CN101671558B - Preparation method of dysprosium zirconate terbium-doped green luminescent material - Google Patents
Preparation method of dysprosium zirconate terbium-doped green luminescent material Download PDFInfo
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- CN101671558B CN101671558B CN2009101536354A CN200910153635A CN101671558B CN 101671558 B CN101671558 B CN 101671558B CN 2009101536354 A CN2009101536354 A CN 2009101536354A CN 200910153635 A CN200910153635 A CN 200910153635A CN 101671558 B CN101671558 B CN 101671558B
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- terbium
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- dysprosium
- luminescent material
- green luminescent
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- 239000000463 material Substances 0.000 title claims abstract description 21
- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 15
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 11
- -1 rare earth cation Chemical class 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 9
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000011049 filling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- 229910052771 Terbium Inorganic materials 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 4
- 239000012720 thermal barrier coating Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of a dysprosium zirconate terbium-doped green luminescent material. The preparation method comprises the following steps: dissolving dysprosium nitrate and terbium nitrate into deionized water according to mol ratio; dissolving zirconium oxychloride into deionized water, stirring, controlling the mol weight of the zirconium oxychloride to be equal to that of total rare earth kations, dipping the zirconium oxychloride drop by drop into the solution, and stirring; adding sodium hydroxide solution drop by drop to obtain white precipitate, and controlling the pH value of the solution to be 8 to 10; putting the solution into a high-pressure kettle with the filling degree of 80 percent, and treating for 5 to 20 hours at the temperature from 180 DEG C to 220 DEG C; and finally centrifuging and drying the well-treated solution to obtain the dysprosium zirconate terbium-doped green luminescent material. The invention adopts a hydrothermal method to realize the synthesis of the dysprosium zirconate terbium-doped green luminescent material, and has good product crystallinity, simple process and mild conditions.
Description
Technical field
The present invention relates to a kind of preparation method of dysprosium zirconate terbium-doped green luminescent material.
Background technology
Rare earth zirconate (Re
2Zr
2O
7) function is numerous, of many uses, as as thermal barrier coating, because therefore very low thermal conductivity, higher chemicalstability receive much concern, in addition, it has advantages of high catalytic activity as photocatalyst, also by broad research.The performance of rare earth zirconate mainly shows: HMP, macroion electroconductibility, high chemical stability, high catalytic activity etc.In recent years, its matrix as embedded photoluminescent material comes into one's own, but correlative study is also less.
Existing research report about rare earth zirconic acid dysprosium material mainly concentrates on thermal barrier coating and photochemical catalysis aspect, and its preparation method is relatively single, and [Zhou Hongming is prone to painting, and thermal barrier coating is used Dy to be mainly co-precipitation-calcination method
2Zr
2O
7Ceramic powder preparation and heat physical properties research thereof, aeronautical material journal, 2008,28 (1): 65-69], high temperature solid-phase sintering method [Q.Xu, W.Pan, Preparation and thermophysical propertiesof Dy
2Zr
2O
7Ceramic for thermal barrier coatings, Materials Letters, 2005,59:2804-2807] and sol-gel method [Y.P.Tong, Z.X.Yu, Rapid preparation andcharacterization of Dy
2Zr
2O
7Nanocrystals; Materials Research Bulletin, 2008,43:2736-2741]; And the synthesis temperature of existing compound method is generally higher; Generally need 1000 ℃ even higher, the synthesis technique relative complex, under the mild conditions almost there be not hydrothermal method synthetic report and adopt comparatively.In addition, the zirconic acid dysprosium is also considerably less as the report that luminescent material matrix is studied, and the synthetic of dysprosium zirconate terbium-doped green luminescent material also do not appear in the newspapers.
Summary of the invention
The object of the present invention is to provide a kind of dysprosium zirconate terbium-doped (Dy
2Zr
2O
7: Tb
3+) preparation method of green luminescent material.Adopt hydro-thermal technology, under lower temperature of reaction, realized the preparation of dysprosium zirconate terbium-doped green luminescent material.
The step of the technical scheme that the present invention adopts is following:
1) Dysprosium trinitrate, Terbium trinitrate are dissolved in the deionized water by mole per-cent, the ratio of control Terbium trinitrate is 4%～7% of a total rare earth cation mole number, stirs;
2) will be dissolved in the basic zirconium chloride of above-mentioned total rare earth cation equimolar amount in the deionized water, stir, and it will dropwise be added in the above-mentioned rare earth nitrate solution, stir;
3) sodium hydroxide solution that dropwise adds 1.0 mol generates white precipitate, and the pH value of control solution is 8～10, continues stirring;
4) with the above-mentioned solution autoclave of packing into, adopt hydro-thermal technology, the solution centrifugal of handling well, drying obtain dysprosium zirconate terbium-doped green luminescent material.
Said hydro-thermal technology, temperature are controlled to be 180～220 ℃, and the treatment time is 5～20 hours.
The beneficial effect that the present invention has is:
The present invention is to be reactant with Dysprosium trinitrate, Terbium trinitrate, basic zirconium chloride, has synthesized dysprosium zirconate terbium-doped green luminescent material through hydro-thermal technology.The product crystallinity is better, and preparation technology is simple, and reaction conditions is gentle, and is significant to exploring the development of new rare earth luminescent material, will expand new field for the research of rare earth luminescent material simultaneously.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom.
Curve (a) and (b), (c), (d) corresponding embodiment 1,2,3 of difference and 4 products therefrom pl-emmission spectrum spectrograms among Fig. 2.
Embodiment
Embodiment 1:
Get 1.3695 gram Dysprosium trinitrate (Dy (NO respectively
3)
36H
2O), 0.0566 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, the volumetric molar concentration of Dysprosium trinitrate, Terbium trinitrate be respectively 0.0750 mol, 0.0031 you/liter, stirred 15 minutes; Get basic zirconium chloride (ZrOCl
28H
2O) 1.0069 grams are dissolved in 40 ml deionized water, and the volumetric molar concentration of basic zirconium chloride is 0.0781 mol, stirs 15 minutes.Zirconium oxychloride solution is dropwise splashed in the mixing solutions of above-mentioned Dysprosium trinitrate and Terbium trinitrate, stirred 15 minutes.Dropwise in above-mentioned mixing solutions, add the sodium hydroxide solution of 1 mol, the pH value of regulator solution is 8.0, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 10 hours down at 200 ℃, the solution centrifugal of handling well, drying, obtained required product, and wherein the doping content of terbium accounts for 4% of total rare earth total mole number.Fig. 1 is the XRD figure spectrum of this routine products therefrom, each diffraction peak position and Dy among the figure
2Zr
2O
7Standard card (JCPDSNO.78-1293) unanimity, be the fluorite structure, the variation that does not cause structure of mixing of Tb is described.Curve among Fig. 2 (a) is its pl-emmission spectrum, has the strongest emission peak in 545 nanometers, is green emission spectrum.
Embodiment 2:
Get 2.2825 gram Dysprosium trinitrate (Dy (NO respectively
3)
36H
2O), 0.1192 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, the volumetric molar concentration of Dysprosium trinitrate, Terbium trinitrate is respectively 0.125 mol, 0.0066 mol, stirs 20 minutes; Get basic zirconium chloride (ZrOCl
28H
2O) 1.6959 grams are dissolved in 40 ml deionized water, and the volumetric molar concentration of basic zirconium chloride is 0.1316 mol, stirs 15 minutes.Zirconium oxychloride solution is dropwise splashed in the mixing solutions of above-mentioned Dysprosium trinitrate and Terbium trinitrate, stirred 20 minutes.Dropwise in above-mentioned mixing solutions, add the sodium hydroxide solution of 1 mol, the pH value of regulator solution is 8.5, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 10 hours down at 180 ℃, the solution centrifugal of handling well, drying, obtained required product, and the doping content of terbium accounts for 5% of total rare earth total mole number.Curve among Fig. 2 (b) is its pl-emmission spectrum, has sharp-pointed green emission spectrum in 545 nanometers.
Embodiment 3:
Get 4.565 gram Dysprosium trinitrate (Dy (NO respectively
3)
36H
2O), 0.2891 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, the volumetric molar concentration of Dysprosium trinitrate, Terbium trinitrate is respectively 0.25 mol, 0.016 mol, stirs 20 minutes; Get basic zirconium chloride (ZrOCl
28H
2O) 3.4279 grams are dissolved in 40 ml deionized water, and the volumetric molar concentration of basic zirconium chloride is 0.266 mol, stirs 15 minutes.Zirconium oxychloride solution is dropwise splashed in the mixing solutions of above-mentioned Dysprosium trinitrate and Terbium trinitrate, stirred 20 minutes.Dropwise in above-mentioned mixing solutions, add the sodium hydroxide solution of 1 mol, the pH value of regulator solution is 9.0, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 5 hours down at 220 ℃, the solution centrifugal of handling well, drying, obtained required product, and the doping content of terbium accounts for 6% of total rare earth total mole number.Curve among Fig. 2 (c) is its pl-emmission spectrum, has sharp-pointed green emission spectrum in 545 nanometers.
Embodiment 4:
Get 3.6520 gram Dysprosium trinitrate (Dy (NO respectively
3)
36H
2O), 0.2728 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, the volumetric molar concentration of Dysprosium trinitrate, Terbium trinitrate is respectively 0.2000 mol, 0.0151 mol, stirs 15 minutes; Get basic zirconium chloride (ZrOCl
28H
2O) 2.7718 grams are dissolved in 40 ml deionized water, and the volumetric molar concentration of basic zirconium chloride is 0.2151 mol, stirs 15 minutes.Zirconium oxychloride solution is dropwise splashed in the mixing solutions of above-mentioned Dysprosium trinitrate and Terbium trinitrate, stirred 20 minutes.Dropwise in above-mentioned mixing solutions, add the sodium hydroxide solution of 1 mol, the pH value of regulator solution is 10.0, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 20 hours down at 190 ℃, the solution centrifugal of handling well, drying, obtained required product, and the doping content of terbium accounts for 7% of total rare earth total mole number.Curve among Fig. 2 (d) is its pl-emmission spectrum, has sharp-pointed green emission spectrum in 545 nanometers.
Claims (1)
1. the preparation method of a dysprosium zirconate terbium-doped green luminescent material is characterized in that the step of this method is following:
1) Dysprosium trinitrate, Terbium trinitrate are dissolved in the deionized water by mole per-cent, the ratio of control Terbium trinitrate is 4%～7% of a total rare earth cation mole number, stirs;
2) will be dissolved in the basic zirconium chloride of above-mentioned total rare earth cation equimolar amount in the deionized water, stir, and it will dropwise be added in the above-mentioned rare earth nitrate solution, stir;
3) sodium hydroxide solution that dropwise adds 1.0 mol generates white precipitate, and the pH value of control solution is 8～10, continues stirring;
4) with the above-mentioned solution autoclave of packing into, adopt hydro-thermal technology, temperature is controlled to be 180～220 ℃, and the treatment time is 5～20 hours, and the solution centrifugal of handling well, drying obtain dysprosium zirconate terbium-doped green luminescent material.
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| CN104974755B (en) * | 2014-12-25 | 2017-01-11 | 陕西科技大学 | Green rare-earth fluorescent powder for LED (Light Emitting Diode) and preparation method of fluorescent powder |
| CN110803926B (en) * | 2019-11-07 | 2022-02-11 | 兰州工业学院 | Preparation method of micro-doped high-surface-area nano zirconium dioxide powder |
| CN115820246A (en) * | 2022-11-21 | 2023-03-21 | 桂林电子科技大学 | Preparation method and application of rare earth terbium-doped gallium oxide fluorescent material |
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