CN116656339A - Rare earth organic polymer phosphorescent material and preparation method and application thereof - Google Patents
Rare earth organic polymer phosphorescent material and preparation method and application thereof Download PDFInfo
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- CN116656339A CN116656339A CN202310420526.4A CN202310420526A CN116656339A CN 116656339 A CN116656339 A CN 116656339A CN 202310420526 A CN202310420526 A CN 202310420526A CN 116656339 A CN116656339 A CN 116656339A
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 36
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims abstract description 88
- 239000004005 microsphere Substances 0.000 claims abstract description 81
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 71
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000011247 coating layer Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 9
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
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- C—CHEMISTRY; METALLURGY
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- 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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Abstract
The invention provides a rare earth organic polymer phosphorescent material, a preparation method and application thereof, wherein the inner layer of the material is scandium/leucine microsphere, and the outer layer of the material is inorganic salt coating layer. According to the invention, scandium/leucine microspheres are treated by inorganic salt solution to prepare the rare earth organic polymer phosphorescent material with ultra-long service life, and the material can emit long-service-life room-temperature phosphorescence under ultraviolet excitation, so that gram-scale quantitative production can be realized, and the adjustment of the phosphorescence property of the luminescent material can be effectively realized by changing the types of inorganic salts. The invention can be applied to luminescent materials of micron order, overcomes the defect that the application range of the traditional room temperature phosphorescent material is limited to nanoscale, provides a powerful strategy for synthesizing phosphorescent materials with ultra-long service life in a large scale and low cost, and is expected to realize biological imaging in cells.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a rare earth organic polymer phosphorescent material, a preparation method and application thereof.
Background
Room temperature phosphorescent materials are a class of luminescent materials that are excited by radiation at room temperature and that release energy to emit phosphorescence visible to the naked eye after the excitation is stopped. The room temperature phosphorescent material with long-life excitons has special advantages in the aspects of low background interference, signal-to-noise ratio enhancement, long-life emission and the like, is widely focused, and has good application prospects in the aspects of biosensing, information encryption, cell imaging, light-emitting diodes (leds) and the like. However, because triplet excitons of room temperature phosphorescent materials are sensitive to a variety of factors (e.g., humidity, ambient oxygen, and rigid substrates, etc.), challenges remain in constructing room temperature phosphorescent materials with high phosphorescent quantum yields and long lifetimes on the order of microseconds. To solve the above problems, efforts are now made to increase the phosphorescence quantum efficiency and to extend the phosphorescence lifetime of materials by molecular design or structure confinement strategies. However, such strategies still have the disadvantages at present, and the matrix is mostly limited by small-sized luminescent materials, complicated preparation process, limited experimental conditions and the like.
The rare earth room temperature phosphorescent organic polymeric material is an emerging room temperature phosphorescent material and consists of rare earth metal and a specific coordination polymer, and has good prospect in numerous practical applications of the room temperature phosphorescent organic polymeric material, but the defects of complex preparation process, limited material size, low phosphorescence emission efficiency and the like exist in the prior art, so that the rare earth room temperature phosphorescent organic polymeric material with simple preparation and long service life is needed.
Disclosure of Invention
The invention aims to provide a rare earth organic polymer phosphorescent material with micron size, high operability and long service life, which not only realizes long service life phosphorescence and has the capability of gram-scale production, but also has simple preparation method and high operability.
A second object of the present invention is to provide a method for preparing a rare earth organic polymer phosphorescent material.
A third object of the present invention is to provide the use of rare earth organic polymer phosphorescent materials.
In order to achieve the first purpose, the invention provides a rare earth organic polymer phosphorescent material, wherein the inner layer of the material is scandium/leucine microsphere, and the outer layer of the material is inorganic salt coating layer.
As a preferred embodiment, the inorganic salt is a metal sulfate.
As a further preferred embodiment, the metal sulfate comprises a sulfate of the metal potassium, calcium, sodium, magnesium, aluminum, zinc, iron, copper or manganese. The adjustment of the phosphorescence property of the luminescent material can be effectively realized by changing the kind of the inorganic salt.
As a preferred embodiment, the material is prepared by the following method:
(1) Scandium/leucine microsphere preparation: dissolving scandium nitrate and leucine powder in water, preparing scandium/leucine microspheres at high temperature by a one-pot hydrothermal method, then cleaning the microspheres, and drying;
(2) Preparation of inorganic salt @ scandium/leucine microsphere: and (3) dissolving scandium/leucine microsphere powder obtained in the step (1) in a metal sulfate solution, and drying to obtain the inorganic salt treated rare earth organic polymer phosphorescent material.
In order to achieve the second object of the present invention, the present invention provides a method for preparing a rare earth organic polymer phosphorescent material, comprising the steps of:
(1) Scandium/leucine microsphere preparation: dissolving scandium nitrate and leucine powder in water, preparing scandium/leucine microspheres at high temperature by a one-pot hydrothermal method, then cleaning the microspheres, and drying;
(2) Preparation of inorganic salt @ scandium/leucine microsphere: and (3) dissolving scandium/leucine microsphere powder obtained in the step (1) in a metal sulfate solution, and drying to obtain the inorganic salt treated rare earth organic polymer phosphorescent material.
As a preferable scheme, the hydrothermal temperature adopted by the one-pot hydrothermal method in the step (1) is 160-260 ℃ and the hydrothermal time is 1-7h.
As a preferred embodiment, the ratio of the amounts of the substances of scandium nitrate and leucine powder in step (1) is (0.80-2.10): 1, or preferably (0.90-1.06): 1.
as a preferred embodiment, the metal sulfate in step (2) comprises a sulfate of the metal potassium, calcium, sodium, magnesium, aluminum, zinc, iron, copper or manganese.
In order to achieve the third object of the invention, the invention provides the application of the rare earth organic polymer phosphorescent material in the manufacture of information encryption products, anti-counterfeiting products and photoelectric device products. The ultraviolet excitation light is adopted to irradiate the ultra-long rare earth organic polymer phosphorescent material, and the rare earth organic polymer phosphorescent material can emit long-life room-temperature phosphorescence after excitation is stopped.
The inorganic salt@scandium/leucine microsphere provided by the invention can emit long-life room-temperature phosphorescence, and the phosphorescence property of the luminescent material is effectively adjusted by changing the type of the inorganic salt. The inorganic salt thermal crystallization method used by the invention has the advantages of simple operation flow, low professional threshold and high reproducibility, can realize gram-scale preparation scale, can be applied to micron-scale luminescent materials, overcomes the defect that the application range of the traditional room-temperature phosphorescent material is limited to nano-scale, and provides a powerful strategy for synthesizing the phosphorescent material with ultra-long service life in a large scale and at low cost.
Drawings
FIG. 1 is a graph showing the anti-counterfeiting function and effect of scandium/leucine microspheres prepared in example 6 under ultraviolet excitation, and the material Al prepared in example 6 2 (SO 4 ) 3 LED lamp prepared based on Sc/Leu-MSs.
FIG. 2 is a phosphorescent emission spectrum of Sc/Leu-MSs showing the ratio of amounts of different substances produced in example 7.
FIG. 3 shows the preparation of Sc/Leu-MSs, K in examples 1 to 6, respectively 2 SO 4 @Sc/Leu-MSs,CaSO 4 @Sc/Leu-MSs,Na 2 SO 4 @Sc/Leu-MSs,MgSO 4 @Sc/Leu-MSs,ZnSO 4 @Sc/Le u-MSs,Al 2 (SO 4 ) 3 Sc/Leu-MSs emit light upon and after ultraviolet light irradiation.
FIG. 4 shows an embodiment 16 Sc/Leu-MSs, K are prepared respectively 2 SO 4 @Sc/Leu-MSs,CaSO 4 @Sc/Leu-MSs,Na 2 SO 4 @Sc/Leu-MSs,MgSO 4 @Sc/Leu-MSs,ZnSO 4 @Sc/Le u-MSs,Al 2 (SO 4 ) 3 Phosphorescent lifetime change data for Sc/Leu-MSs at different excitations.
FIG. 5 shows inorganic salt @ scandium/leucine microspheres (K) obtained in examples 1 to 6 and subjected to treatment with an inorganic salt solution and heat recrystallization 2 SO 4 @Sc/Leu-MSs,CaSO 4 @Sc/Leu-MSs,Na 2 SO 4 @Sc/Leu-MSs,MgSO 4 @Sc/Leu-MSs,ZnSO 4 @Sc/Leu-MSs,Al 2 (SO 4 ) 3 Sc/Leu-MSs).
FIG. 6 is a scanning electron microscope image of scandium/leucine microspheres (Sc/Leu-MSs) of example 1.
FIG. 7 shows the ultralong rare earth organic polymer phosphorescent materials (K) obtained in examples 1 to 6, respectively 2 SO 4 @Sc/Leu-MSs,CaSO 4 @Sc/Leu-MSs,Na 2 SO 4 @Sc/Leu-MSs,MgSO 4 @Sc/Leu-MSs,ZnSO 4 @Sc/Leu-MSs,Al 2 (SO 4 ) 3 Sc/Leu-MSs).
FIG. 8 is a three-dimensional phosphorescence spectrum of Sc/Leu-MSs of example 1.
FIG. 9 shows K prepared in each of examples 1 to 6 2 SO 4 @Sc/Leu-MSs,CaSO 4 @Sc/Leu-MSs,Na 2 SO 4 @Sc/Leu-MSs,MgSO 4 @Sc/Leu-MSs,ZnSO 4 @Sc/Le u-MSs,Al 2 (SO 4 ) 3 Three-dimensional phosphorescence spectrum of Sc/Leu-MSs.
Detailed Description
Hereinafter, the technology of the present invention will be described in detail with reference to the specific embodiments. It should be understood that the following detailed description is merely intended to aid those skilled in the art in understanding the invention, and is not intended to limit the invention.
Example 1
(1) Preparation of scandium/leucine microsphere
1.5mmolSc (NO) 3 ) 3 ·6H 2 O and 1.5 mmole of Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. The obtained product is washed and centrifuged for 5 times at a rotating speed of 3000 rpm for 2min each time, and then is put into a vacuum drying oven for drying, thus obtaining scandium/leucine microsphere (Sc/Leu-MSs) powder for further utilization.
(2) Preparation of Potassium sulfate @ scandium/leucine microsphere
Dissolving 40mgSc/Leu-MSs in K by ultrasound 2 SO 4 In a salt solution. Then evaporating water by heating at 90deg.C with vacuum drying oven to obtain treated potassium sulfate @ scandium/leucine microsphere (K) 2 SO 4 Sc/Leu-MSs) powder for further use.
Example 2
(1) Preparation of scandium/leucine microsphere
1.5mmolSc (NO) 3 ) 3 ·6H 2 O and 1.5 mmole of Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. The obtained product is washed and centrifuged for 5 times at a rotating speed of 3000 rpm for 2min each time, and then is put into a vacuum drying oven for drying, thus obtaining scandium/leucine microsphere (Sc/Leu-MSs) powder for further utilization.
(2) Preparation of calcium sulfate @ scandium/leucine microsphere
Dissolving 40mgSc/Leu-MSs in CaSO by sonication 4 In a salt solution. Then evaporating water by heating at 90deg.C in vacuum drying oven to obtain treated calcium sulfate @ scandium/leucine microsphere (CaSO) 4 Sc/Leu-MSs) powder for further use.
Example 3
(1) Preparation of scandium/leucine microsphere
1.5mmolSc (NO) 3 ) 3 ·6H 2 O and 1.5 mmole of Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. Washing and centrifuging the obtained product at 3000 rpm for 5 times for 2min, and vacuum dryingDrying in a box to obtain scandium/leucine microsphere (Sc/Leu-MSs) powder for further use.
(2) Preparation of sodium sulfate @ scandium/leucine microsphere
40mgSc/Leu-MSs were dissolved in 1.5 mmoles of Na by sonication 2 SO 4 In a salt solution. Then evaporating water by heating at 90deg.C in a vacuum drying oven to obtain treated sodium sulfate @ scandium/leucine microsphere (Na 2 SO 4 Sc/Leu-MSs) powder for further use.
Example 4
(1) Preparation of scandium/leucine microsphere
1.5mmolSc (NO) 3 ) 3 ·6H 2 O and 1.5 mmole of Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. The obtained product is washed and centrifuged for 5 times at a rotating speed of 3000 rpm for 2min each time, and then is put into a vacuum drying oven for drying, thus obtaining scandium/leucine microsphere (Sc/Leu-MSs) powder for further utilization.
(2) Preparation of magnesium sulfate @ scandium/leucine microsphere
40mgSc/Leu-MSs were dissolved in MgSO by sonication 4 In a salt solution. Then evaporating the water by heating at 90deg.C in a vacuum drying oven to obtain treated magnesium sulfate @ scandium/leucine microsphere (MgSO) 4 Sc/Leu-MSs) powder for further use.
Example 5
(1) Preparation of scandium/leucine microsphere
1.5mmolSc (NO) 3 ) 3 ·6H 2 O and 1.5 mmole of Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. The obtained product is washed and centrifuged for 5 times at a rotating speed of 3000 rpm for 2min each time, and then is put into a vacuum drying oven for drying, thus obtaining scandium/leucine microsphere (Sc/Leu-MSs) powder for further utilization.
(2) Preparation of Zinc sulfate @ scandium/leucine microsphere
Dissolving 40mgSc/Leu-MSs in ZnSO by ultrasound 4 In a salt solution. Then evaporating water by heating at 90deg.C with vacuum drying oven to obtain treated zinc sulfate @ scandium/leucine microsphere (ZnSO) 4 Sc/Leu-MSs) powder for further use.
Example 6
(1) Preparation of scandium/leucine microsphere
1.5mmolSc (NO) 3 ) 3 ·6H 2 O and 1.5 mmole of Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. The obtained product is washed and centrifuged for 5 times at a rotating speed of 3000 rpm for 2min each time, and then is put into a vacuum drying oven for drying, thus obtaining scandium/leucine microsphere (Sc/Leu-MSs) powder for further utilization.
(2) Preparation of aluminum sulfate @ scandium/leucine microsphere
Dissolving 40mgSc/Leu-MSs in Al by ultrasonic wave 2 (SO 4 ) 3 In a salt solution. Then evaporating water by heating at 90deg.C in vacuum drying oven to obtain treated aluminum sulfate @ scandium/leucine microsphere (Al) 2 (SO 4 ) 3 Sc/Leu-MSs) powder for further use.
(3) Preparation of anti-counterfeiting pattern
The scandium/leucine microsphere powder is used as a raw material, and is used together with other fluorescent powder (Eu microcrystal and Tb microcrystal) to construct an anti-counterfeiting pattern. The shape of the anti-counterfeiting pattern is changed after the excitation light source is removed by utilizing the characteristic of whether phosphorescence exists, so that the anti-counterfeiting function is realized, and the result is shown in fig. 1 (a).
And ultrasonically dispersing the scandium/leucine microsphere powder serving as a raw material in water to obtain a suspension serving as luminous ink, so that the anti-counterfeiting pattern is drawn. The color of the anti-counterfeiting pattern is changed after the excitation light source is removed by utilizing the characteristic that the ultraviolet excitation emits light before and after the ultraviolet excitation, so that the anti-counterfeiting function is realized, and the result is shown in fig. 1 (b). Therefore, as can be seen from fig. 1, the prepared scandium/leucine microsphere powder can be applied to anti-counterfeiting.
(4) LED lamp preparation
The DUV-LED lamp is prepared by using the aluminum sulfate@scandium/leucine microsphere powder as a raw material. When the driving current was increased from 20mA to 120mA, the values of chromaticity coordinates, color rendering index and color purity of the DUV-LED were slightly changed, while the emission intensity was gradually increased, demonstrating that the prepared material had great potential in the development of a novel DUV-LED, and the result is shown in fig. 1. Thus, as can be seen from fig. 1, the prepared inorganic salt@scandium/leucine microsphere powder treated by the inorganic salt thermal crystallization strategy can be applied to the field of photoelectric devices.
Example 7
Scandium/leucine microsphere with the quantity ratio of different substances is prepared in the embodiment, and the specific process is as follows:
the ratio of the amounts of the substances taken was Sc (NO) of 0.80,0.90,1.00,1.06,1.20,2.10:1, respectively 3 ) 3 ·6H 2 O and Leu ligand were dissolved in 5.0mL of ultrapure water. Subsequently, the mixed solution was transferred to a 25mL teflon lined stainless steel autoclave and heated to 200 ℃ for 300min. The obtained product is washed and centrifuged for 5 times at a rotating speed of 3000 rpm for 2min each time, and then is put into a vacuum drying oven for drying, so that scandium/leucine microsphere (Sc/Leu-MSs) powder with different mass ratios is obtained for further utilization.
Test examples
The present test example compares the luminescence properties of scandium/leucine microspheres having different amounts of substance. All phosphorescence performance tests of the material are carried out on an Edinburgh FLS1000 steady state transient fluorescence spectrometer, and the specific process is as follows:
the phosphorescent emission spectra of scandium/leucine microspheres for the ratios of amounts of different substances (n (Sc: leu) -0.80,0.90,1.00,1.06,1.20, 2.10:1) are shown in FIG. 2. As can be seen from fig. 2, scandium/leucine microspheres can emit cyan phosphorescence when the ratio of the amounts of substances of scandium nitrate to leucine is in the range of (0.80-2.10); also, when the ratio of the amounts of substances of scandium nitrate to leucine is in the range of (0.90-1.06), the scandium/leucine microsphere may exhibit dual emission characteristics, i.e. may emit both cyan and red phosphorescence under the same excitation. From the above series of data, it is found that scandium/leucine microspheres have good luminescence properties when the ratio of scandium nitrate to leucine is in the range of (0.80-2.10), and can be used as a raw material for subsequent thermal crystallization of inorganic salts.
The test example tests the performance of scandium/leucine microsphere and scandium/leucine microsphere treated by inorganic salt, and the specific process is as follows:
scandium/leucine microspheres (Sc/Leu-MSs) and inorganic salt treated scandium/leucine microspheres (K) 2 SO 4 @Sc/Leu-MSs,CaSO 4 @Sc/Leu-MSs,Na 2 SO 4 @Sc/Leu-MSs,MgSO 4 @Sc/Leu-MSs,ZnSO 4 @Sc/Leu-MSs,Al 2 (SO 4 ) 3 Sc/Leu-MSs) is shown in fig. 3 when irradiated with an ultraviolet lamp and after being turned off.
As can be seen from FIGS. 3, 4 and 5, inorganic salt treatment of scandium/leucine microspheres can produce ultra-long room temperature phosphorescence, the phosphorescence lifetime can be increased by 4.42 times at most in room temperature air, from 208.37ms (Sc/Leu-MSs) to 920.08ms (Al) 2 (SO 4 ) 3 Sc/Leu-MSs). Meanwhile, when scandium/leucine microsphere is treated by inorganic salt, the luminous quality of the material is greatly improved, and the maximum luminous quality can be from 40mg (Sc/Leu-MSs) to 1.0864g (Al) 2 (SO 4 ) 3 Sc/Leu-MSs), i.e. a 27.16-fold improvement in quality.
As can be seen from fig. 3, fig. 4 and fig. 5, the prepared super-long rare earth organic polymer phosphorescent material can be applied to the fields of anti-counterfeiting, information encryption, functional ink, photoelectric devices and the like by utilizing the advantages of super-long phosphorescent life and Kernel production of the prepared material.
The structure and performance of the ultra-long rare earth organic polymer phosphorescent materials prepared in examples 1 to 6 were tested, and the structural change and phosphorescent performance change of the target materials were mainly examined. All phosphorescence performance tests were performed on an Edinburgh FLS1000 steady state transient fluorescence spectrometer. The results are shown in FIGS. 6 to 9.
Fig. 6 and 7 are scanning electron microscope images of room temperature phosphorescent materials prepared in examples 1 to 6. It can be seen from fig. 6 that the prepared scandium/leucine microsphere has a rough surface quasi-microsphere structure, and from fig. 7, it can be seen that the inorganic salt-treated scandium/leucine microsphere prepared in examples 1 to 6 has a different kind of inorganic salt, and the resulting materials have a large difference in structure. However, the method can be divided into two types, one type is that the structure of the microsphere is not changed, and only the surface of the microsphere forms a coating layer; the other type not only forms a coating layer on the surface, but also damages the structure of the microsphere. The result further shows that the morphology of the super-long rare earth organic polymer phosphorescent material can be regulated and controlled by changing the type of inorganic salt and utilizing an inorganic salt recrystallization strategy so as to regulate and control the luminous performance.
Fig. 8 and 9 show three-dimensional phosphorescence spectra of room temperature phosphorescent materials prepared in examples 1 to 6. As can be seen from FIG. 8, scandium/leucine microsphere is a room temperature phosphorescent material with blue and red double emission, and as can be seen from FIG. 9, the inorganic salt treated scandium/leucine microsphere prepared in examples 1-6 has different kinds of inorganic salt, and the generated materials have larger difference in phosphorescence property, but the materials can be roughly divided into two kinds, namely, the luminescence emission peak of the microsphere is not changed, and only the phosphorescence luminescence property of the microsphere is improved, namely, the luminescence intensity and service life are improved to a certain extent; the other is to change the double emission peak of the material into a single emission peak of cyan, so that the phosphorescence service life and the intensity are greatly improved, the service life can be improved by 4.42 times at most, and the intensity can be even improved to 24.08 times. The result further shows that the phosphorescence performance of the super-long rare earth organic polymer phosphorescent material can be regulated and controlled by changing the type of the inorganic salt and utilizing the inorganic salt recrystallization strategy.
In summary, in the embodiment of the invention, scandium/leucine microsphere is prepared by hydrothermal method, and the prepared organic room-temperature phosphorescent material can emit phosphorescence with high quality, long service life and high efficiency in room-temperature air by an inorganic salt heating recrystallization strategy. And by changing the types of inorganic salts, the properties of the rare earth organic room temperature phosphorescent material, such as phosphorescence emission life, efficiency and the like, can be regulated and controlled. Meanwhile, the application of the prepared material in the aspects of information encryption, anti-counterfeiting ink, photoelectric devices and the like can be effectively realized by utilizing the unique super-long rare earth organic polymer phosphorescent material. Therefore, the inorganic salt thermal crystallization strategy has the advantages of simple operation flow, low professional threshold and high reproducibility, and meanwhile, the long-life luminescent material prepared by the method has the characteristics of long service life, high quality, adjustable luminescent performance and the like, so that a powerful strategy is provided for synthesizing the super-long rare earth organic polymer phosphorescent material in large scale and low cost to be applied to the fields of data encryption, functional ink and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The rare earth organic polymer phosphorescent material is characterized in that the inner layer of the material is scandium/leucine microsphere, and the outer layer is inorganic salt coating layer.
2. A rare earth organic polymer phosphorescent material according to claim 1, characterized in that the inorganic salt is a metal sulfate.
3. A rare earth organic polymer phosphorescent material according to claim 2, characterized in that the metal sulphate comprises sulphate of the metals potassium, calcium, sodium, magnesium, aluminium, zinc, iron, copper or manganese.
4. A rare earth organic polymer phosphorescent material according to any of claims 1-3, characterized in that the material is prepared by the following method:
(1) Scandium/leucine microsphere preparation: dissolving scandium nitrate and leucine powder in water, preparing scandium/leucine microspheres at high temperature by a one-pot hydrothermal method, then cleaning the microspheres, and drying;
(2) Preparation of inorganic salt @ scandium/leucine microsphere: and (3) dissolving scandium/leucine microsphere powder obtained in the step (1) in a metal sulfate solution, and drying to obtain the inorganic salt treated rare earth organic polymer phosphorescent material.
5. The method for preparing a rare earth organic polymer phosphorescent material according to claim 1, comprising the steps of:
(1) Scandium/leucine microsphere preparation: dissolving scandium nitrate and leucine powder in water, preparing scandium/leucine microspheres at high temperature by a one-pot hydrothermal method, then cleaning the microspheres, and drying;
(2) Preparation of inorganic salt @ scandium/leucine microsphere: and (3) dissolving scandium/leucine microsphere powder obtained in the step (1) in a metal sulfate solution, and drying to obtain the inorganic salt treated rare earth organic polymer phosphorescent material.
6. The method for preparing a rare earth organic polymer phosphorescent material according to claim 5, wherein the hydrothermal temperature of the one-pot hydrothermal method in the step (1) is 160-260 ℃ and the hydrothermal time is 1-7h.
7. The method for producing a rare earth organic polymer phosphorescent material according to claim 5, wherein the ratio of the amounts of substances of scandium nitrate and leucine powder in step (1) is (0.8-2.1): 1.
8. use of the rare earth organic polymer phosphorescent material according to claim 1 in the manufacture of information encryption products, security products and optoelectronic device products.
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