CN104944433A - Preparation method of rare earth orthoborate nanocrystal - Google Patents
Preparation method of rare earth orthoborate nanocrystal Download PDFInfo
- Publication number
- CN104944433A CN104944433A CN201510418417.4A CN201510418417A CN104944433A CN 104944433 A CN104944433 A CN 104944433A CN 201510418417 A CN201510418417 A CN 201510418417A CN 104944433 A CN104944433 A CN 104944433A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- solution
- orthoborate
- product
- deionized water
- 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
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of a rare earth orthoborate nanocrystal. The method comprises the steps that a rare earth oxide is completely dissolved in nitric acid to prepare a rare earth nitrate solution, the solution is evenly stirred, and the rare earth element of the rare earth oxide is one of Y, La, Sm or Gd; the pH value of the rare earth nitrate solution is adjusted by utilizing a sodium hydroxide solution to be 9-10; the rare earth nitrate solution with the pH value well adjusted is placed into a high pressure hydro-thermal reactor to react on the condition that the temperature ranges from 180 DEG C to 220 DEG C for 20-40 h, the reacted solution is naturally cooled to be the room temperature, and the reacted product is washed through deionized water to obtain an intermediate product; the obtained intermediate product is mixed with a boric acid solution and stirred evenly; the evenly stirred mixture is placed into the high pressure hydro-thermal reactor to react on the condition that the temperature ranges from 200 DEG C to 220 DEG C for 40-60 h, the reacted solution is naturally cooled to be the room temperature, the reacted product is washed through the deionized water and dried, and the rare earth orthoborate nanocrystal is obtained. According to the preparation method of the rare earth orthoborate nanocrystal, the synthetic temperature is low, only ranges from 180 DEG C to 220 DEG C and is 800 DEG C lower than a traditional solid phase reaction method, ball milling does not need to be conducted on the product, and the luminous intensity and the applicability of materials are improved.
Description
Technical field
The present invention relates to the preparation method that a kind of rare earth orthoborate is nanocrystalline, belong to technical field of fine.
Background technology
Rare earth orthoborate material, as the luminescent material that a class is important, there is excellent photoluminescence efficiency, chemical stability and wider light-emitting zone, have the good transparency in ultraviolet and vacuum ultraviolet region, rare earth orthoborate material is had a wide range of applications, as YBO
3: Eu and GdBO
3: Eu is used to the red illuminating material of plasma display device, and YBO
3: Tb is used as green luminescent material.General rare earth orthoborate adopts solid reaction process synthesis, temperature of reaction is more than 1100 DEG C, the loss that excessive boric acid or boron trioxide compensate boron in high-temperature burning process need be added, and high-temperature calcination easily causes caking phenomenon, obtain suitable granularity, the granularity of fluorescent material need be reduced by ball milling, thus the luminous intensity of fluorescent material can be reduced, and be difficult to the pattern controlling fluorescent material.And nano luminescent material is due to surface effects, the crystal field residing for atom on surface is different from inner atom, and symmetry reduces, and just likely produces and the different luminescent properties of body material.Meanwhile, material particle size reduces, homogeneity improves, and will contribute to the coating of fluorescent material, reduces the scattering of light of phosphor surface, contributes to improving luminous efficiency.
Summary of the invention
The present invention seeks to: for above the deficiencies in the prior art, the invention provides that a kind of reaction conditions is relatively gentle, synthesis temperature is low, preparation method that the rare earth orthoborate of product particle size and morphology controllable is nanocrystalline, it is by introducing sodium hydroxide as mineralizer, adopt two step hydro-thermal reaction methods, preparing chemical formula is REBO
3rare earth orthoborate nanocrystalline.
Technical scheme of the present invention is: the preparation method that a kind of rare earth orthoborate is nanocrystalline, and the chemical formula of described rare earth orthoborate is REBO
3, described RE be selected from rare earth element y, La, Sm or Gd any one, this preparation method comprises concrete following steps:
1. stoichiometrically take required material rare earth oxide, be dissolved in nitric acid make rare earth nitrate solution completely, stir, the rare earth element of described rare earth oxide is Y, La, Sm or Gd;
2. sodium hydroxide solution is prepared;
3. utilize the described sodium hydroxide solution prepared, regulate the pH value of described rare earth nitrate solution, until the pH value of rare earth nitrate solution is stablized to 9 ~ 10;
4. the rare earth nitrate solution mixing up pH value is placed in hydro-thermal autoclave, reacts after 20 ~ 40h under 180 ~ 220 DEG C of conditions, Temperature fall to room temperature, by reacted product deionized water wash 3 ~ 5 times;
5. stoichiometrically take required material boric acid, be dissolved in deionized water make boric acid solution completely, product step 4. obtained mixes with described boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, reacts after 40 ~ 60h under 200 ~ 220 DEG C of conditions, Temperature fall to room temperature, reacted product deionized water wash 3 ~ 5 times;
7. the product after step 6. being washed is dried, and obtains rare earth orthoborate nanocrystalline.
The present invention, on the basis of technique scheme, also comprises following preferred version:
Described step 2. in, the concentration of the sodium hydroxide solution prepared is 1 ~ 2mol/L.
Advantage of the present invention is:
1, the rare earth orthoborate LaBO of the present invention's synthesis
3, YBO
3and GdBO
3as the substrate material of luminescent material, by doping Eu
3+or Tb
3+deng light emitting ionic ultraviolet and vacuum ultraviolet-excited under there is good luminescent properties, the present invention synthesis SmBO
3as optical absorbing material, to 1.06 μm, 1.54 μm and 10.6 μm of near infrared lights, there is good optical absorption characteristics.
2, synthesis temperature of the present invention is low, only has 180 ~ 220 DEG C, lower than traditional solid reaction process 800 DEG C; Product does not need ball milling, can improve luminous intensity and the applicability of material.
Embodiment:
The present invention's sodium hydroxide is as mineralizer, and adopt two step hydro-thermal reaction methods, preparative chemistry formula is REBO
34 specific embodiments that the rare earth orthoborate of (wherein RE represents rare earth element, be specifically selected from any one in Y, La, Sm or Gd) is nanocrystalline are as follows:
Embodiment 1:
1. required material is stoichiometrically taken: the Y of 0.3387g
2o
3, and by this Y
2o
3be dissolved in completely in nitric acid and make Y (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 1mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described Y (NO
3)
3the pH value of solution, until Y (NO
3)
3the pH value of solution is stablized to 9;
4. the solution mixing up pH value is placed in hydro-thermal autoclave, react 20h at 180 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 3 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, and be dissolved in deionized water completely by this boric acid and make boric acid solution, product step 4. obtained mixes with this boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 40h at 200 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 3 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with six side YBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Embodiment 2:
1. required material is stoichiometrically taken: the La of 0.4887g
2o
3, and by this La
2o
3be dissolved in completely in nitric acid and make La (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 1.5mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described La (NO
3)
3the pH value of solution, until La (NO
3)
3the pH value of solution is stablized to 9.5;
4. the solution 3. step being mixed up pH value is placed in hydro-thermal autoclave, react 30h at 200 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 4 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, and be dissolved in deionized water completely by this boric acid and make boric acid solution, product step 4. obtained mixes with boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 50h at 210 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 4 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with orthogonal LaBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Embodiment 3:
1. required material is stoichiometrically taken: the Sm of 0.5231g
2o
3, and by this Sm
2o
3be dissolved in completely in nitric acid and make Sm (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 2mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described Sm (NO
3)
3the pH value of solution, until Sm (NO
3)
3the pH value of solution is stablized to 10;
4. the solution mixing up pH value is placed in hydro-thermal autoclave, react 40h at 220 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 5 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, be dissolved in deionized water make boric acid solution completely, product step 4. obtained mixes with this boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 60h at 220 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 5 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with six side SmBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Embodiment 4:
1. required material is stoichiometrically taken: the Gd of 0.5437g
2o
3, and by this Gd
2o
3be dissolved in completely in nitric acid and make Gd (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 2mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described Gd (NO
3)
3the pH value of solution, until Gd (NO
3)
3the pH value of solution is stablized to 9.5;
4. the solution 3. step being mixed up pH value is placed in hydro-thermal autoclave, react 35h at 200 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 5 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, and be dissolved in deionized water completely by this boric acid and make boric acid solution, product step 4. obtained mixes with this boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 50h at 210 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 4 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with six side GdBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Certainly, above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to people can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to the spirit of main technical schemes of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (2)
1. the preparation method that rare earth orthoborate is nanocrystalline, the chemical formula of described rare earth orthoborate is REBO
3, described RE be selected from rare earth element y, La, Sm or Gd any one, it is characterized in that the nanocrystalline preparation method of this rare earth orthoborate comprises the following steps:
1. stoichiometrically take required material rare earth oxide, be dissolved in nitric acid make rare earth nitrate solution completely, stir, the rare earth element of described rare earth oxide is Y, La, Sm or Gd;
2. sodium hydroxide solution is prepared;
3. utilize the described sodium hydroxide solution prepared, regulate the pH value of described rare earth nitrate solution, until the pH value of rare earth nitrate solution is stablized to 9 ~ 10;
4. the rare earth nitrate solution mixing up pH value is placed in hydro-thermal autoclave, reacts after 20 ~ 40h under 180 ~ 220 DEG C of conditions, Temperature fall to room temperature, by reacted product deionized water wash 3 ~ 5 times;
5. stoichiometrically take required material boric acid, be dissolved in deionized water make boric acid solution completely, product step 4. obtained mixes with described boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, reacts after 40 ~ 60h under 200 ~ 220 DEG C of conditions, Temperature fall to room temperature, reacted product deionized water wash 3 ~ 5 times;
7. the product after step 6. being washed is dried, and obtains rare earth orthoborate nanocrystalline.
2. the preparation method that rare earth orthoborate as claimed in claim 1 is nanocrystalline, is characterized in that: described step 2. in, the concentration of the sodium hydroxide solution prepared is 1 ~ 2mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418417.4A CN104944433B (en) | 2015-07-16 | 2015-07-16 | The preparation method that a kind of rare earth orthoborate is nanocrystalline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418417.4A CN104944433B (en) | 2015-07-16 | 2015-07-16 | The preparation method that a kind of rare earth orthoborate is nanocrystalline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104944433A true CN104944433A (en) | 2015-09-30 |
| CN104944433B CN104944433B (en) | 2016-04-13 |
Family
ID=54159577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510418417.4A Active CN104944433B (en) | 2015-07-16 | 2015-07-16 | The preparation method that a kind of rare earth orthoborate is nanocrystalline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104944433B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972457A (en) * | 2010-07-12 | 2011-02-16 | 泰一和浦（北京）中医药研究院有限公司 | Chinese medicinal composition for treating edema during menstruation and preparation method thereof |
| CN103800881A (en) * | 2014-02-20 | 2014-05-21 | 柳晖 | Traditional Chinese medicine composition for treating heart-spleen deficiency syndrome |
-
2015
- 2015-07-16 CN CN201510418417.4A patent/CN104944433B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972457A (en) * | 2010-07-12 | 2011-02-16 | 泰一和浦（北京）中医药研究院有限公司 | Chinese medicinal composition for treating edema during menstruation and preparation method thereof |
| CN103800881A (en) * | 2014-02-20 | 2014-05-21 | 柳晖 | Traditional Chinese medicine composition for treating heart-spleen deficiency syndrome |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104944433B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jia et al. | Synthesis and enhanced luminescence of uniform and well-dispersed quasispherical YVO 4: Ln 3+(Ln= Eu, Dy) nanoparticles by a solvothermal method | |
| CN106544025B (en) | A kind of preparation method of rear-earth-doped gadolinium oxysulfide fluorescent powder | |
| Zhang et al. | Facile synthesis of monodisperse YAG: Ce 3+ microspheres with high quantum yield via an epoxide-driven sol–gel route | |
| Lian et al. | Co-precipitation synthesis of Y2O2SO4: Eu3+ nanophosphor and comparison of photoluminescence properties with Y2O3: Eu3+ and Y2O2S: Eu3+ nanophosphors | |
| CN106520121A (en) | Preparation method of rare earth-doped gadolinium oxysulfide and oxygen-containing gadolinium sulphate up-conversion phosphor | |
| CN109133922B (en) | Double-doped rare earth ion garnet structure optical function ceramic powder and preparation method thereof | |
| CN105733584B (en) | Yttrium Orthovanadate nanoparticle and rare earth ion doped Yttrium Orthovanadate nanoparticle and preparation method thereof | |
| Liu et al. | EDTA-assisted hydrothermal synthesis of KLa (MoO4) 2: Eu3+ microcrystals and their luminescence properties | |
| Li et al. | Rapid, morphology-controllable synthesis of GdOF: Ln 3+(Ln= Eu, Tb) crystals with multicolor-tunable luminescence properties | |
| Chen et al. | Photoluminescence properties of YBO3: Eu3+ phosphors prepared via the solvothermal synthesis under supercritical conditions | |
| CN104804733A (en) | Rare-earth strontium aluminate luminous nanorod and preparation method thereof | |
| Wu et al. | Improved photoluminescence behavior of Eu3+-activated Ca5 (PO4) 3F red nanophosphor by adding Li+, Au3+, and Bi3+ as co-dopants | |
| Leng et al. | Synthesis and luminescent properties of ellipsoid-like YBO3: Ln3+ (Ln= Eu, Tb) | |
| Muresan et al. | Structural and luminescence characterization of yttrium oxide based phosphors prepared by wet-chemical method | |
| Li et al. | A novel synthetic route towards monodisperse LaOF: Ln 3+(Ln= Eu, Tb) hollow spheres with multicolor luminescence properties | |
| Li et al. | Synthesis and characterizations of pompon-like Y2O2SO4: Eu3+ phosphors using a UBHP technique based on UAS system | |
| CN104944433B (en) | The preparation method that a kind of rare earth orthoborate is nanocrystalline | |
| Zhang et al. | Spherical Lu2O2S: Eu3+ micro/nano-structure: Controlled synthesis and luminescence properties | |
| Ping et al. | Synthesis and luminescent characteristic of Eu3+-doped (Gd, Lu) 2O3 nanopowders | |
| CN105752957A (en) | Method for preparing nano-scale rare-earth phosphate phosphor by self-sacrificing template method | |
| CN102618279B (en) | Preparation method of shape-controllable aluminate luminous materials | |
| Du et al. | Morphology-controlled hydrothermal synthesis and multifunctional luminescence properties of micro-crystals Gd 6 O 5 F 8: Eu 3+/Tb 3+/Tm 3+ | |
| CN103694998B (en) | A kind of oxysulfide red long afterglow luminous material and preparation method thereof | |
| CN101648726B (en) | Hydrothermal synthesis method of LuO(OH) nanorods and Lu2O3 nanorods luminescent powder | |
| Shinde et al. | Luminescence optimization of Y0. 94− xEu0. 06VO4: Mx (M= Zn, Al, Bi) Red phosphors by the solution combustion method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201130 Address after: 334500 Jiangxi city of Shangrao Province Qianshan County Industrial Park Patentee after: Qianshan qirainbow Crystal Technology Co., Ltd Address before: 224051 Yancheng City hope road, Jiangsu, No. 1 Patentee before: YANCHENG INSTITUTE OF TECHNOLOGY |