CN108328640B - NaREF4Method for preparing solid spherical particles - Google Patents
NaREF4Method for preparing solid spherical particles Download PDFInfo
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- CN108328640B CN108328640B CN201810111698.2A CN201810111698A CN108328640B CN 108328640 B CN108328640 B CN 108328640B CN 201810111698 A CN201810111698 A CN 201810111698A CN 108328640 B CN108328640 B CN 108328640B
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- 239000007787 solid Substances 0.000 title claims abstract description 28
- 239000012798 spherical particle Substances 0.000 title claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 nitric acid compound Chemical class 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 16
- 238000004140 cleaning Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 238000012876 topography Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910021266 NaErF4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910019264 NaLaF4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7732—Halogenides
- C09K11/7733—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the field of material science, and provides NaREF4The invention discloses a preparation method of solid spherical particles, which adopts the technical scheme that the steps are as follows: reacting a nitric acid compound of a rare earth element withMixing disodium ethylene diamine tetraacetate in deionized water to prepare solution with RE element ion concentration of 0.01-0.20 mol/L, adding ammonium fluoride solution while stirring, and introducing F‑Ion to obtain suspension, transferring the suspension into a reaction kettle, carrying out hydrothermal reaction at 100-200 ℃ for 12-48h, and carrying out centrifugal separation, cleaning and drying on the reaction product to obtain white powder particles NaREF4(RE L a-L u, Y) the technical scheme of the invention is simple and easy to implement, and NaREF is easy to obtain4Monodisperse nano solid spherical particles.
Description
Technical Field
The invention belongs to the technical field of material science, and relates to a NaREF4A method for preparing solid spherical particles.
Background
Rare earth fluoride has higher refractive index (1.56) and lower phonon energy (350-500 cm)-1) The fluorescent material based on rare earth fluoride is considered to be the best host for the up/down conversion luminescent material because of its advantages such as stable physicochemical properties and strong energy for carrying ions, and the fluorescent material based on rare earth fluoride has been the focus of research in recent years. The shape and size control of the fluoride fluorescent material is the focus of research at present, the fluoride fluorescent materials with different shapes and sizes can be obtained by different synthesis methods, and the fluoride fluorescent materials mainly have hexagonal sheets, blocks, sheets, hexagonal prisms, hollow spheres and the like, but the large size and easy agglomeration are two problems in the process of synthesizing the rare earth fluoride fluorescent material. Compared with other shapes, the monodisperse spherical particles can improve the resolution of the display, and can be easily arranged into a compact fluorescent layer, so that the scattering of exciting light can be reduced, and the optimal fluorescent efficiency is presented.
In conclusion, the rare earth fluoride NaREF4The solid spherical particles are an excellent fluorescent material matrix and are in-situ grownOn one hand, the solid spherical particles can greatly improve the signal-to-dryness ratio of the material due to the unique structural characteristics, and on the other hand, the fluoride fluorescent material with uniform size and good monodispersity has wider application range, at present, the NaREF of the whole rare earth system (including L a-L u, Y)4The synthesis of solid spherical particles of the type compound has technical bottlenecks, and the application of the fluoride fluorescent material is greatly limited.
The prior literature has relatively few reports on fluoride fluorescent materials with the solid spherical particle morphology, so that the fluoride fluorescent materials have great investigatability.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a rare earth fluoride NaREF4A method for preparing solid spherical particles. Control of F by hydrothermal method-The ratio of ions to rare earth ions to obtain solid spherical NaREF4The (RE-L a-L u, Y) nano-particles are a great breakthrough in rare earth fluoride and have good application prospect.
The technical scheme of the invention is as follows:
NaREF4The preparation method of the solid spherical particles comprises the following process steps:
(1) uniformly mixing a nitric acid compound of a rare earth element and disodium ethylene diamine tetraacetate in deionized water to prepare a solution with the total concentration of rare earth ions of 0.01-0.20 mol/L, wherein the rare earth element is one of lanthanide elements or Y elements, and the lanthanide elements do not include Pm;
(2) adding NH to the solution4F, obtaining a suspension; the mol ratio of the ammonium fluoride to the rare earth elements is 5: 1;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction for 12-48h at 100-200 ℃ under a sealed condition;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, and drying at 50-70 ℃ to obtain the monodisperse solid spherical NaREF4Particles;
compared with the prior art, the invention has the characteristics and beneficial effects that:
the invention utilizes a hydrothermal method to obtain NaREF4Solid spherical nano particles define NaREF in the whole lanthanide4The generation range of (1); the technical scheme is simple, and the obtained NaREF4The size of the solid nano spherical particle (RE: L a-L u, Y) is between 100 and 300nm, the rare earth fluoride nano particle is solid spherical, the spherical shape is favorable for obtaining a high-quality fluorescent powder coating with high density and thin thickness, and the absorption and scattering of light can be reduced, so that the luminous intensity and the fluorescent service life of the fluorescent powder are improved, and the functionalization of the material is realized.
Drawings
FIG. 1 shows Na L aF prepared in example 1 of the present invention4XRD pattern of white powder;
FIG. 2 shows Na L aF prepared in example 1 of the present invention4SEM topography of white powder;
FIG. 3 is NaEuF prepared according to example 2 of the invention4XRD pattern of white powder
FIG. 4 is NaEuF prepared according to example 2 of the invention4SEM topography of white powder;
FIG. 5 is NaErF prepared in example 3 of the present invention4XRD pattern of white powder;
FIG. 6 is NaErF prepared in example 3 of the present invention4SEM topography of white powder;
FIG. 7 shows Na L uF prepared in example 4 of the present invention4XRD pattern of white powder;
FIG. 8 shows Na L uF prepared in example 4 of the present invention4SEM topography of white powder;
FIG. 9 shows NaYF prepared in example 5 of the present invention4XRD pattern of white powder;
FIG. 10 shows NaYF prepared in example 5 of the present invention4SEM topography of white powder;
FIG. 11 shows NaYF prepared in example 5 of the present invention4TEM topography of white powder;
FIG. 12 is a NaYF prepared in example 5 of the present invention4HR-TEM image of white powder.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
The nitric acid compound of rare earth elements, disodium ethylene diamine tetraacetate (EDTA-2Na), ammonium fluoride solution and other reagents adopted by the implementation of the invention are all commercially available analytical pure chemical reagents.
The rare earth fluoride prepared in the embodiment of the invention adopts an X' Pert Pro X-ray diffractometer (PANALYTICAL B.V. Netherlands) with model number PW3040/60 to carry out XRD phase analysis, adopts a JSM-7001F JEO L field emission scanning electron microscope to carry out morphology observation and analysis, and adopts a JEM-1010 TEM of Japan JEO L company to observe the morphology (TEM) of a sample.
The inner container of the hydrothermal reaction kettle is made of polytetrafluoroethylene with the specification of 100ml, the steel sleeve is made of stainless steel, the oven is an electronic temperature control blast oven, and the temperature difference is less than 1 ℃;
example 1
NaREF4The preparation method of the solid spherical particles comprises the following steps:
(1) l a (NO)3)3·6H2Mixing O and disodium ethylene diamine tetraacetate uniformly in deionized water to prepare a solution with the rare earth ion concentration of 0.01 mol/L;
(2) stirring for 15min, adding ammonia fluoride solution, and continuously stirring for 15min to obtain suspension;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction at 100 ℃ for 12 hours;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, and drying at 50 ℃ to obtain white powdery particles Na L aF4；
NaLaF4The XRD pattern of the powder is shown as figure 1 and shows pure phase, the SEM topography is shown as figure 2, and the obtained Na L aF can be seen4The product showed a solid spherical morphology.
Example 2
NaREF4The preparation method of the solid spherical particles comprises the following steps:
(1) eu (NO)3)3·6H2Mixing O and disodium ethylene diamine tetraacetate uniformly in deionized water to prepare a solution with the rare earth ion concentration of 0.05 mol/L;
(2) stirring for 15min, and adding 10mmol NH4Continuing stirring the solution F for 15min to obtain a suspension;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 18 h;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, and drying at 50 ℃ to obtain white powdery particles NaEuF4；
NaEuF4The XRD pattern of the powder is shown in FIG. 3, which shows pure phase; the SEM topography is shown in FIG. 4, and the obtained NaEuF can be seen4The product presents a solid spherical shape;
example 3
NaREF4The preparation method of the solid spherical particles comprises the following steps:
(1) er (NO)3)3·6H2Mixing O and disodium ethylene diamine tetraacetate uniformly in deionized water to prepare a solution with the rare earth ion concentration of 0.10 mol/L;
(2) stirring for 15min, adding ammonium fluoride, and continuously stirring for 15min to obtain a suspension;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24 hours;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, and drying at 60 ℃ to obtain white powdery particles NaErF4；
NaErF4The XRD pattern of the powder is shown in FIG. 5, which shows pure phase; the SEM topography is shown in FIG. 6, and the NaErF obtained can be seen4The product showed a solid spherical morphology.
Example 4
NaREF4The preparation method of the solid spherical particles comprises the following steps:
(1) l u (NO)3)3·6H2Mixing O and disodium ethylene diamine tetraacetate uniformly in deionized water to prepare a solution with the rare earth ion concentration of 0.15 mol/L;
(2) stirring for 15min, adding ammonium fluoride, and continuously stirring for 15min to obtain a suspension;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 36 hours;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, and drying at 60 ℃ to obtain white powdery particles Na L uF4；
NaLuF4The XRD pattern of the powder is shown in figure 7 and shows pure phase, the SEM topography is shown in figure 8, and the obtained Na L uF can be seen4The product showed a solid spherical morphology.
Example 5
NaREF4The preparation method of the solid spherical particles comprises the following steps:
(1) mixing Y (NO)3)3·6H2Mixing O and disodium ethylene diamine tetraacetate uniformly in deionized water to prepare a solution with the rare earth ion concentration of 0.20 mol/L;
(2) stirring for 15min, adding NH4Continuing stirring the solution F for 15min to obtain a suspension;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 48 hours;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and cleaning a reaction product, and drying at 70 ℃ to obtain white powdery particles NaYF4；
NaYF4The XRD pattern of the powder is shown in FIG. 9, which shows pure phase; the SEM topography is shown in FIG. 10, and the obtained NaYF can be seen4The product showed a solid spherical morphology. The TEM topography is shown in FIG. 11; FIG. 12 is an HR-TEM image, in which the interplanar spacing of 0.134nm is close to the (400) plane of NaYF4 (d (400) — 0.137nm, JCPDS No.77-2042), further illustrating that the synthesized nanoparticles belong to the cubic structurePhase NaYF4。
Claims (2)
1. NaREF4The preparation method of the solid spherical particles is characterized by comprising the following steps:
(1) uniformly mixing a nitric acid compound of a rare earth element and disodium ethylene diamine tetraacetate in deionized water to prepare a solution with the total concentration of rare earth ions of 0.01-0.20 mol/L, wherein RE is one of L a, Eu, Er, L u and Y;
(2) adding ammonia fluoride solution and stirring uniformly to obtain suspension; the mol ratio of the ammonium fluoride to the rare earth elements is 5: 1;
(3) transferring the suspension into a reaction kettle, and carrying out hydrothermal reaction for 12-48h at 100-200 ℃ under a sealed condition;
(4) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating and drying a reaction product to obtain the solid nano spherical particles NaREF4。
2. The method according to claim 1, wherein the drying conditions of the step (4) are: the temperature is 50-70 ℃, and the time is 12-24 h.
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| CN103074065A (en) * | 2013-01-08 | 2013-05-01 | 上海交通大学 | Method for preparing upconversion nanometer material taking NaLuF4 as base material |
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Inventor after: Zhu Qi Inventor after: Song Caiyun Inventor after: Li Xiaodong Inventor after: Sun Xudong Inventor before: Zhu Qi Inventor before: Song Caiyun Inventor before: Li Jiguang Inventor before: Li Xiaodong Inventor before: Sun Xudong |
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