CN112341502A - Preparation method of core-shell type rare earth complex - Google Patents
Preparation method of core-shell type rare earth complex Download PDFInfo
- Publication number
- CN112341502A CN112341502A CN202011093202.7A CN202011093202A CN112341502A CN 112341502 A CN112341502 A CN 112341502A CN 202011093202 A CN202011093202 A CN 202011093202A CN 112341502 A CN112341502 A CN 112341502A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- atpa
- sio
- earth complex
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 20
- 239000011258 core-shell material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 19
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- WBHAQAZAYAMWIV-UHFFFAOYSA-K europium(3+) triperchlorate hexahydrate Chemical compound O.O.O.O.O.O.Cl(=O)(=O)(=O)[O-].[Eu+3].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] WBHAQAZAYAMWIV-UHFFFAOYSA-K 0.000 claims description 5
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 5
- NAPXFYQZNZUQDE-UHFFFAOYSA-K terbium(3+);triperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Tb+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O NAPXFYQZNZUQDE-UHFFFAOYSA-K 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 22
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 abstract description 22
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- -1 rare earth ions Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229910008051 Si-OH Inorganic materials 0.000 abstract description 2
- 229910006358 Si—OH Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 239000013110 organic ligand Substances 0.000 description 6
- 229910052771 Terbium Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- UFITZXXHLWZPNO-UHFFFAOYSA-N perchloric acid;hexahydrate Chemical compound O.O.O.O.O.O.OCl(=O)(=O)=O UFITZXXHLWZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the technical field of rare earth complex nano materials, and particularly relates to a preparation method of a core-shell type rare earth complex, which takes 2-amino terephthalic acid as a raw material to react with isopropyl Triethoxysilane (TEPIC) to synthesize a novel organic bridging ligand ATPA-Si, and finally, ethoxy and SiO of the organic bridging ligand ATPA-Si2Hydrolytic condensation of Si-OH on the surface to fix ATPA-Si to SiO2On the surface, based on the residual fluorescence (blue light) of the organic bridging ligand, the core-shell type rare earth complex with warm white light emission is successfully synthesized by adjusting the proportion of Eu (red light) and Tb (green light) rare earth ions; the preparation method of the material is simple and the equipment is simpleThe method has the advantages of low synthesis temperature, low raw material price, no need of expensive surfactant as a template agent, no environmental pollution, energy conservation, high conversion rate and easy industrial production.
Description
Technical Field
The invention belongs to the technical field of rare earth complex nano materials, and particularly relates to a preparation method of a core-shell type rare earth complex.
Background
White light diodes (WLEDs) are considered as the next generation of lighting industry and display systems due to their unique characteristics of energy saving, environmental protection, small size, good durability, etc. The pc-WLEDs currently in commercial use employ YAG to Ce coated on blue LEDs3+Yellow phosphor, due to insufficient emission in the red spectral region, has a higher Correlated Color Temperature (CCT) and a lower Color Rendering Index (CRI). As is well known, Eu3+The ions can emit red light with excellent color purity.
Thus, Eu is adjusted3+Ions co-doped as red component to YAG: ce3+Industrial WLED can be obtained from yellow phosphor. However, there are major problems in that the excitation wavelength of these white light materials is generally below 350nm, the products have irregular morphologies, and a large amount of expensive rare earth elements are required, which severely limits the applications thereof in the actual illumination field.
Therefore, it is important to find a white light material which can be excited in a near ultraviolet region, has a regular shape and is low in cost. Lanthanide organic ligands absorb a large amount of energy in the near ultraviolet region and transfer the excitation energy to rare earth ions through the "antenna effect", which has become a hot spot of recent research. With SiO2The core-shell type rare earth complex has the advantages of high stability, low cost and the like. Therefore, it is of great significance to develop a method for producing warm white light nano material which has high stability and low cost and can be practically applied to the illumination field.
Disclosure of Invention
The invention provides a preparation method of a core-shell type rare earth complex for solving the technical problems.
The technical scheme for solving the technical problems is as follows: a preparation method of a core-shell type rare earth complex comprises the following steps:
A. placing 2-amino terephthalic acid (ATPA) and isocyanatopropyl Triethoxysilane (TEPIC) in a solvent for reaction to generate an organic bridging ligand ATPA-Si, and adjusting the pH value to 3-4;
B. dispersing silicon dioxide in a solvent, then dropwise adding the solvent into the organic bridging ligand obtained in the step A for reaction, centrifuging and drying to obtain a product, namely SiO2@ATPA-Si；
C. Dispersing the product obtained in the step B in absolute ethyl alcohol, and then adding terbium (Tb (ClO) perchlorate hexahydrate4)3·6H2O) and europium perchlorate hexahydrate (Eu (ClO)4)3·6H2O) reaction to obtain the warm white light core-shell rare earth complex SiO2@ATPA-Si-Eu(a)/Tb。
The invention has the beneficial effects that: the rare earth complex prepared by the invention is excited under an ultraviolet lamp (360nm) to emit warm white light, and the novel core-shell rare earth complex SiO2@ATPA-Si-Eu(a)/Tb(SiO2The method takes 2-amino terephthalic acid (ATPA) as a raw material, synthesizes a novel organic bridging ligand ATPA-Si by reacting with isocyanatopropyl Triethoxysilane (TEPIC), and finally synthesizes ethoxy and SiO of the organic bridging ligand ATPA-Si2Hydrolytic condensation of Si-OH on the surface to fix ATPA-Si to SiO2A surface.
Based on the residual fluorescence (blue light) of the organic bridging ligand, the core-shell type rare earth complex with warm white light emission is successfully synthesized by adjusting the proportion of Eu (red light) and Tb (green light) rare earth ions; the preparation method is simple and easy to implement, the raw materials are low in price, an expensive surfactant is not needed to be used as a template agent, the warm white light nanometer material which does not pollute the environment, saves resources, has high conversion rate and higher stability and can be practically applied to the field of illumination is synthesized, the method has good repeatability, the synthesized product has better stability, and stronger warm white light is emitted under the excitation of near ultraviolet light of 360nm, so that the method is an ideal green process.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step A, the molar ratio of the 2-amino terephthalic acid to the isocyanatopropyl triethoxysilane is (0.5-1): (2-4).
Further, in step a, the reaction temperature was controlled at 55 ℃.
Further, in step a, the solvent is acetone.
Further, in step B, the mass ratio of the silica to the 2-aminoterephthalic acid in step A is (0.1-0.2): (0.1643-0.3682).
Further, in the step C, the mass ratio of the terbium perchlorate hexahydrate and the europium perchlorate hexahydrate to the product obtained in the step B is (0.04-0.08): (0.02-0.06): 0.1.
further, in step C, the reaction temperature was controlled at 40 ℃.
Explanation of compound name:
ATPA: 2-amino terephthalic acid;
TEPIC: isocyanatopropyltriethoxysilane;
Tb(ClO4)3·6H2o: terbium perchlorate hexahydrate;
Eu(ClO4)3·6H2o: europium perchlorate hexahydrate;
SiO2@ATPA-Si-Eu(a)/Tb：SiO2as a nucleus, @ represents cladding, ATPA-Si-Eu/Tb is a rare earth complex doped with Eu and Tb, and a is the charge ratio of Eu.
Drawings
FIG. 1 is a thermogravimetric plot (TGA) of the product of the invention prepared in example 3;
FIG. 2 is a schematic diagram of the preparation process of the product of the present invention;
FIG. 3 is a fluorescence emission spectrum of the product obtained by adding different Eu/Tb ratios during the preparation process of the present invention;
FIG. 4 is a CIE coordinate diagram of products of the present invention at different Eu/Tb ratios;
FIG. 5 is SiO2And example 3 SiO2@ATPA-Si-Eu(0.02)Transmission electron micrograph of/Tb, FIG. 5a is SiO2FIG. 5b, FIG. 5c and FIG. 5d are the transmission electron micrographs of SiO in example 32@ATPA-Si-Eu(0.02)Tb transmission electron micrograph；
FIG. 6 shows SiO as a product of example 32@ATPA-Si-Eu(0.02)Energy spectrum analysis plot of/Tb (EDS).
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
FIG. 1 is SiO2@ATPA-Si-Eu(0.02)The thermal weight loss (TGA) curve of Tb it is evident from fig. 1 that when the temperature is 30 ℃ to 200 ℃, the nanoparticle has a 5.32% weight loss, here due to the loss of crystal water in the nanoparticle, and 44.71% weight loss between 200 ℃ to 800 ℃, here due to the weight loss of the organic ligand, and more importantly, a large exothermic peak at 334.36 ℃ is evident from the heat flow curve, this is due to the onset of decomposition of the organic ligand, thus confirming that the synthesized nanomaterial remains stable before 334.36 ℃ and has high stability.
FIG. 2 is a synthetic route diagram of the present invention, specifically, the stober method is used to prepare SiO with uniform particle size2Microsphere, 2-amino terephthalic acid and silane coupling agent isopropyltriethoxysilane are reacted to synthesize novel organic ligand ATPA-Si with structure as shown in figure, and the organic ligand is grafted to SiO by grafting method2And (3) coordinating carboxyl on the surface of the microsphere with rare earth ions, adding perchlorates of Eu and Tb in different charge ratios to obtain the nano material with warm white light emission, and observing obvious warm white light under excitation of 360 nm.
FIG. 3 is a fluorescence emission spectrum of samples with different Eu/Tb doping ratios, and it can be clearly seen from FIG. 3 that the samples with three different ratios have stronger fluorescence, specifically, the emission peak of Eu ion at 616nm and the emission peak of Tb ion at 543nm are shown, and as the ratio of Eu ion is increased, we can clearly see that the peak at 616nm is gradually increased, therefore, the SiO synthesized by us is gradually increased2@ATPA-Si-Eu(0.02)the/Tb has stronger fluorescence property.
Fig. 4 is a color Coordinate (CIE) diagram of samples with different Eu/Tb doping ratios, from which we can see that when Eu is doped with 0.02g and 0.03g, the corresponding color coordinates fall into the white light region, and when Eu is doped with 0.06g, the color coordinates fall into the light red region, and by comparison, it is found that when Eu is doped with 0.02g, the coordinates are (x-0.3892, y-0.3447), and the correlated color temperature is 3550K, which is warm white light.
FIG. 5 is SiO of sample2And SiO2@ATPA-Si-Eu(0.02)Comparative transmission electron micrograph of/Tb, FIG. 5a shows the SiO produced2Microspheres, whose surface is seen to be very smooth and have a good monodispersity; FIG. 5b, FIG. 5c and FIG. 5d are transmission electron microscope images of the nano-material after coordination of rare earth with different resolutions, from which we can clearly see that the surface of the microsphere becomes very rough and still has better monodispersity after coordination of rare earth ions, and the thickness of rare earth after measurement is about 2nm, which confirms that the rare earth complex is successfully grafted to SiO2The surface of the microsphere.
FIG. 6 is SiO2@ATPA-Si-Eu(0.02)The energy spectrum analysis chart of/Tb shows that the nano material has energy spectrum content analysis to prove its components, from said chart we can see that Si, O, C, N, Cl, Eu and Tb all exist, in which Eu content is 2.48%, Tb content is 1.49%, and the SiO is proved2@ATPA-Si-Eu(0.02)Successful synthesis of/Tb nano material.
Example 1
Weighing 0.1643g of 2-aminoterephthalic acid, dissolving in 35mL of acetone, stirring for 20 minutes, adding 0.5mL of TEPIC, reacting with the raw materials at 55 ℃, reacting for 12 hours to generate an organic bridged ligand ATPA-Si, adjusting the pH value of the ligand to 3-4 by using HCl solution, and standing for later use. Weighing 0.1gSiO2Ultrasonically dispersing the mixture in a mixed solvent of 10mL of ethanol and 10mL of water to obtain SiO2Dropwise adding the mixture into a ligand, reacting at room temperature for 12h, centrifuging, collecting a solid sample, drying at 60 ℃, and naming as SiO2@ ATPA-Si (i.e., the synthetic organic ligand ATPA-Si is grafted onto the silica surface, @ denotes coating). 0.1g of the collected solid was dispersed in 10mL of anhydrous ethanol, and 0 was added.04g Tb(ClO4)3·6H2O and 0.06g Eu (ClO)4)3·6H2The O participates in the coordination, the temperature is set to be 40 ℃, the reaction is carried out for 12 hours and then the centrifugation is carried out, a solid sample is collected and dried at the temperature of 60 ℃, and the white solid SiO is obtained2@ATPA-Si-Eu(0.06)/Tb。
Example 2
Weighing 0.1643g of 2-aminoterephthalic acid, dissolving in 35mL of acetone, stirring for 20 minutes, adding 0.5mL of TEPIC, reacting with the raw materials at 55 ℃, reacting for 12 hours to generate an organic bridged ligand ATPA-Si, adjusting the pH value of the ligand to 3-4 by using HCl solution, and standing for later use. 0.15g of SiO are weighed2Ultrasonically dispersing the mixture in a mixed solvent of 10mL of ethanol and 10mL of water to obtain SiO2Dropwise adding the mixture into a ligand, reacting at room temperature for 12h, centrifuging, collecting a solid sample, drying at 60 ℃, and naming as SiO2@ ATPA-Si. 0.1g of the collected solid was dispersed in 10mL of anhydrous ethanol, and 0.07g of Tb (ClO) was added4)3·6H2O and 0.03g Eu (ClO)4)3·6H2The O participates in the coordination, the temperature is set to be 40 ℃, the reaction is carried out for 12 hours and then the centrifugation is carried out, a solid sample is collected and dried at the temperature of 60 ℃, and the white solid SiO is obtained2@ATPA-Si-Eu(0.03)/Tb。
Example 3
Weighing 0.1643g of 2-aminoterephthalic acid, dissolving in 35mL of acetone, stirring for 20 minutes, adding 0.5mL of EPIC to react with the raw materials, setting the reaction temperature at 55 ℃, generating an organic bridging ligand ATPA-Si after reacting for 12 hours, adjusting the pH value of the ligand to 3-4 by using an HCl solution, and standing for later use. Weighing 0.2gSiO2Ultrasonically dispersing the mixture in a mixed solvent of 10mL of ethanol and 10mL of water to obtain SiO2Dropwise adding the mixture into a ligand, reacting at room temperature for 12h, centrifuging, collecting a solid sample, drying at 60 ℃, and naming as SiO2@ ATPA-Si, 0.1g SiO was taken as a collected solid2@ ATPA-Si was dispersed in 10mL of absolute ethanol, and 0.08g of Tb (ClO)4)3·6H2O and 0.02g Eu (ClO)4)3·6H2The O participates in the coordination, the temperature is set to be 40 ℃, the reaction is carried out for 12 hours and then the centrifugation is carried out, a solid sample is collected and dried at the temperature of 60 ℃, and the white solid SiO is obtained2@ATPA-Si-Eu(0.02)/Tb。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The preparation method of the core-shell type rare earth complex is characterized by comprising the following steps:
A. placing 2-amino terephthalic acid and isocyanatopropyl triethoxysilane in a solvent for reaction to generate an organic bridging ligand, and adjusting the pH value to 3-4;
B. dispersing silicon dioxide in a solvent, then dropwise adding the silicon dioxide into the organic bridging ligand obtained in the step A for reaction, and then centrifuging and drying to obtain a product;
C. and D, dispersing the product obtained in the step B into absolute ethyl alcohol, and then adding terbium perchlorate hexahydrate and europium perchlorate hexahydrate for reaction to obtain the product.
2. The method of claim 1, wherein in step a, the molar ratio of 2-amino terephthalic acid to isopropyltriethoxysilane is (0.5-1): (2-4).
3. The method of claim 1, wherein in step A, the reaction temperature is controlled at 55 ℃.
4. The method of claim 1, wherein in step a, the solvent is acetone.
5. The method of claim 1, wherein in step B, the mass ratio of the silica to the 2-aminoterephthalic acid in step a is (0.1-0.2): (0.1643-0.3682).
6. The method for preparing the core-shell rare earth complex according to claim 1, wherein in the step C, the mass ratio of the terbium perchlorate hexahydrate and the europium perchlorate hexahydrate to the product obtained in the step B is (0.04-0.08): (0.02-0.06): 0.1.
7. the method of claim 1, wherein in step C, the reaction temperature is controlled at 40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011093202.7A CN112341502B (en) | 2020-10-14 | 2020-10-14 | Preparation method of core-shell rare earth complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011093202.7A CN112341502B (en) | 2020-10-14 | 2020-10-14 | Preparation method of core-shell rare earth complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112341502A true CN112341502A (en) | 2021-02-09 |
| CN112341502B CN112341502B (en) | 2023-10-24 |
Family
ID=74360743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011093202.7A Active CN112341502B (en) | 2020-10-14 | 2020-10-14 | Preparation method of core-shell rare earth complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112341502B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735216A (en) * | 2009-11-26 | 2010-06-16 | 上海大学 | Europium complex silicon dioxide fluorescent nano particles and preparation method thereof |
| CN101864298A (en) * | 2010-05-26 | 2010-10-20 | 上海大学 | Double rare earth coordination compound, Ag at SiO2 fluorescent nano particle doped with the same and preparation method thereof |
| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
-
2020
- 2020-10-14 CN CN202011093202.7A patent/CN112341502B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735216A (en) * | 2009-11-26 | 2010-06-16 | 上海大学 | Europium complex silicon dioxide fluorescent nano particles and preparation method thereof |
| CN101864298A (en) * | 2010-05-26 | 2010-10-20 | 上海大学 | Double rare earth coordination compound, Ag at SiO2 fluorescent nano particle doped with the same and preparation method thereof |
| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
Non-Patent Citations (4)
| Title |
|---|
| XINGTANG RAO ET AL.: "Color tunable and white light emitting Tb3+ and Eu3+ doped lanthanide metal–organic framework materials", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| YAN QIAO ET AL.: "Controlled synthesis and luminescence properties of core-shell-shell structured SiO2@AIPA-S-Si-Eu@SiO2 and SiO2@AIPA-S-Si-Eu-phen@SiO2 nanocomposites", 《SCIENTIFIC REPORT》 * |
| ZHI-FA LIU ET AL.: "Eu3+-doped Tb3+ metal–organic frameworks emitting tunable three primary colors towards white light", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| ZHI-FANG FU ET AL.: "Synthesis, characterization and luminescence of europium perchlorate with MABA-Si complex and coating structure SiO2@Eu(MABA-Si) luminescence nanoparticles", 《LUMINESCENCE》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112341502B (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108034418B (en) | All-inorganic lead-halogen perovskite nano composite luminescent material, and preparation method and application thereof | |
| CN102071027B (en) | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof | |
| JP3875027B2 (en) | Method for producing spherical zinc orthosilicate-based green light-emitting phosphor | |
| Yoshizawa et al. | Synthesis of Zn 2 SiO 4: Mn 2+ by homogeneous precipitation using propylene glycol-modified silane | |
| CN113025316B (en) | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED | |
| WO2009046392A1 (en) | Synthesis of bio-functionalized rare earth doped upconverting nanophosphors | |
| CN106350057A (en) | Preparation method of fluorescent hybrid nanoparticles | |
| CN112680213A (en) | Preparation method of perovskite nanocrystalline coated by ethyl orthosilicate | |
| KR100547522B1 (en) | Method for producing high brightness small particle red emitting phosphor | |
| JP5619989B2 (en) | Method for producing zinc manganese silicate | |
| KR100425404B1 (en) | Small Particle Terbium Activated Yttrium Gadolinium Borate Phosphors and Method of Making | |
| Shao et al. | Multicomponent assembly of luminescent hybrid materials of ZnO-lanthanide polymer complex functionalized SBA-15 mesoporous host by chemical bonds | |
| Chen et al. | Multicolor tunable luminescence and energy transfer of core–shell structured SiO 2@ Gd 2 O 3 microspheres co-activated with Dy 3+/Eu 3+ under single UV excitation | |
| Mou et al. | Synthesis and luminescent properties of monodisperse SiO 2@ SiO 2: Eu (DBM) 3 phen microspheres with core-shell structure by sol–gel method | |
| CN105505388B (en) | A kind of preparation method of BCNO Illuminant nanometers piece | |
| Yu et al. | Multi-color carbon dots from cis-butenedioic acid and urea and highly luminescent carbon dots@ Ca (OH) 2 hybrid phosphors with excellent thermal stability for white light-emitting diodes | |
| CN112341502B (en) | Preparation method of core-shell rare earth complex | |
| CN112646581A (en) | Rare earth up-conversion material with up-conversion luminescence color changed by speed change, and preparation method and application thereof | |
| WO2014067433A1 (en) | Nitride red fluorescent powder and preparation method thereof | |
| JP2001172620A (en) | Method for producing red light emitting fluorescent microparticle | |
| Lu et al. | In situ synthesis of monodisperse luminescent terbium complex-silica nanocomposites | |
| CN113956872B (en) | Terbium-doped calcium fluoride nano particle, sol-gel hybrid material and preparation method | |
| CN109211850B (en) | Epinephrine detection method based on copper-zinc-tin-sulfur alloy quantum dots | |
| CN111333072B (en) | Fluorescent silicon quantum dot and preparation method and application thereof | |
| CN114471387B (en) | Aerogel containing quantum dots and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |