CN1335349A - Rare earth subsulfate luminous material and its hot synthesis in solvent - Google Patents
Rare earth subsulfate luminous material and its hot synthesis in solvent Download PDFInfo
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- CN1335349A CN1335349A CN 00108496 CN00108496A CN1335349A CN 1335349 A CN1335349 A CN 1335349A CN 00108496 CN00108496 CN 00108496 CN 00108496 A CN00108496 A CN 00108496A CN 1335349 A CN1335349 A CN 1335349A
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- rare earth
- solvent
- subsulphate
- subsulfate
- ohso
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Abstract
Single or mixed RE nitrate and the water solution of thiocarbamide, RE nitrate and the alkali solution of ammonium sulfate, or the alkali solution of RE sulfate are made to react inside one sealed pressure container at 200-400 deg.c for at least 3 hr. The one-step hot reaction process in solution ot synthesize subsulfate has relatively low temperature, mild conditions and simple operation, and its product has controllable chemical composition and thus different luminous performance.
Description
The present invention relates to rare earth subsulphate luminescent material, comprise the subsulphate of single rare earth and mixed rare earth ions, and solvent process for thermosynthesizing.
Existing conventional rare earth luminescent material, as oxide compound, sulfide, halogen-phosphate has been widely used in chromoscope, fluorescent tube bulb, health care etc.Comparatively speaking, the research of relevant rare earth subsulphate then seldom.
USSR (Union of Soviet Socialist Republics) " structural chemistry magazine " (Zh.Strukt.Khim.,, the 13rd volume, 260-265 page or leaf in 1972) had once been reported CeO
2-SO
3-H
2The research of O reaction system, this system can generate aqueous rare earth subsulphate Ce
2(OH)
2(SO
4)
34H
2O.U.S.'s " solid state chemistry magazine " Journal of Solid State Chemistry, 1988, the 73rd volume, 71-79 page or leaf) reported LaOHSO
4, PrOHSO
4And LaOHSO
4Hydro-thermal synthetic, this method adopts the aqueous solution of rare earth oxide-oxyhydroxide-vitriol to carry out at 450 ± 50 ℃.These work mainly are conceived to the chemical equilibrium of system and the research of crystalline structure, and all the luminosity of this type of subsulphate of undetermined does not recognize that they might be class advanced luminescent materials.
The present invention proposes rare earth subsulphate luminescent material and thermal synthesis production method of solvent thereof.
This class rare earth luminescent material is characterized in that they are that molecular formula can be expressed as Ln
xLn '
1-xOHSO
4The rare earth subsulphate, wherein: Ln, Ln ' are different rare earth elements, comprise La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y; 0≤x≤1; When x=0 or x=1, Lrn
xLn '
1-xOHSO
4Be single rare earth rare earth subsulphate; When 0＜x＜1, Ln
xLn '
1-xOHSO
4Subsulphate for mixed rare earth ions.
The thermal synthesis production method of solvent of the rare earth subsulphate luminescent material that the present invention proposes, it is characterized in that, with the aqueous solution of single or mixed rare earth nitrates and thiocarbamide or with the basic solution of rare earth nitrate and ammonium sulfate or with the basic solution of rare earth sulfate, in airtight voltage-resistant reactor, be no less than 3 hours in 200-400 ℃ of reaction, reaction finishes the back and collects solid product, washes with water, obtains product after the drying; Described basic solution comprises the mixing solutions of hydrazine hydrate, ammoniacal liquor, pyridine and water or the mixing solutions of amine and water.
The present invention has broken through the blind area of former studies, finds and proposed the new rare earth subsulphate luminescent material of a class; Set up the method for a step solvent thermal reaction synthesizing rare-earth subsulphate.The required temperature (200-400 ℃) of this method is lower than the temperature (450 ± 50 ℃) of synthetic other similar compound of bibliographical information in the past, and preparation condition is comparatively gentle, easy to operation.Adopt the inventive method to prepare the rare earth subsulphate, the chemical constitution of product is controlled: when selecting the single rare earth reactant for use, can obtain the single rare earth subsulphate; And when selecting the mishmetal reactant for use, then can obtain the subsulphate of mixed rare earth ions, wherein the latter is synthetic first in the world for the present invention.By adjusting the stoicheiometry of different types of rare earth reactant, can synthesize a series of rare earth subsulphates that different chemical is formed that have, along with the difference of its chemical constitution, corresponding luminescent properties also can change to some extent.Therefore, by regulating the chemical constitution of synthetic materials, can regulate and control the luminescent properties of this material.
Because the atomic radius of rare earth element is close, character is very similar, shows similar chemical conduct in reaction usually.If certain rare earth compound has specific physical properties, as luminosity, the similar compound of other rare earth element also shows similar character.
The solvent thermal building-up reactions of the rare earth subsulphate that the present invention proposes, temperature of reaction should be decided on concrete starting material, generally at 200-400 ℃.If temperature is crossed low or too high, may generate impurity such as oxide compound or subcarbonate.For obtaining purer rare-earth alkali formula vitriol, for preventing to generate other impurity because of solution leaks in final product, reaction needs to carry out in airtight voltage-resistant reactor; For avoiding the pollution of reactor material, adopt the limit planted agent of temperature permission to have the teflon-lined autoclave to reaction product as far as possible.
Below be some embodiments of the present invention.
Embodiment 1.LaOHSO
4Hydro-thermal synthetic:
With 1.0 gram La (NO
4)
3NH
2O and 0.50 gram CS (NH
2)
2(thiocarbamide) adds volume is in the stainless steel autoclave of 25ml, is solvent with distilled water, and the compactedness that makes autoclave is 85%, 400 ℃ of reactions 3 hours, is cooled to room temperature; The product deionized water wash, (vacuum-drying 1 hour obtains LaOHSO at 60 ℃
4Crystal.This crystalline maximum excitation wavelength is at 280-290nm, and glow peak is at 365-289nm.
Embodiment 2.CeOHSO
4Hydro-thermal synthetic:
Ce (NO with 1.0 gram analytical pure levels
4)
36H
2CS (the NH of O and 0.45 gram
2)
2Adding volume is in the stainless steel autoclave of 25ml, is solvent with distilled water, and the compactedness that makes autoclave is 85%, 300 ℃ of reactions 6 hours, is cooled to room temperature; Product washing back obtains LaOHSO 60 ℃ of vacuum-dryings 1 hour
4Crystal.This crystalline maximum excitation wavelength is at-250nm, and glow peak illustrates that it is a kind of potential ultra-violet light-emitting material about 390nm.
Embodiment 3.CeOHSO
4The solvent solvent thermal synthetic:
With 1.0 gram Ce
2(SO
4)
3Adding volume with 5ml ammoniacal liquor is in the stainless steel autoclave of 25ml, and adding distilled water again, to make the compactedness of autoclave be 85%, 250 ℃ of reactions 6 hours, is cooled to room temperature; Product washes with water, 60 ℃ of vacuum-dryings 1 hour, obtains CeOHSO
4Crystal.The suitable excitation wavelength of this crystalline has the glow peak of a broadening at 205-248nm at the 392nm place.
In the present embodiment,, all can obtain same products as if being the mixing solutions of hydrazine hydrate or pyridine and water or the mixing solutions of amine and water with solvent replacing.
Embodiment 4.CeOHSO
4Solvent thermal synthetic:
Take by weighing 0.87 gram Ce (NO
3)
36H
2O and 0.40 gram (NH
4)
2SO
4(ammonium sulfate), adding volume are 25ml, have in the teflon-lined autoclave that the mixed solution of using distilled water and pyridine makes the compactedness of reactor reach 85% as solvent, 200 ℃ of reactions 10 hours, naturally cool to room temperature.Product with deionized water wash repeatedly 60 ℃ of vacuum-dryings 1 hour, obtains CeOHSO
4Crystal.The suitable excitation wavelength of this crystalline has the glow peak of a broadening at 205-250nm at the 391nm place.
Embodiment 5.EuOHSO
4Hydro-thermal synthetic:
With 0.8 gram Eu
2O
3With nitric acid it is just dissolved, insert in the stainless steel autoclave that volume is 25ml, add 0.6 gram CS (NH subsequently
2)
2And distilled water, the compactedness that makes autoclave is 85%, 350 ℃ of reactions 5 hours, naturally cools to room temperature; The product deionized water wash 60 ℃ of vacuum-dryings 1 hour, obtains EuOHSO
4Crystal.This crystal sends the visible light of 620nm under the exciting of its maximum excitation wavelength 487nm.
Present embodiment is if adopt La
2O
3, Ce
2O
3, Pr
2O
3, Nd
2O
3, Sm
2O
3, Gd
2O
3, Tb
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3, Sc
2O
3, Y
2O
3Deng replacing Eu respectively
2O
3, behind nitric acid dissolve, with CS (NH
2)
2One reacts, and all can obtain corresponding subsulphate.
Embodiment 6.La
xCe
1-xOHSO
4The hydro-thermal of (0＜x＜1) is synthetic:
Take by weighing La (NO
3)
36H
2O and Ce (NO
3)
36H
2O (can adopt different mol ratios, for example La/Ce=1,5,9) is totally 1.0 grams, with 0.45 gram CS (NH
2)
2Placing volume is the stainless steel autoclave of 25ml, uses dissolved in distilled water, makes the compactedness of autoclave reach 85%, 300 ℃ of reactions 6 hours, naturally cools to room temperature.Product washes with water, 60 ℃ of vacuum-dryings 1 hour, obtains La
xCe
1-xOHSO
4Crystal.
For two kinds of rare earth nitrate that adopt different proportionings, for example control initial molar ratio and be respectively La/Ce=1,5,9, with CS (NH
2)
2The result of reaction has obtained La respectively
0.1Ce
0.9OHSO
4, La
0.5Ce
0.5OHSO
4And La
0.9Ce
0.1OHSO
4Crystal.
Because these crystalline chemical constitution differences, between their exciting separately and variant slightly between the emission wavelength, but suitable excitation wavelength is all at 205-250nm, and the strongest emission wavelength is at 365-395nm.Along with the increase of Ce content in the compound, the also corresponding enhancing of its luminous intensity.Therefore by regulating the chemical constitution of rare earth subsulphate, can regulate and control the luminescent properties of this material easily.
Claims (2)
1, rare earth luminescent material is characterised in that it is that molecular formula can be expressed as Ln
xLn '
1-xOHSO
4The rare earth subsulphate, wherein Ln, Ln ' are different rare earth elements, comprise La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y; 0≤x≤1.
2, rare earth luminescent material Ln
xLn '
1-xOHSO
4Solvent process for thermosynthesizing, it is characterized in that, with the aqueous solution of single or mixed rare earth nitrates and thiocarbamide or with the basic solution of rare earth nitrate and ammonium sulfate or with the basic solution of rare earth sulfate, in airtight voltage-resistant reactor, be no less than 3 hours in 200-400 ℃ of reaction; Described basic solution comprises the mixing solutions of hydrazine hydrate, ammoniacal liquor, pyridine and water or the mixing solutions of amine and water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00108496 CN1335349A (en) | 2000-07-21 | 2000-07-21 | Rare earth subsulfate luminous material and its hot synthesis in solvent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00108496 CN1335349A (en) | 2000-07-21 | 2000-07-21 | Rare earth subsulfate luminous material and its hot synthesis in solvent |
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Family
ID=4579235
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314776C (en) * | 2004-01-15 | 2007-05-09 | 山东大学 | Method for preparing long aftergrow nano luminous material at low temperature |
| CN100575454C (en) * | 2008-01-10 | 2009-12-30 | 同济大学 | Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof |
| CN106006703A (en) * | 2016-05-25 | 2016-10-12 | 中国科学院大学 | Method for preparing nano flaky cerium oxide and lanthanum-cerium hydroxysulfate by hydrothermal process |
-
2000
- 2000-07-21 CN CN 00108496 patent/CN1335349A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314776C (en) * | 2004-01-15 | 2007-05-09 | 山东大学 | Method for preparing long aftergrow nano luminous material at low temperature |
| CN100575454C (en) * | 2008-01-10 | 2009-12-30 | 同济大学 | Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof |
| CN106006703A (en) * | 2016-05-25 | 2016-10-12 | 中国科学院大学 | Method for preparing nano flaky cerium oxide and lanthanum-cerium hydroxysulfate by hydrothermal process |
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