CN114437712B - Fluorescence-adjustable dye molecule/ZIF-8 membrane, and preparation method and application thereof - Google Patents
Fluorescence-adjustable dye molecule/ZIF-8 membrane, and preparation method and application thereof Download PDFInfo
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012528 membrane Substances 0.000 title claims description 17
- 239000000975 dye Substances 0.000 claims abstract description 66
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 38
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 32
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000004528 spin coating Methods 0.000 claims description 27
- JBNOVHJXQSHGRL-UHFFFAOYSA-N 7-amino-4-(trifluoromethyl)coumarin Chemical compound FC(F)(F)C1=CC(=O)OC2=CC(N)=CC=C21 JBNOVHJXQSHGRL-UHFFFAOYSA-N 0.000 claims description 24
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical group Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- -1 imidazole ester Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical group O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the field of photoluminescent composite films, and particularly relates to a dye molecule/ZIF-8 film with adjustable fluorescence, a preparation method and application thereof. The composite film comprises the following components in molar volume: 2-methylimidazole, 1,2, 4-benzene tricarboxylic acid, zinc acetate dihydrate, fluorescent dye and solvent, wherein the molar ratio of 2-methylimidazole to zinc acetate dihydrate is 2.5-4:1, 2-methylimidazole (Hmim) to 1,2, 4-benzene tricarboxylic acid (H 3 BTC) is 100:0-16, and the molar ratio of 2-methylimidazole to solvent is 0.03-1.46:1, the molar ratio of zinc acetate dihydrate to dye is 5-100000:1. The preparation method is simple, and the film forming quality, the process repeatability and the film stability are good.
Description
Technical Field
The invention belongs to the field of photoluminescent composite films, and particularly relates to a dye molecule/ZIF-8 film with adjustable fluorescence, a preparation method and application thereof.
Background
The metal organic framework is a coordination polymer formed by self-assembling a multidentate organic ligand (most of aromatic polyacids and polybasic) containing oxygen, nitrogen and the like and a transition metal ion/metal cluster, is an organic-inorganic hybrid material, and is different from an inorganic porous material and a common organic complex. Has both the rigidity of inorganic materials and the flexibility of organic materials. Early, MOFs of the first class were synthesized, but were not highly porous and chemically stable. Later studies on coordination polymers formed by novel cationic, anionic and neutral ligands have emerged. In MOFs, the arrangement of organic ligands and metal ions or clusters has significant directionality, and different framework pore structures can be formed, thereby exhibiting different adsorption properties, optical properties, electromagnetic properties, and the like.
Currently, a large number of metal organic framework materials have been synthesized, mainly based on carboxyl-containing organic anionic ligands or used in combination with nitrogen-containing heterocyclic organic neutral ligands. Most of the metal-organic frameworks have the characteristics of larger porosity, adjustable pore diameter, higher specific surface area, diversified structures, good chemical stability, multiple metal sites and the like. Because of the controllable pore structure and large specific surface area, MOFs have wider application prospects than other porous materials, such as adsorption separation of H2, catalysts, magnetic materials, optical materials and the like.
The Zeolite Imidazole Frameworks (ZIFs) are a branch of MOFs, are a typical MOFs material, have the remarkable characteristic of high chemical stability, have good thermal stability under boiling water, naOH solution, organic solvent and even high pressure conditions, and are widely applied to a plurality of application fields. The compound is a porous crystal material, and consists of tetrahedral metal nodes and imidazole ligands, wherein organic imidazole ester is connected to transition metal in a crosslinking way to form a tetrahedral framework.
Wherein ZIF-8 is a three-dimensional sodalite topological structure formed by zinc ions and 2-methylimidazole ligand and has larger pore diameterAnd is chemically inert, is a good carrier. On the other hand, the organic fluorescent dye has various fluorescent colors and wider fluorescent peaks, and can regulate and control the luminous color of the organic fluorescent dye to be compounded into white light through a certain proportion. However, organic fluorescent dyes have fluorescence quenching due to aggregation at higher solid state or solution concentrations, which limits their use in fluorescence. In order to improve the stable and excellent fluorescence performance of the organic fluorescent dye in a solid state, MOFs and the dye are compounded to stabilize the fluorescence performance and reduce fluorescence quenching effect caused by aggregation.
Disclosure of Invention
In order to solve the technical problems, the invention provides a dye molecule/ZIF-8 with adjustable fluorescence, a preparation method and application thereof, and the preparation method is simple, and has good film forming quality, process repeatability and film stability.
The invention solves the technical problems, and the dye molecule/ZIF-8 membrane with adjustable fluorescence is characterized in that: the film comprises the following components: 2-methylimidazole, 1,2, 4-benzene tricarboxylic acid, zinc acetate dihydrate, fluorescent dye and solvent, wherein the molar ratio of the 2-methylimidazole to the 1,2, 4-benzene tricarboxylic acid is 100:0-16, and the molar ratio of the 2-methylimidazole to the solvent is 0.03-1.46:1, in the optimized scheme, the molar ratio of the 2-methylimidazole to the solvent is 0.73:1, the molar ratio of the 2-methylimidazole to the zinc acetate dihydrate is 2.5-4:1, and the molar ratio of the zinc acetate dihydrate to the dye is 5-100000:1.
The concentration of the 2-methylimidazole is 0.5-25mol/L, and the concentration of the 2-methylimidazole is the concentration in the composite sol.
The fluorescent dye is rhodamine 6G and/or coumarin 151.
The molar dosage concentration of the fluorescent dye rhodamine 6G is 0-0.005mol/L, and the molar dosage concentration of coumarin 151 is 0-0.025mol/L. The concentration of the fluorescent dye is the concentration of the dye in the composite sol formed after the dye is added, and the concentration is the concentration before film formation. The amount of dye in the prepared corresponding film can be regulated and controlled by controlling the amount of dye in the composite sol, so that the fluorescence of different colors of the film can be regulated and controlled.
The solvent is an alcohol solvent, and in the optimized scheme, the solvent is ethanol. .
Coumarin 151, also known as 7-amino-4-trifluoromethylcoumarin, has a molecular formula of C 10H6F3NO2 and exhibits a greenish fluorescence in ethanol solvent. Coumarin 151 belongs to other coumarin classes, and has substituents on the α -pyrone ring.
Rhodamine 6G, also called R6G, a water-soluble cationic fluorescent dye, of which aqueous solution emits green-yellow fluorescence under ultraviolet irradiation, alkaline solution shows dark-green fluorescence, and ethanol solution shows red-yellow green-yellow fluorescence, and is widely used for fluorescent labeling or quantitative analysis.
According to the invention, an organic fluorescent dye coumarin 151 and rhodamine 6G are uniformly dispersed in ZIF-8 sol in a spin-coating sol manner, so that a dye molecule/ZIF-8 composite film structure with good luminous performance is successfully prepared, the prepared composite film structure has adjustable fluorescence and good fluorescence stability, the problem of fluorescence quenching caused by aggregation of fluorescent dye is solved, and meanwhile, the fluorescent dye and the fluorescence of dye are successfully compounded into a white light film structure by virtue of the fluorescence of MOFs, so that the fluorescent dye is beneficial to being used in a white light LED device.
The invention relates to a dye molecule/ZIF-8 composite film with adjustable fluorescence and a preparation method thereof, comprising the following steps:
(1) Mixing ligand 2-methylimidazole (C 4H6N2) and 1,2, 4-benzene tricarboxylic acid (C 9H6O6) uniformly in a solvent; (2) And (3) adding zinc acetate dihydrate (Zn (CH 3COO)2·2H2 O) into the step (1) and magnetically stirring to form transparent ZIF-8 sol, wherein the H 3 BTC ligand is ensured to be completely dissolved in the solvent before adding the zinc acetate dihydrate, magnetically stirring to form colorless transparent sol, and then aging for more than or equal to 10 hours.
(3) Uniformly dissolving a certain proportion of fluorescent dye rhodamine 6G and coumarin 151 in ZIF-8 sol serving as a dye molecule solution to obtain composite sol; the viscosity of the obtained dye molecule/ZIF-8 composite sol can be regulated and controlled by the amount of a solvent and the ligand H 3 BTC, and no additional auxiliary agent is required to be added. After adding the fluorescent dye, magnetically stirring and aging for at least 10 hours, and reserving the mixture for spin coating.
(4) Performing spin coating and film plating on the composite sol obtained in the step (3);
(5) And carrying out heat treatment on the wet film after spin coating.
As the optimization of the technical scheme, the dye molecule/ZIF-8 composite film with adjustable fluorescence and the preparation method thereof further comprise part or all of the following technical characteristics:
the spin coating speed in the step (4) is 500 10000rp/s, and the film thickness can be controlled by different spin coating speeds.
As an improvement of the technical scheme, the heat treatment process of the dye molecule/ZIF-8 composite wet film after spin-coating in the step (5) is as follows: the dye molecule/ZIF-8 composite wet film after spin coating is placed in a heating table at 60 ℃ for curing for 0.5h, then the temperature of the heating table is adjusted to be 20 ℃ to 120 ℃ at intervals of 0.5h, and the temperature is kept at 120 ℃ for 5 h.
The application of the dye molecule/ZIF-8 film with adjustable fluorescence is that the film can be applied to the preparation of a white light LED device comprising the film, thereby achieving the purposes of decoration and outdoor night illumination.
The invention combines ZIF-8 after surface modification with organic fluorescent dye rhodamine 6G and coumarin 151, and combines blue light emission of ZIF-8 and luminescence of fluorescent dye into white fluorescence, and the fluorescence quantum efficiency of white light can reach about 60%. Meanwhile, the color of fluorescence can be regulated and controlled by changing the doping amount of the fluorescent dye.
The preparation method of the fluorescence-adjustable ZIF-8 and dye composite membrane structure is simple, and the membrane forming quality, the process repeatability and the membrane stability are good.
The invention has the following beneficial effects:
The ligand H 3 BTC adopted by the invention can modify the surface of ZIF-8, regulate and control the optical band gap of the ZIF-8, and can be better compounded with fluorescent dye; the color of fluorescence emission can be regulated and controlled by regulating and controlling the concentration of the organic fluorescent dye rhodamine 6G and coumarin 151, and finally white light emission is formed; in the fluorescence regulation process, ZIF-8 not only serves as a carrier for dye molecules to load so as to reduce fluorescence quenching effect caused by aggregation, but also blue fluorescence from ZIF-8 participates in the fluorescence regulation of the composite membrane dye molecules/ZIF-8; the viscosity of the sol compounded by ZIF-8 and dye can be regulated and controlled by adding the amount of ligand H 3 BTC and the volume of solvent ethanol, no addition of any auxiliary agent is needed, the sol film forming quality is high, and the film thickness is controllable.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and appreciated, as well as other objects, features and advantages of the present invention, as described in connection with the following detailed description of the preferred embodiments.
Drawings
FIG. 1 is an XRD pattern of a modified ZIF-8 film and dye molecule/ZIF-8 composite film prepared in example 4 of the present invention
FIG. 2 is an ultraviolet-visible light absorption spectrum of a modified ZIF-8 film and dye molecule/ZIF-8 composite film prepared in example 4 of the present invention
FIG. 3 is a Photoluminescence (PL) spectrum and a fluorescence quantum efficiency (PLQY) spectrum of a white fluorescent film prepared by compounding dye molecules/ZIF-8 according to example 4 of the invention
FIG. 4 is an ultraviolet-visible absorption spectrum of a composite film of ZIF-8 and different dye amounts prepared in example 5 of the present invention
FIG. 5 shows photoluminescence spectra of different dye doping amounts and ZIF-8 composite films prepared in example 5 of the invention
Detailed Description
The following detailed description of specific embodiments of the invention, which are included as part of the specification, illustrate the principles of the invention and together with the description serve to explain the principles of the invention.
Example 1
A fluorescence-adjustable dye molecule/ZIF-8 film consists of the following components: 2-methylimidazole, 1,2, 4-benzene tricarboxylic acid, zinc acetate dihydrate, fluorescent dye and solvent, wherein the molar ratio of 2-methylimidazole to zinc acetate dihydrate is 2.5:1, the molar ratio of 2-methylimidazole to 1,2, 4-benzene tricarboxylic acid is 100:10, and the molar ratio of 2-methylimidazole to solvent is 0.583:1, the molar ratio of zinc acetate dihydrate to dye rhodamine 6G is 2000:1, and the molar ratio of zinc acetate dihydrate to coumarin 151 is 400:1. The solvent is ethanol.
The molar dosage concentration of the 2-methylimidazole is 10mol/L, which is the concentration in the composite sol. The fluorescent dye is rhodamine 6G and coumarin 151, the molar dosage concentration of the rhodamine 6G is 0.002mol/L, and the molar dosage concentration of the coumarin 151 is 0.01mol/L.
The application of the dye molecule/ZIF-8 film with adjustable fluorescence is that the film can be applied to the preparation of a white light LED device comprising the film, thereby achieving the purposes of decoration and outdoor night illumination.
The preparation method comprises the following steps:
(1) Mixing ligand 2-methylimidazole (C 4H6N2) and 1,2, 4-benzene tricarboxylic acid (C 9H6O6) uniformly in a solvent; (2) And (3) adding zinc acetate dihydrate (Zn (CH 3COO)2·2H2 O) into the step (1) and magnetically stirring to form transparent ZIF-8 sol, wherein the H 3 BTC ligand is ensured to be completely dissolved in the solvent before adding the zinc acetate dihydrate, magnetically stirring to form colorless transparent sol, and then aging for more than or equal to 10 hours.
(3) Uniformly dissolving a certain proportion of fluorescent dye rhodamine 6G and coumarin 151 in ZIF-8 sol serving as a dye molecule solution to obtain composite sol; the viscosity of the obtained dye molecule/ZIF-8 composite sol can be regulated and controlled by the amount of a solvent and the ligand H 3 BTC, and no additional auxiliary agent is required to be added. After adding the fluorescent dye, magnetically stirring and aging for at least 10 hours, and reserving the mixture for spin coating.
(4) Performing spin coating and film plating on the composite sol obtained in the step (3); the spin coating speed is 5000rp/s, and the film thickness can be controlled by different spin coating speeds.
(5) And carrying out heat treatment on the wet film after spin coating. The specific heat treatment process of the dye molecule/ZIF-8 composite wet film after spin coating is as follows: the dye molecule/ZIF-8 composite wet film after spin coating is placed in a heating table at 60 ℃ for curing for 0.5h, then the temperature of the heating table is adjusted to be 20 ℃ to 120 ℃ at intervals of 0.5h, and the temperature is kept at 120 ℃ for 5 h.
Example 2
A fluorescence-adjustable dye molecule/ZIF-8 film consists of the following components: 2-methylimidazole, 1,2, 4-benzene tricarboxylic acid, zinc acetate dihydrate, fluorescent dye and solvent, wherein the molar ratio of 2-methylimidazole to zinc acetate dihydrate is 4:1, the molar ratio of 2-methylimidazole to 1,2, 4-benzene tricarboxylic acid is 100:0, and the molar ratio of 2-methylimidazole to solvent is 0.03:1, the molar ratio of zinc acetate dihydrate to dye is 5:1.
The concentration of the 2-methylimidazole is 0.5mol/L, which is the concentration in the composite sol. The fluorescent dye is coumarin 151, and the molar dosage concentration of the coumarin 151 is 0.025mol/L. The solvent is ethanol.
The preparation process was otherwise as in example 1, wherein the spin coating film speed in step (4) was 500rp/s.
Example 3
A fluorescence-adjustable dye molecule/ZIF-8 film consists of the following components: 2-methylimidazole, 1,2, 4-benzene tricarboxylic acid, zinc acetate dihydrate, fluorescent dye and solvent, wherein the molar ratio of 2-methylimidazole to zinc acetate dihydrate is 2.5:1, the molar ratio of 2-methylimidazole to 1,2, 4-benzene tricarboxylic acid is 100:16, and the molar ratio of 2-methylimidazole to solvent is 1.46:1, the molar ratio of zinc acetate dihydrate to dye is 100000:1.
The concentration of the 2-methylimidazole is 25mol/L, which is the concentration in the composite sol. The fluorescent dye is rhodamine 6G, and the molar dosage concentration of the rhodamine 6G is 0.0001mol/L. The solvent is ethanol.
The preparation method is as in example 1, wherein the spin coating speed in the step (4) is 10000rp/s, and the film thickness can be controlled by different spin coating speeds.
Example 4
(1) Preparation of ligand H 3 BTC modified ZIF-8 sol: weighing 0, 0.00025mol, 0.00075mol, 0.001mol, 0.002mol and 0.004mol of ligand H 3 BTC (1, 2, 4-benzene tricarboxylic acid) respectively, placing into glass bottles filled with magnetons, then adding 2mL of solvent ethanol into the glass bottles respectively, placing the glass bottles on a magnetic stirrer for stirring uniformly, adding 0.025mol of ligand Hmim (2-methylimidazole) into each glass bottle after 10min, and continuing magnetic stirring until H 3 BTC in the bottle is completely dissolved;
(2) And adding 0.01mol of zinc acetate dihydrate into each glass bottle, magnetically stirring until the solution is colorless and transparent, and aging for at least 10 hours to obtain H 3 BTC modified ZIF-8 sol with different molar quantities.
(3) Preparation of dye molecule/ZIF-8 composite sol: the prepared ZIF-8 sol with the molar weight of H 3 BTC of 0.00075mol is selected as a solvent, a mixed sol with the dye rhodamine 6G concentration of 0.001mol/L and the coumarin 151 concentration of 0.001mol/L is prepared, and after fluorescent dye is added, the mixed sol is magnetically stirred for 2 hours and then aged for 10 hours, and the mixed sol is reserved for spin coating.
(4) The prepared ZIF-8 sol modified by H 3 BTC with different amounts, dye and ZIF-8 composite sol are coated on a cleaned quartz glass sheet in a spin coating mode, and the coating parameters are as follows: the first step is 1000rp/s 10s, and the second step is 5000rp/s 20s, so that each sample wet film can be obtained.
(5) And (3) placing the wet film of each sample obtained in the step (4) on a heating table at 60 ℃ for curing for 0.5h, then raising the temperature of the heating table by 20 ℃ to 120 ℃ every 0.5h, namely, the temperatures are 60, 80, 100 and 120 ℃ respectively, and preserving the temperature at 120 ℃ for 5h to obtain each cured film sample.
As shown in fig. 1,2 and 3, which are the characterization of the samples in example 4, as can be seen from fig. 1, ligand H 3 BTC is added to ZIF-8 sol to modify, and the structure of the plated film sample is still amorphous ZIF-8 film as a whole, which illustrates that ligand H 3 BTC does not affect the formation of its ZIF-8 structure; after adding dye molecules to the sol, the phase of the dye is undetectable due to the very small amount added. FIG. 2 is an absorption spectrum of each of the film samples of example 4, from which it can be seen that the addition of H 3 BTC reduced the optical bandgap of ZIF-8 to shift its spectrum toward longer wavelengths, and the absorption spectrum also detected the specific absorption wavelength of the fluorescent dye molecules in the ZIF-8 film, indicating successful dye complexing with ZIF-8. FIG. 3 is a graph showing the fluorescence performance of one of the samples of ZIF-8 and dye, wherein the film after compounding is white light emitting, chromaticity coordinates are 0.323,0.347, and the fluorescence quantum efficiency (under 395nm excitation) of the composite film is 63.9753%. Therefore, the film has better luminous performance and can be applied to white light LED devices.
Example 5
(1) Weighing 0.00075mol of H 3 BTC, placing the mixture into a glass bottle filled with a magneton, adding 2mL of ethanol into the glass bottle, placing the glass bottle on a magnetic stirrer for uniformly stirring, adding 0.025mol of ligand Hmim into the glass bottle after 10 minutes, and continuing stirring until the H 3 BTC in the bottle is completely dissolved;
(2) Then adding 0.01mol of zinc acetate dihydrate into the mixture, magnetically stirring the mixture uniformly until the mixture is colorless and transparent sol, and aging the mixture for 10 hours to obtain ZIF-8 sol;
(3) The prepared colorless transparent ZIF-8 sol is taken as a solvent, the concentration of coumarin 151 is controlled to be 0.0025mol/L, and the sol of the two dye composite ZIF-8 with the rhodamine 6G concentration of 0.0001mol/L, 0.0003mol/L, 0.0005mol/L, 0.001mol/L and 0.002mol/L is prepared respectively, magnetically stirred for 2 hours after fluorescent dye is added, aged for 10 hours, and is reserved for spin coating.
(4) Coating each composite sol prepared in the step (3) on a cleaned quartz glass sheet in a spin coating mode, wherein coating parameters are as follows: the first step is 1000rp/s 10s, and the second step is 5000rp/s 20s, so that each sample wet film can be obtained.
(5) And (3) placing the wet film of each sample obtained in the step (4) on a heating table at 60 ℃ for curing for half an hour, then raising the temperature of the heating table by 20 ℃ to 120 ℃ every half an hour, namely, keeping the temperature at 60, 80, 100 and 120 ℃ for 5 hours respectively, and obtaining each cured film sample.
Fig. 4 and 5 are representations of the samples of example 5. As can be seen from fig. 4, as the rhodamine 6G content in the composite sol increases, the absorption peak at about 550nm in the absorption spectrum of the film prepared from each sol gradually increases, indicating that the rhodamine 6G content in the composite film also gradually increases. FIG. 5 shows the PL spectra of the respective composite membrane samples, and it can be seen from the figures that the fluorescence peak derived from ZIF-8 itself (at about 443 nm), the fluorescence peak derived from coumarin 151 (at about 476 nm) and the fluorescence peak derived from rhodamine 6G (at about 580 nm) are involved in the regulation of the fluorescence of the whole membrane system together, so that the fluorescent membrane can emit fluorescence of different colors. Meanwhile, the relative intensity of the fluorescence peak is correspondingly changed along with the change of the doping amount of the fluorescent dye rhodamine 6G (because the fluorescence of ZIF-8 is similar to that of coumarin 151, the fluorescence is overlapped into one peak). The composite film prepared when the concentration of coumarin 151 is 0.0025M and the concentration of rhodamine 6G is 0.001M shows white light emission, chromaticity coordinates are 0.326,0.357, and fluorescence quantum efficiency is 62.1634%.
The fluorescence-adjustable dye molecule/ZIF-8 composite film and the preparation method thereof can regulate and control the fluorescence performance through the technical parameters such as H 3 BTC content, dye concentration, sol concentration and the like. The method for preparing the composite film has the advantages of simple process, controllable film thickness and optical performance, and good film stability and repeatability.
Specifically, the composite film is dried after being washed by alcohol or water, the surface of the film is unchanged, fluorescence is unchanged, and the film stability is good; and the film has stable fluorescence performance under the condition of 120 ℃ after the curing temperature of the film is 120 ℃. In addition, the fluorescence colors of the films prepared by the invention are consistent under the same experimental environment and parameters, the fluorescence performance of a batch of films prepared by the same sol is consistent, and the repeatability of the films is good. For controllable optical performance, the above embodiment 5 proves that the optical performance is controllable, other conditions such as the concentration of coumarin 151 are controlled to be consistent by adopting a variable control mode, and the doping amount of rhodamine 6G is changed, so that the prepared composite film presents different CIE coordinates, and thus, fluorescence of different colors is corresponding. Therefore, the amount of the dye in the prepared corresponding film can be regulated and controlled by controlling the amount of the dye in the composite sol, so that the fluorescence of different colors of the film can be regulated and controlled.
The present invention can be realized by the respective raw materials listed in the present invention, and the upper and lower limits and interval values of the respective raw materials, and the upper and lower limits and interval values of the process parameters (such as temperature, concentration, etc.), and examples are not shown here.
The above examples/experiments are only examples for clarity of illustration and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. Fluorescence-tunable dye molecule/ZIF-8 membrane, characterized in that: the film comprises the following components: 2-methylimidazole, 1,2, 4-benzene tricarboxylic acid, zinc acetate dihydrate, fluorescent dye and solvent, wherein the molar ratio of the 2-methylimidazole to the 1,2, 4-benzene tricarboxylic acid is 100:0-16, and the molar ratio of the 2-methylimidazole to the solvent is 0.03-1.46: the molar ratio of the 1, 2-methylimidazole to the zinc acetate dihydrate is 2.5-4:1, and the molar ratio of the zinc acetate dihydrate to the dye is 5-100000:1;
the fluorescent dye is rhodamine 6G and coumarin 151;
the solvent is ethanol;
The preparation method of the fluorescence-adjustable dye molecule/ZIF-8 membrane comprises the following steps:
(1) Mixing ligand 2-methylimidazole and 1,2, 4-benzene tricarboxylic acid uniformly in a solvent;
(2) Adding a certain amount of zinc acetate dihydrate into the step (1), and magnetically stirring to form transparent ZIF-8 sol;
(3) Uniformly dissolving a certain proportion of fluorescent dye rhodamine 6G and coumarin 151 in ZIF-8 sol serving as a dye molecule solution to obtain dye molecule/ZIF-8 composite sol;
(4) Performing spin coating and film plating on the composite sol obtained in the step (3);
(5) And carrying out heat treatment on the dye molecule/ZIF-8 composite wet film after spin coating.
2. The fluorescence-tunable dye molecule/ZIF-8 membrane of claim 1, wherein: the concentration of the 2-methylimidazole is 0.5 mol/L-25 mol/L.
3. The fluorescence-tunable dye molecule/ZIF-8 membrane of claim 1, wherein: the molar dosage concentration of the fluorescent dye rhodamine 6G is 0-0.005 mol/L, and the molar dosage concentration of coumarin 151 is 0-0.025 mol/L.
4. The fluorescence-tunable dye molecule/ZIF-8 membrane of claim 1, wherein: the spin coating speed in the step (4) is 500-10000 rp/s.
5. The fluorescence-tunable dye molecule/ZIF-8 membrane of claim 1, wherein: the heat treatment process of the dye molecule/ZIF-8 composite wet film after spin coating in the step (5) is as follows, the dye molecule/ZIF-8 composite wet film after spin coating is placed in a heating table at 60 ℃ for curing for half an hour, then the temperature of the heating table is regulated to be 20 ℃ to 120 ℃ every half an hour, and the temperature is kept at 120 ℃ for 5 hours.
6. Use of a fluorescence-tunable dye molecule/ZIF-8 membrane according to claim 1, characterized in that: the film is applied to the preparation of a white light LED device comprising the film.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3081616A1 (en) * | 2015-04-17 | 2016-10-19 | Universidad de Castilla La Mancha | White light emitting zirconium-based mofs |
| CN108690201A (en) * | 2018-07-12 | 2018-10-23 | 南开大学 | A kind of high quantum production rate white fluorescence powder material and preparation method thereof that MOF/ dyestuffs are compound |
| CN108892392A (en) * | 2018-07-13 | 2018-11-27 | 武汉理工大学 | A method of based on regulation ZIF-8 film exposure crystal face ratio |
| CN110734761A (en) * | 2019-10-29 | 2020-01-31 | 南京邮电大学 | Preparation method and application of two-primary-color white light OLED material |
| CN111675812A (en) * | 2020-07-14 | 2020-09-18 | 河南理工大学 | Chiral MOF-dye composite material with high quantum yield and preparation method and application thereof |
| WO2021105759A1 (en) * | 2019-11-29 | 2021-06-03 | Latvian Institute Of Organic Synthesis | New metal-organic frameworks and their use for encapsulation of fluorescent dyes |
| CN113652228A (en) * | 2021-08-09 | 2021-11-16 | 西北大学 | Preparation method of color-adjustable fluorescent MOF-dye composite material |
-
2022
- 2022-01-11 CN CN202210026220.6A patent/CN114437712B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3081616A1 (en) * | 2015-04-17 | 2016-10-19 | Universidad de Castilla La Mancha | White light emitting zirconium-based mofs |
| CN108690201A (en) * | 2018-07-12 | 2018-10-23 | 南开大学 | A kind of high quantum production rate white fluorescence powder material and preparation method thereof that MOF/ dyestuffs are compound |
| CN108892392A (en) * | 2018-07-13 | 2018-11-27 | 武汉理工大学 | A method of based on regulation ZIF-8 film exposure crystal face ratio |
| CN110734761A (en) * | 2019-10-29 | 2020-01-31 | 南京邮电大学 | Preparation method and application of two-primary-color white light OLED material |
| WO2021105759A1 (en) * | 2019-11-29 | 2021-06-03 | Latvian Institute Of Organic Synthesis | New metal-organic frameworks and their use for encapsulation of fluorescent dyes |
| CN111675812A (en) * | 2020-07-14 | 2020-09-18 | 河南理工大学 | Chiral MOF-dye composite material with high quantum yield and preparation method and application thereof |
| CN113652228A (en) * | 2021-08-09 | 2021-11-16 | 西北大学 | Preparation method of color-adjustable fluorescent MOF-dye composite material |
Non-Patent Citations (2)
| Title |
|---|
| MOF-74及其复合物：多样合成与广泛应用;耿莹 等;《化学进展》;第33卷(第12期);第2283-2308页 * |
| 基于镉的MOF/染料复合材料的制备及荧光性能研究;刘明珠 等;《无机材料学报》(第10期);第55-61页 * |
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