proper amount of concentrated nitric acid is added and stirred to be completely dissolved, deionized water is added and the volume is determined to be 50 m L, 1.7596 g of europium oxide powder with the purity of 99.99% is weighed, a proper amount of concentrated nitric acid is added and stirred to be completely dissolved, deionized water is added and the volume is determined to be 50 m L, 0.0150 g of sodium dodecyl sulfate powder is weighed, and deionized water is added and dissolved to be 50 m L.
Example 2: synthesis of rare earth metal organic framework multicolor fluorescent material:
feeding 0.1 mol/L of rare earth nitrate according to the volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solutions of 3:7:0, 5:14:1, 2:7:1, 3:14:3, 1:7:2, 1:14:5, 0:7:3 and 7:0:3 respectively, wherein the total volume of the rare earth nitrate is 2.8 m L, adding 0.08 g of 1,3, 5-benzenetricarboxylic acid, 0.025g of anhydrous sodium acetate, 8 m L of anhydrous ethanol, 8 m L N, N-dimethylformamide and 3.6 m L of deionized water, uniformly mixing, placing in an oven for reacting for 48 hours at 75 ℃, taking out, centrifuging for 5 minutes at 4000 rpm, washing and centrifuging for multiple times by using the deionized water and the anhydrous ethanol, drying, grinding in an agate mortar, and obtaining the rare earth metal organic framework powder sample.
Example 3: preparation of multi-color fluorescent anti-counterfeiting ink based on rare earth metal organic framework
Rare earth metal organic framework powder 0.1 g
Anhydrous ethanol 22.5m L
Ethylene glycol 22.5m L
Glycerol 2.5m L
Diethylene glycol 2.5m L
Sodium dodecyl sulfate solution 2 m L
Uniformly mixing the raw materials, performing ultrasonic dispersion for 30 min, centrifuging the mixture on a centrifuge at the rotating speed of 1000 rpm for 5min, and taking supernatant to obtain the multicolor fluorescent anti-counterfeiting ink based on the rare earth metal organic framework.
Example 4: test experiments
1. Regarding the structural properties of the rare earth metal organic frameworks in the above examples 1-2, as shown in the results of FIG. 1, the rare earth metal organic frameworks with adjustable colors from green to red obtained by the preparation method of the present invention all have L a (BTC). sub.6H2O (the crystal structure data has been included in the Cambridge Crystal Structure data center (CCDC) with CCDC number: 290771).
2. The morphology of the green light emitting metal organic framework in the above examples 1-2 according to the feeding volume ratio of the yttrium nitrate solution, the terbium nitrate solution and the europium nitrate solution of 3:7:0 is shown in the result of fig. 2. The rare earth metal organic framework is a uniform rod-shaped structure, the width of the rare earth metal organic framework is 100-200 nm, and the length of the rare earth metal organic framework reaches several micrometers.
3. Spectral test conditions of the rare earth metal organic frameworks in examples 1 to 2.
The ultraviolet excited emission spectrum adopts Xe lamp as excitation light source, the excitation wavelength is adjusted to 300nm by a monochromator, and the spectrum test range is 450 nm-750 nm.
4. The results of the spectroscopic test of the rare earth metal organic frameworks in examples 1 to 2.
FIG. 3 is an emission spectrum of the color-tunable rare-earth metal organic framework fluorescent material of examples 1-2. Under the excitation of 300nm, a plurality of narrower emission peaks with the peak values positioned at 541nm are obtained according to a green light emission sample with the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solution of 3:7:0, and the emission peaks belong to f-f transition of terbium element in a metal organic framework, and the metal organic framework has the advantages thatThe body attributes are as follows: at about 486, 541, 581, 617 nm, respectively5D4–7FJ(J = 6, 5, 4, 3). According to a red light emission sample with the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate of 7:0:3, a plurality of narrow emission peaks with the peak values positioned at 613nm are obtained, and the emission peaks belong to f-f transition of europium element in a metal organic framework, and are specifically attributed as follows: at about 580, 590, 613, 647, 687 nm5D0–7FJ’(J' = 0, 1, 2, 3, 4). The other codoped samples simultaneously obtain emission peaks attributed to terbium element and europium element.
FIG. 4 is a color coordinate diagram of the color-tunable rare-earth metal organic framework fluorescent material in examples 1-2. Wherein, the color coordinates marked as "a-h" respectively represent the feeding volume ratio of yttrium nitrate, terbium nitrate and europium nitrate solution in examples 1-2: color coordinates of 8 samples of 3:7:0, 5:14:1, 2:7:1, 3:14:3, 1:7:2, 1:14:5, 0:7:3, 7:0: 3. The color range varies from green to red, and the variation is obvious.
Fig. 5, 6 and 7 show the effect of the multi-color fluorescent anti-counterfeiting ink based on the rare earth metal organic framework under a 254nm ultraviolet lamp after the pattern is printed on an ink-jet printer in the embodiments 1 to 4. Taking green, yellow and red fluorescent anti-counterfeiting inks as examples, the green fluorescent anti-counterfeiting ink is used for printing a school badge pattern of Zhongshan university; printing a Sun Zhongshan portrait and a SunYat-sen character by using yellow fluorescent anti-counterfeiting ink; and printing a two-dimensional code pattern by using red ink.
FIG. 8 shows the effect of the multi-color fluorescent anti-counterfeiting ink based on the rare earth metal organic framework in the embodiment 1-4 under the fluorescent lamp after the pattern is printed on the ink-jet printer. By taking the yellow light emitting metal organic framework fluorescent anti-counterfeiting ink with the feeding volume ratio of yttrium nitrate solution to terbium nitrate solution to europium nitrate solution of 5:14:1 as an example, the printed pattern is invisible under sunlight, and the defect that some anti-counterfeiting inks are not strong in concealment under the sunlight is well overcome.
Claims (4)
1. A multicolor fluorescent material based on a rare earth metal organic framework is characterized by being prepared by the following method: uniformly mixing a rare earth nitrate solution, 1,3, 5-benzenetricarboxylic acid, anhydrous sodium acetate, anhydrous ethanol, N-dimethylformamide and deionized water, placing the mixture in an oven to react at 75 ℃, taking out the mixture for centrifugation, washing and drying the mixture by using the deionized water and the anhydrous ethanol, and grinding the mixture in an agate mortar to obtain the multicolor fluorescent material based on the rare earth metal organic framework;
the rare earth nitrate solution is a mixed solution of yttrium nitrate, terbium nitrate and europium nitrate.
2. The multicolor fluorescent material based on rare-earth metal organic framework according to claim 1, characterized in that the preparation method of the rare-earth nitrate solution comprises the following steps: dissolving yttrium nitrate hexahydrate in deionized water to constant volume; taking terbium oxide powder, adding a proper amount of concentrated nitric acid, stirring until the terbium oxide powder is completely dissolved, and adding deionized water to a constant volume; taking europium oxide powder, adding a proper amount of concentrated nitric acid, stirring until the europium oxide powder is completely dissolved, and adding deionized water to a constant volume.
3. The anti-counterfeiting ink prepared by the multicolor fluorescent material based on the rare earth metal organic framework as claimed in claim 1 is characterized by comprising the following components in parts by weight:
rare earth metal organic framework powder 0.1 g
20-25m L of absolute ethyl alcohol
Ethylene glycol 20-25m L
1-4m L glycerol
Diethylene glycol 1-4m L
Sodium dodecyl sulfate solution 2 m L.
4. A process for preparing a security ink as claimed in claim 3, comprising the steps of: the components are uniformly mixed, ultrasonically dispersed, centrifuged and then supernatant fluid is taken, and the anti-counterfeiting ink prepared from the multicolor fluorescent material based on the rare earth metal organic framework is obtained.
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