CN107722964B - perfusion silica gel microsphere rare earth hybrid luminescent material and preparation method thereof - Google Patents
perfusion silica gel microsphere rare earth hybrid luminescent material and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000741 silica gel Substances 0.000 title claims abstract description 85
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 85
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 83
- 230000010412 perfusion Effects 0.000 title claims abstract description 82
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 rare earth ions Chemical class 0.000 claims abstract description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 229910052771 Terbium Inorganic materials 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 7
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract description 2
- 239000012769 display material Substances 0.000 abstract description 2
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention belongs to the field of rare earth luminescent materials, and relates to a perfusion silica gel microsphere rare earth hybrid luminescent material and a preparation method thereof. The hybrid luminescent material is prepared by taking perfusion silica gel microspheres as a mesoporous main material, performing carboxyl modification on the surface of the mesoporous main material, and then coordinating with rare earth ions. The perfusion silica gel microspheres adopted by the invention have a hierarchical pore structure of macropores and mesopores, the mesopores can ensure that the material has a larger specific surface area, the penetrating micron-sized macropores can provide faster mass transfer, small molecules can be favorably diffused in the microspheres, the content of rare earth complexes in the perfusion silica gel microspheres is improved, and the inherent silica gel framework of the perfusion silica gel microspheres further endows the obtained hybrid luminescent material with excellent light and heat stability. The perfusion silica gel microsphere rare earth hybrid luminescent material has higher fluorescence intensity, can emit fluorescence of various colors under the irradiation of ultraviolet light, and can be widely applied to the fields of anti-counterfeiting mark materials, display materials and the like.
Description
Technical Field
The invention belongs to the field of rare earth luminescent materials, and particularly relates to a perfusion silica gel microsphere rare earth hybrid luminescent material and a preparation method thereof.
background
Rare earth elements are known as a treasure house of new materials due to the characteristics of light, electricity, magnetism, catalysis and the like because of the abundant electronic energy level and 4f electronic transition characteristics. The rare earth fluorescent material prepared by taking rare earth ions as a luminescent center has the advantages of high photon conversion efficiency, high photochromic purity, long service life and the like, and is applied to high-tech fields such as flat panel display, biomedicine, nonlinear optics, lasers and the like. China is a rare earth big country, has rich rare earth resources, the rare earth reserves are the first in the world and complete in variety, and the nano composite luminescent material with excellent development and design performance has great scientific significance in theory, has wide prospect in application and has important significance for the rare earth high and new technology industry.
Among rare earth luminescent materials, rare earth organic complexes have attracted general attention because of their characteristics of high emission light intensity and narrow-band emission. But the light and heat stability is poor, and the application is limited to a certain extent. The rare earth complex is used as a guest molecule and assembled into an inorganic matrix with good light and heat stability to prepare the rare earth hybrid material, so that the light and heat stability of the rare earth complex can be improved, and the luminescence property of the rare earth complex can be improved. Currently, the most widely used and studied inorganic substrates are: sol-gel materials, mesoporous materials, inorganic heteropolyacids, and the like. Among the representative mesoporous materials are: MCM-41S series, SBA-15 series, etc. The assembly of guest molecules into mesoporous host materials has been widely reported, but the traditional doping is to physically mix the rare earth complex and the matrix, only a weak intermolecular force exists between the two, the problems of phase separation, agglomeration, rare earth complex precipitation from the matrix and the like are easy to occur, and the obtained material is brittle and easy to crack. In order to overcome the defects and prepare a luminescent material with more excellent luminescent performance, people modify the surface of a central hole, introduce a proper organic ligand and graft a rare earth complex onto a matrix skeleton through a covalent bond. It should be noted that in these research works, there are the following major problems: by covalent bond grafting, the amount of rare earth complex loaded in the mesopores is small. Taking the SBA-15 with a relatively large pore size as an example, although the SBA-15 has a large specific surface area and a large pore volume, the content of rare earth elements is generally within 4% as measured by inductively coupled plasma emission spectroscopy (ICP-OES). The content of the rare earth complex is low, so that fewer luminescent centers are determined, and the luminous intensity of the material is greatly influenced. Therefore, how to load more rare earth luminescent centers in the mesoporous material and improve the luminescent intensity of the hybrid material is very important from the application point of view.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a perfusion silica gel microsphere rare earth hybrid luminescent material, wherein a luminescent center is bonded on the wall of a middle hole of the perfusion silica gel microsphere through a chemical bond, and a penetrating micron-sized macropore is beneficial to small molecule mass transfer, so that the amount of rare earth complexes loaded in the microsphere is higher, the content of rare earth elements can reach 8 percent, and the fluorescence intensity of the obtained hybrid luminescent material is obviously improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
a perfusion silica gel microsphere rare earth hybrid luminescent material takes perfusion silica gel microspheres as a mesoporous main material, rare earth ions form rare earth complexes, and the rare earth complexes are bonded on the mesoporous walls of the perfusion silica gel microspheres through chemical bonds.
According to the scheme, the content of rare earth ions in the perfusion silica gel microsphere rare earth hybrid luminescent material is 4-8 wt%.
according to the scheme, the particle size of the perfusion silica gel microspheres is 3-50 μm.
according to the scheme, the perfusion silica gel microspheres have a hierarchical pore structure of macropores and mesopores, wherein the pore diameter of the mesopores is 5-20nm, and the pore diameter of the macropores is 0.5-1.5 mu m.
According to the scheme, the rare earth ions are one or a mixture of europium ions and terbium ions in any proportion.
The preparation method of the perfusion silica gel microsphere rare earth hybrid luminescent material comprises the following steps:
1) Dispersing the perfusion silica gel microspheres in an anhydrous organic solvent, heating and refluxing, adding the aminopropyl silane coupling agent under stirring, and reacting for 6-36 hours; filtering, washing to remove unreacted silane coupling agent, and preparing to obtain amido modified perfusion silica gel microspheres;
2) Dissolving a carboxyl modifier in a polar organic solvent, adding the amido modified perfusion silica gel microspheres under the stirring condition, reacting for 6-48 hours at room temperature, filtering, washing, and re-dispersing the prepared carboxyl modified perfusion silica gel microspheres in the polar organic solvent;
3) And adding rare earth salt into the dispersion liquid, adding alkali to absorb protons generated in the coordination process, stirring and reacting for 2-24 hours at the temperature of 20-100 ℃, and filtering, washing and drying to obtain the perfusion silica gel microsphere rare earth hybrid luminescent material.
according to the scheme, the anhydrous organic solvent is one or a mixture of several of toluene, xylene, tetrahydrofuran and carbon tetrachloride according to any proportion. Wherein the mass ratio of the anhydrous organic solvent to the perfusion silica gel microspheres is (10-50): 1.
According to the scheme, the aminopropyl silane coupling agent is one or a mixture of aminopropyl trimethoxysilane and aminopropyl triethoxysilane according to any proportion.
According to the scheme, the carboxyl modifier is aromatic dicarboxylic acid or aromatic acid anhydride, preferably one or a mixture of more of terephthalic acid, isophthalic acid, phthalic acid, trimellitic anhydride and pyromellitic anhydride in any proportion.
according to the scheme, the polar organic solvent is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone according to any proportion. Wherein the mass ratio of the polar organic solvent to the silica gel microspheres is (10-30) to 1.
According to the scheme, the rare earth salt is one or a mixture of more of rare earth salts such as rare earth nitrate or rare earth chloride according to any proportion. According to the scheme, the mass ratio of the perfusion silica gel microspheres, the aminopropyl silane coupling agent, the carboxyl modifying agent and the rare earth salt is 1 (0.2-0.8) to (0.2-0.5).
According to the scheme, the alkali is one or a mixture of several of trimethylamine, triethylamine, pyridine and hexamethylenetetramine in any proportion.
The principle of the invention is as follows:
The perfusion silica gel microspheres adopted by the invention have a hierarchical porous structure and simultaneously contain macropores and mesopores, wherein the mesopores with the nanoscale can ensure that the material has a larger specific surface area, so that the surfaces of the microspheres contain a large amount of reactive silicon hydroxyl groups; the penetrated micro-scale macropores are beneficial to medium transmission and small molecular reactants (aminopropyl silane coupling agent, rare earth salt and the like) to be transmitted into the nano-scale holes, so that the silicon hydroxyl on the surface is chemically modified, and a rare earth organic complex is introduced; based on the existence of the mesopores and the micron-sized perfusion macropores, a large amount of silicon hydroxyl on the surface is easy to be converted into organic ligand groups, so that the content of rare earth complexes in the perfusion silica gel microsphere rare earth hybrid material is effectively improved, and the luminous intensity of the material is improved; after the rare earth complex is introduced, the residual silicon hydroxyl on the surface of the microsphere is less, so that the fluorescence quenching effect of the hydroxyl can be effectively reduced, and the improvement of the luminous intensity of the material is facilitated. According to the invention, the rare earth ions are coordinated with the carboxyl and chelated on the surface of the framework, so that the phenomenon that the concentration quenching effect is generated due to the agglomeration of the rare earth ions to reduce the luminous intensity of the material is avoided. Under the combined action of the above factors, the hybrid luminescent material provided by the invention has high luminescent intensity. In addition, in the hybrid material provided by the invention, the main material is perfused with the inherent silica gel skeleton of the silica gel microspheres, so that the obtained hybrid luminescent material is further endowed with excellent light and heat stability; moreover, the rare earth complex is bonded on the main material through chemical bonds, so that the defects of leakage, precipitation and the like of the rare earth complex are avoided, and the long-time stability of the fluorescence intensity of the material is ensured.
Compared with the prior art, the invention has the beneficial effects that:
1. The perfusion silica gel microsphere rare earth hybrid luminescent material contains high-content rare earth elements, and the fluorescence intensity of the luminescent material can be enhanced along with the increase of the content of the rare earth elements;
2. the preparation method provided by the invention is simple, and the hybrid luminescent material containing different rare earth complexes can be easily prepared by changing the types of the carboxyl modifiers.
3. The perfusion silica gel microsphere rare earth hybrid luminescent material prepared by the invention is a powdery solid product, has high fluorescence intensity, can emit fluorescence of various colors under the irradiation of ultraviolet light, and is suitable for the fields of anti-counterfeiting mark materials, display materials and the like.
4. the perfusion silica gel microsphere rare earth hybrid luminescent material has high luminous intensity and excellent light and heat stability, and can effectively widen the application field.
drawings
FIG. 1 is an SEM photograph of the perfused silica gel microsphere terbium hybrid luminescent material prepared in example 1.
FIG. 2 shows fluorescence spectra and intensity of the perfusion silica gel microsphere terbium hybrid luminescent material prepared in example 1 and the terbium hybrid material prepared by using SBA-15 as a mesoporous host material under the same conditions under 295nm ultraviolet light excitation.
FIG. 3 shows the fluorescence spectrum of the perfusion silica gel microsphere europium hybrid luminescent material prepared in example 2 under the excitation of 295nm ultraviolet light.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
fluorescence spectra in the following examples were measured using a varian eclipse FL0910M014 fluorescence spectrometer. The content of rare earth elements was measured by ICP-OES using ICAP 6300 inductively coupled plasma spectrometer (Thermoscientific, USA).
In the following examples, the particle size of the perfusion silica gel microspheres is 3-50 μm, the perfusion silica gel microspheres have a hierarchical structure of macropores and mesopores, the pore size of the mesopores is 5-20nm, the pore size of the through macropores is 0.5-1.5 μm, the preparation method comprises the following steps,
1) 30g of tetraethoxysilane, 5.0g of polyethylene oxide (weight average molecular weight: 10000) and 50mL of 0.01 mol. L-1The hydrochloric acid is stirred and mixed evenly by magnetic force, reacts for 4 hours at the temperature of 60 ℃, and the generated ethanol is removed in vacuum after complete hydrolysis;
2) Shearing, emulsifying and dispersing the mixed solution obtained in the step 1) into liquid paraffin, reacting for 24 hours at the temperature of 60 ℃, filtering, and sequentially cleaning generated precipitates by using ethanol and water;
3) Burning the precipitate obtained in the step 2) at 600 ℃ for 2h to obtain the perfusion silica gel microspheres.
Example 1
a perfusion silica gel microsphere rare earth hybrid luminescent material is prepared by taking perfusion silica gel microspheres as a mesoporous main material, modifying by carboxyl, and coordinating with rare earth terbium ions in N, N-dimethylformamide, and the specific preparation method is as follows:
1) Dispersing 1g of perfusion silica gel microspheres in 30mL of anhydrous toluene, heating and refluxing at 110 ℃, adding 0.5g of aminopropyl trimethoxy silane under the stirring condition, reacting for 24 hours, filtering, washing with acetone, ethanol and tetrahydrofuran in sequence, and removing unreacted silane coupling agent to obtain amino modified perfusion silica gel microspheres;
2) Dissolving 0.5g of terephthalic acid in N, N-dimethylformamide, adding 1g of amido modified perfusion silica gel microspheres under the stirring condition, reacting for 12 hours at room temperature, filtering, washing for 3 times by using N, N-dimethylformamide, and re-dispersing the obtained carboxyl modified perfusion silica gel microspheres in the N, N-dimethylformamide;
3) And (3) adding 0.2g of terbium trichloride into the dispersion liquid obtained in the step 2), adding 0.1g of triethylamine to absorb protons generated in the coordination process, stirring and reacting for 8 hours at the temperature of 20 ℃, filtering, washing with N, N-dimethylformamide, tetrahydrofuran and acetone in sequence, and drying to obtain the perfusion silica gel microsphere terbium hybrid luminescent material.
the SEM photograph of the perfusion silica gel microsphere terbium hybrid luminescent material obtained in the embodiment is shown in figure 1, the fluorescence spectrum is shown in figure 2 (Tb-PSM), and the ICP-OES test shows that the content of terbium ions is 7.92 wt%.
Comparative example
SBA-15 is adopted to replace the perfusion silica gel microspheres to prepare the luminescent material, the preparation method is the same as the steps in the embodiment, the SBA-15 terbium luminescent material is prepared, the fluorescence spectrum diagram of the luminescent material is shown in figure 2(Tb-SBA-15), and the content of terbium ions in ICP-OES tests is 3.79 wt%.
As can be seen from fig. 2: in the figure, 4 emission bands are respectively: 489nm, 545nm, 585nm and 621nm, Tb3+Corresponding to a characteristic fluorescence emission peak of Tb3+Is/are as follows5D4→7F6，5D4→7F5，5D4→7F4And5D4→7F3Transition; the emission peak at 545nm is the strongest emission peak and corresponds to5D4→7F5The transition, belonging to the electric dipole transition, is Tb3+Characteristic green ofand (4) emitting light. Meanwhile, the fluorescence intensity of the perfusion silica gel microsphere terbium hybrid luminescent material obtained by the invention is far higher than that of the SBA-15 terbium luminescent material obtained by the comparative example.
example 2
A preparation method of a perfusion silica gel microsphere rare earth hybrid luminescent material is approximately the same as that of the embodiment 1, and the difference is that: anhydrous toluene is replaced by anhydrous dimethylbenzene, the heating reflux temperature is replaced by 140 ℃ at 110 ℃, aminopropyl trimethoxysilane is replaced by aminopropyl triethoxysilane, and terbium trichloride is replaced by europium trichloride.
The product perfusion silica gel microsphere europium luminescent material obtained in the embodiment has red light emission, a fluorescence spectrum shown in figure 3, and the content of europium ions in the product perfusion silica gel microsphere europium luminescent material is 7.13 wt% in an ICP-OES test.
As can be seen from fig. 3: in the figure, 4 emission bands are respectively: 592nm, 615nm, 652nm and 693nm, being Eu3+Corresponding to a characteristic fluorescence emission peak of Eu3+Is/are as follows5D0→7F1，5D0→7F2，5D0→7F3And5D0→7F4Transition; at 616nm5D0→7F2The transition peak belongs to electric dipole transition and is Eu3+The characteristic red luminescence of (1), where the intensity of fluorescence emitted by the transition is maximal.
Example 3
A preparation method of a perfusion silica gel microsphere rare earth hybrid luminescent material is approximately the same as that of the embodiment 1, and the difference is that: terephthalic acid is replaced by trimellitic anhydride, and terbium trichloride is replaced by europium nitrate.
The europium hybrid luminescent material of the perfusion silica gel microsphere obtained in the embodiment is tested by ICP-OES, wherein the content of europium ions is 7.56 wt%.
example 4
A preparation method of a perfusion silica gel microsphere rare earth hybrid luminescent material is approximately the same as that of the embodiment 1, and the difference is that: n, N-dimethylformamide is replaced by dimethyl sulfoxide, and terephthalic acid is replaced by isophthalic acid.
The perfusion silica gel microsphere terbium hybrid luminescent material obtained in the embodiment is tested by ICP-OES, wherein the content of terbium ions is 7.40 wt%.
example 5
a perfusion silica gel microsphere rare earth hybrid luminescent material is prepared by the following steps:
1) dispersing 1g of perfusion silica gel microspheres in 10mL of anhydrous toluene, heating and refluxing at 110 ℃, adding 0.3g of aminopropyltriethoxysilane under the condition of stirring, reacting for 6 hours, filtering, washing with acetone, ethanol and tetrahydrofuran in sequence, and removing unreacted silane coupling agent to obtain amino modified perfusion silica gel microspheres;
2) Dissolving 0.2g of phthalic acid in N, N-dimethylformamide, adding 1g of amido modified perfusion silica gel microspheres under the stirring condition, reacting for 12 hours at room temperature, filtering, washing for 3 times by using N, N-dimethylformamide, and re-dispersing the obtained carboxyl modified perfusion silica gel microspheres in the N, N-dimethylformamide;
3) And (3) adding 0.2g of terbium trichloride into the dispersion liquid obtained in the step 2), adding 0.1g of triethylamine to absorb protons generated in the coordination process, heating to 100 ℃, stirring to react for 2 hours, filtering, washing with N, N-dimethylformamide, tetrahydrofuran and acetone in sequence, and drying to obtain the perfusion silica gel microsphere terbium hybrid luminescent material.
The perfusion silica gel microsphere terbium hybrid luminescent material obtained in the embodiment is tested by ICP-OES, wherein the content of terbium ions is 4.80 wt%.
Example 6
A perfusion silica gel microsphere rare earth hybrid luminescent material is prepared by the following steps:
1) Dispersing 1g of perfusion silica gel microspheres in 30mL of anhydrous toluene, heating and refluxing at 110 ℃, adding 0.2g of aminopropyl trimethoxy silane under the stirring condition, reacting for 36 hours, filtering, washing with acetone, ethanol and tetrahydrofuran in sequence, and removing unreacted silane coupling agent to obtain amino modified perfusion silica gel microspheres;
2) Dissolving 0.5g of terephthalic acid in N-methylpyrrolidone, adding 1g of amido modified perfusion silica gel microspheres under the stirring condition, reacting for 12 hours at room temperature, filtering, washing for 3 times by using N, N-dimethylformamide, and re-dispersing the obtained carboxyl modified perfusion silica gel microspheres in the N, N-dimethylformamide;
3) Adding 0.2g of europium trichloride into the dispersion liquid obtained in the step 2), adding 0.1g of triethylamine to absorb protons generated in the coordination process, heating to 80 ℃, stirring for reaction for 24 hours, filtering, washing with N, N-dimethylformamide, tetrahydrofuran and acetone in sequence, and drying to obtain the perfusion silica gel microsphere europium hybrid luminescent material.
the europium hybrid luminescent material of the perfusion silica gel microsphere obtained in the embodiment is tested by ICP-OES, wherein the content of europium ions is 6.80 wt%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (10)
1. A perfusion silica gel microsphere rare earth hybrid luminescent material takes perfusion silica gel microspheres as a mesoporous main material, and a rare earth complex is bonded on the mesoporous walls of the perfusion silica gel microspheres through chemical bonds; the perfusion silica gel microspheres have a hierarchical pore structure of macropores and mesopores, wherein the pore diameter of the mesopores is 5-20nm, and the pore diameter of the macropores is 0.5-1.5 mu m.
2. The perfusion silica gel microsphere rare earth hybrid luminescent material of claim 1, wherein the content of rare earth ions in the perfusion silica gel microsphere rare earth hybrid luminescent material is 4-8 wt%.
3. The perfusion silica gel microsphere rare earth hybrid luminescent material as claimed in claim 1, wherein the particle size of the perfusion silica gel microsphere is 3-50 μm.
4. The perfusion silica gel microsphere rare earth hybrid luminescent material of claim 1, wherein the rare earth ions are one or a mixture of europium ions and terbium ions in any proportion.
5. The preparation method of the perfusion silica gel microsphere rare earth hybrid luminescent material of any one of claims 1 to 4, which is characterized by comprising the following steps:
1) Dispersing the perfusion silica gel microspheres in an anhydrous organic solvent, heating and refluxing, adding the aminopropyl silane coupling agent under stirring, and reacting for 3-36 hours; filtering, washing to remove unreacted silane coupling agent, and preparing to obtain amido modified perfusion silica gel microspheres;
2) Dissolving a carboxyl modifier in a polar organic solvent, adding the amido modified perfusion silica gel microspheres under the stirring condition, reacting for 6-48 hours at room temperature, filtering, washing, and re-dispersing the prepared carboxyl modified perfusion silica gel microspheres in the polar organic solvent;
3) And adding rare earth salt into the dispersion liquid, adding alkali to absorb protons generated in the coordination process, stirring and reacting for 2-24 hours at the temperature of 20-100 ℃, and filtering, washing and drying to obtain the perfusion silica gel microsphere rare earth hybrid luminescent material.
6. the preparation method according to claim 5, wherein the anhydrous organic solvent is one or a mixture of toluene, xylene, tetrahydrofuran and carbon tetrachloride in any proportion.
7. The preparation method according to claim 5, wherein the aminopropylsilane coupling agent is one or a mixture of aminopropyltrimethoxysilane and aminopropyltriethoxysilane in any proportion.
8. The method according to claim 5, wherein the carboxyl modifier is an aromatic dicarboxylic acid or an aromatic acid anhydride.
9. The preparation method according to claim 5, wherein the polar organic solvent is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.
10. The preparation method according to claim 5, wherein the rare earth salt is a mixture of one or more of rare earth nitrate or rare earth chloride in any proportion.
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