CN1315981C - Dual wave section fluorescent material and its preparaton method - Google Patents
Dual wave section fluorescent material and its preparaton method Download PDFInfo
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- CN1315981C CN1315981C CNB2004100234180A CN200410023418A CN1315981C CN 1315981 C CN1315981 C CN 1315981C CN B2004100234180 A CNB2004100234180 A CN B2004100234180A CN 200410023418 A CN200410023418 A CN 200410023418A CN 1315981 C CN1315981 C CN 1315981C
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Abstract
The present invention provides a dual wave section fluorescent material and a preparation method. The fluorescent material has the formula of (Mx Eu<1-x>) AyBz, wherein the M in the formula is one of gadolinium (Gd), yttrium (Y), terbium (Tb), dysprosium (Dy) and lanthanum (La) or the combination of the elements according to any proportion, the A is a beta-diketone compound, the B is selected from a heteroaromatic compound of 2, 2' dipyridine, phenanthroline and 8-hydroxyquinoline or is selected from a compound containing of P and O, such as trioctylphosphine oxide, triphenylphosphine oxide and tributylphosphine oxide, the x is smaller than 1 and is larger than 0, the y is equal to 2 or 3 or 4, and the z is equal to 1 or 2. The preparation method comprises the following steps: firstly, rare earth chloride or rare earth nitrate is dissolved in absolute alcohol to obtain a solution I; secondly, organic ligand is respectively taken according to the molar ratio in the formula to be mixed and dissolved in the absolute alcohol to obtain a solution II; thirdly, the solution I and the solution II are mixed to be agitated, heated, statically placed, washed and filtered, and obtained deposit is dried to obtain a product.
Description
Technical field
The invention belongs to field of light emitting materials, relate in particular to a kind of two waveband fluorescent material and preparation method.
Background technology
The light of different-waveband has different effects to growth and development of plants in the solar spectrum, and UV-light has detrimentally affect to the growth of plant, and yellow green light is sharp for the harmless nothing of plant, and blue light helps the growth of plant stem-leaf etc., and ruddiness then helps the reproductive growth of plant.Exploitation can absorb the agricultural light conversion film of ultraviolet light emission blue light and ruddiness, more science utilize sun power, promote the development of the high-tech ecological agriculture, key is to have the commentaries on classics light additive of efficient stable.
The plastic sheeting for farm use of having developed at present is broadly divided into three classes with changeing the light additive: inorganics, organism and rare earth organic complex.Wherein organism class fluorescent material mainly is organic reducing dyestuff and high-visibility pigment, and oxidation and Degradation easily take place under action of ultraviolet radiation this class fluorescent material, and photo and thermal stability is poor, and work-ing life is shorter.Inorganics class fluorescent material mostly is rare earth element oxysulfide or rare earth doped alkaline earth sulfide, aluminate, borate, silicate etc., and photo and thermal stability is superior, long service life, but add in the plastic sheeting for farm use poor with the consistency of resin.Comparatively speaking, rare earth organic complex class fluorescent material has photo and thermal stability and good with resin compatible preferably, is that comparatively the ideal plastic sheeting for farm use changes the light additive.
Because the superior performance of rare earth organic complex class fluorescent material, this field becomes the focus of research in recent years.The CN 1098326C that CN 1052493C, the 2003.1.8 that announces as the disclosed CN 1105040A of Chinese patent 1995.7.12, the disclosed CN 1132219A of 1996.10.2, the disclosed CN 1140744A of 1997.1.22, the disclosed CN 1186835A of 1998.7.8, the disclosed CN 1221005A of 1999.6.30,2000.5.17 announces, its fluorescence additive are the rare earth organic complex of rare earth element and organic ligand formation.Yet, above-mentioned fluorescent material only possesses the single band that absorbs ultraviolet light emission ruddiness changes the light function, can not realize the two band optical energy conversion of bionical attitude.
Goal of the invention
One of purpose of the present invention is to provide a kind of two waveband fluorescent material that can carry out the two band optical energy conversion at demand of plant growth, to carry out the exploitation of light conversion film, promotes agricultural development; Two of purpose provides simple, the mild condition of a kind of technology, the two waveband Preparation of Fluorescent Material method of easy handling.
One of purpose of the present invention can realize by following technical measures:
By selecting suitable part, synthetic two waveband fluorescent material can absorb UV-light red-emitting and blue light simultaneously, and its general formula is: (M
xEu
1-x) A
yB
z, M is one or more the arbitrary proportion combination in gadolinium (Gd), yttrium (Y), terbium (Tb), dysprosium (Dy), the lanthanum (La) in the formula; A is a thenoyltrifluoroacetone; B is phenanthroline: 0.9＜x＜0.95, and y is 3, and z is 1.
Two of purpose of the present invention can realize by following technical measures:
A, get rare earth oxide earlier in composition in the general formula and ratio, be dissolved in dilute hydrochloric acid or the rare nitric acid, fall unnecessary water and acid with the water-bath heated volatile, obtain the mixture of corresponding rare earth chloride or rare earth nitrate, be dissolved in the dehydrated alcohol again, perhaps get rare earth chloride or rare earth nitrate and be dissolved in the dehydrated alcohol, get solution I;
B, get organic ligand respectively by mol ratio in the general formula, mixed dissolution obtains solution II in dehydrated alcohol;
C, solution I and solution II are mixed, through stirring, heat, leaving standstill, washing and suction filtration, gained precipitate drying and get product.
The fluorescent material that the present invention makes is the pulverulent solids of uniform and smooth, particle diameter is about 0.2 μ m, can absorb the UV-light of 270～410nm, and be blue light and ruddiness with the energy transformation that absorbs, possess two waveband and change the light function, light intensity height and good stability, being suitable as plastic sheeting for farm use changes the light additive, meets demand of plant growth.UV-light concentrates irradiation experiment to show that fluorescent material has good light stability.The fusing point of fluorescent material is more than 220 ℃, and differential thermal and thermogravimetric experiment show that fluorescent material has good thermostability.One of two waveband fluorescent material characteristics provided by the invention be can be by changing M in the general formula composition and the value of x change the relative power that institute launches blue light and ruddiness, therefore, both can be used as the plastic sheeting for farm use additive that satisfies common proportion of crop planting demand (blue light and red light intensity are suitable), also can be used as satisfy special plantation demand (as a little less than the Lan Qianghong or blue weak red strong) the plastic sheeting for farm use additive, applicability is strong.In addition, fluorescent material provided by the invention also can be used as photic or electroluminescent material is applied to other field.Preparation method's technology of the present invention is simple, mild condition, and facility investment is few, easy handling.
Embodiment
Take by weighing Dy
2O
30.0537g (2.375 * 10
-4Mol) Eu
2O
30.0044g (1.25 * 10
-5Mol), be dissolved in excessive 6mol l
-1In the dilute hydrochloric acid,, vapor away unnecessary water and acid, obtain the mixed microcrystalline of Yttrium trichloride and Europium trichloride, and then be dissolved in about 5ml dehydrated alcohol, obtain solution I with 80 ℃ of left and right sides heating in water bath; Take by weighing TTA0.3333g (1.50 * 10
-3Mol), phen 0.0991g (0.50 * 10
-3Mol), be dissolved in about 5ml dehydrated alcohol, obtain solution II; Under the normal temperature solution I and solution II are mixed, stir and, left standstill under the normal temperature 3-5 days, obtain milky white precipitate with 80 ℃ of left and right sides heating in water bath 5 minutes.To gained precipitation absolute ethanol washing, suction filtration, the dry multi-kernel rare-earth organic coordination compound two waveband fluorescent material product that gets.This material has wide band absorption at ultraviolet region, and maximum absorption band lays respectively at 290nm and 400nm, and fluorescence emission peak is 423mn and 614nm.
Take by weighing Dy
2O
30.0839g (2.25 * 10
-4Mol), Eu
2O
30.0088g (2.5 * 10
-5Mol), be dissolved in excessive 6mol l
-1In the dilute hydrochloric acid,, vapor away unnecessary water and acid, obtain the mixed microcrystalline of Dysprosium trichloride and Europium trichloride, and then be dissolved in about 5ml dehydrated alcohol, obtain solution I with 80 ℃ of left and right sides heating in water bath; Take by weighing TTA0.3333g (1.50 * 10
-3Mol), phen 0.0991g (0.50 * 10
-3Mol), be dissolved in about 5ml dehydrated alcohol, obtain solution II; Under the normal temperature solution I and solution II are mixed, stir and, left standstill under the normal temperature 3-5 days, obtain milky white precipitate with 80 ℃ of left and right sides heating in water bath 5 minutes.To gained precipitation absolute ethanol washing, suction filtration, the dry multi-kernel rare-earth organic coordination compound two waveband fluorescent material product that gets.This material has wide band absorption at ultraviolet region, and maximum absorption band is positioned at 290nm and 398nm, and fluorescence emission peak is 422nm and 614nm.
Embodiment 3
Take by weighing Tb
4O
70.0842g (1.125 * 10
-4Mol), Eu
2O
30.0088g (2.5 * 10
-5Mol), be dissolved in excessive 6mol l
-1In the dilute hydrochloric acid,, vapor away unnecessary water and acid, obtain the mixed microcrystalline of terbium chloride and Europium trichloride, and then be dissolved in about 5ml dehydrated alcohol, obtain solution I with 80 ℃ of left and right sides heating in water bath; Take by weighing TTA0.3333g (1.50 * 10
-3Mol), phen 0.0991g (0.50 * 10
-3Mol), be dissolved in about 5ml dehydrated alcohol, obtain solution II; Under the normal temperature solution I and solution II are mixed, stir and, left standstill under the normal temperature 3-5 days, obtain milky white precipitate with 80 ℃ of left and right sides heating in water bath 5 minutes.To gained precipitation absolute ethanol washing, suction filtration, the dry multi-kernel rare-earth organic coordination compound two waveband fluorescent material product that gets.This material has wide band absorption at ultraviolet region, and maximum absorption band is positioned at 276nm and 390nm, and fluorescence emission peak is 423nm and 614mn.
Embodiment 4
Get Gd
2O
30.0408g (1.125 * 10
-4Mol), Dy
2O
30.0420g (1.125 * 10
-4Mol), Eu
2O
30.0088g (2.5 * 10
-5Mol), be dissolved in excessive 6mol l
-1In the hydrochloric acid,, vapor away unnecessary water and acid, obtain the mixed microcrystalline of rare earth chloride, and then be dissolved in about 5ml dehydrated alcohol, obtain solution I with 80 ℃ of left and right sides heating in water bath; Get TTA 0.3333g (1.50 * 10
-3Mol), phen 0.0991g (0.50 * 10
-3Mol), be dissolved in about 5ml dehydrated alcohol, obtain solution II; Under the normal temperature solution I and solution II are mixed, stir and, left standstill under the normal temperature 3-5 days, obtain milky white precipitate with 80 ℃ of left and right sides heating in water bath 5 minutes.To gained precipitation absolute ethanol washing, suction filtration, the dry multi-kernel rare-earth organic coordination compound two waveband fluorescent material product that gets.This material has wide band absorption at ultraviolet region, and maximum absorption band lays respectively at 277nm and 391nm, and fluorescence emission peak is 423nm and 614nm.
Take by weighing Dy
2O
30.0420g (1.125 * 10
-4Mol), Tb
4O
70.0421g (5.625 * 10
-5Mol), Eu
2O
30.0088g (2.5 * 10
-5Mol), be dissolved in excessive 6mol l
-1In the hydrochloric acid,, vapor away unnecessary water and acid, obtain the mixed microcrystalline of rare earth chloride, and then be dissolved in about 5ml dehydrated alcohol, obtain solution I with 80 ℃ of left and right sides heating in water bath; Take by weighing TTA 0.3333g (1.50 * 10
-3Mol), phen 0.0991g (0.50 * 10
-3Mol), be dissolved in about 5ml dehydrated alcohol, obtain solution II; Under the normal temperature solution I and solution II are mixed, stir and, left standstill under the normal temperature 3-5 days, obtain milky white precipitate with 80 ℃ of left and right sides heating in water bath 5 minutes.To gained precipitation absolute ethanol washing, suction filtration, the dry multi-kernel rare-earth organic coordination compound two waveband fluorescent material product that gets.This material has wide band absorption at ultraviolet region, and maximum absorption band lays respectively at 278nm and 393nm, and fluorescence emission peak is 423nm and 614nm.
Description of drawings
Fig. 1 is the solid fluorescence spectrogram of embodiment 1 products obtained therefrom;
Fig. 2 is the solid fluorescence spectrogram of embodiment 2 products obtained therefroms;
Fig. 3 is the solid fluorescence spectrogram of embodiment 3 products obtained therefroms;
Fig. 4 is the solid fluorescence spectrogram of embodiment 4 products obtained therefroms;
The emission spectrogram that Fig. 5 obtains with the ultraviolet excitation of 380nm for embodiment 4 products obtained therefroms;
Fig. 6 is the solid fluorescence spectrogram of embodiment 5 products obtained therefroms;
The emission spectrogram that Fig. 7 obtains with the ultraviolet excitation of 380nm for embodiment 5 products obtained therefroms;
Fig. 8 is the transmission electron microscope picture of fluorescent material.
Claims (2)
1, a kind of two waveband fluorescent material is characterized in that this fluorescent material can absorb UV-light red-emitting and blue light simultaneously, and its general formula is (M
xEu
1-x) A
yB
z
In the formula
M is one or more the arbitrary proportion combination in gadolinium, yttrium, terbium, dysprosium, the lanthanum;
A is a thenoyltrifluoroacetone;
B is phenanthroline: 0.9＜x＜0.95, and y is 3, and z is 1.
2, the described two waveband Preparation of Fluorescent Material of a kind of claim 1 method is characterized in that
A, get rare earth oxide earlier, be dissolved in dilute hydrochloric acid or the rare nitric acid, fall unnecessary water and acid with the water-bath heated volatile, obtain the mixture of corresponding rare earth chloride or rare earth nitrate, be dissolved in again in the dehydrated alcohol, perhaps get rare earth chloride or rare earth nitrate and be dissolved in the dehydrated alcohol, get solution I;
B, get organic ligand respectively by mol ratio in the general formula, mixed dissolution obtains solution II in dehydrated alcohol;
C, solution I and solution II are mixed, through stirring, heat, leaving standstill, washing and suction filtration, gained precipitate drying and get product.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792508B (en) * | 2010-02-10 | 2012-06-06 | 黑龙江大学 | Unconjugated organic phosphorus, oxide and rare earth coordination polymer as well as preparation method and application thereof |
| CN105622981B (en) * | 2015-01-05 | 2019-02-22 | 侯培毅 | A kind of preparation method of rare-earth fluorescent auxiliary agent |
| CN106947462A (en) * | 2017-05-11 | 2017-07-14 | 长春工业大学 | A kind of rare earth organic light conversion agents and preparation method thereof |
| CN108103609B (en) * | 2017-11-16 | 2020-06-30 | 北京石油化工学院 | Dual-wavelength fluorescent anti-counterfeiting composite nanofiber with phase change function and preparation method thereof |
| CN107946412B (en) * | 2017-12-25 | 2020-08-04 | 青岛大学 | Preparation method of rare earth complex solution and modified solar cell |
| CN110885676A (en) * | 2018-09-10 | 2020-03-17 | 阜阳师范学院 | Double-core double-ligand rare earth composite fluorescent material and preparation method thereof |
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2004
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Non-Patent Citations (6)
| Title |
|---|
| 二苯甲酰基甲烷2,2'-联吡噻混合稀土配合物中钆,钇对铕发光的影响 赵永亮，赵凤英，发光学报，第23卷第3期 2002 * |
| 二苯甲酰基甲烷2,2'-联吡噻混合稀土配合物中钆,钇对铕发光的影响 赵永亮，赵凤英，发光学报，第23卷第3期 2002;稀土与HTTA和PHEN配合物的合成及其共发光效应的研究 高改玲，张安支，黄凤霞，钱博，陕西师范大学学报(自然科学版)，第25卷第1期 1997;稀土酯位化合物光转换剂的设计 李建宇，张颂培，曾红，中国塑料，第13卷第1期 1999;在有机电致发光中TB(III)对EU(III)的发光增强现象 赵东旭，李文连，洪自荐，梁春军，赵丹，彭俊彪，刘星元，发光学报，第19卷第4期 1998;铕(111)多核配合物的形成及其荧光增强效应 刘德文，闫爱华，吴爱萍，发光学报，第20卷第3期 1999 * |
| 在有机电致发光中TB(III)对EU(III)的发光增强现象 赵东旭，李文连，洪自荐，梁春军，赵丹，彭俊彪，刘星元，发光学报，第19卷第4期 1998 * |
| 稀土与HTTA和PHEN配合物的合成及其共发光效应的研究 高改玲，张安支，黄凤霞，钱博，陕西师范大学学报(自然科学版)，第25卷第1期 1997 * |
| 稀土酯位化合物光转换剂的设计 李建宇，张颂培，曾红，中国塑料，第13卷第1期 1999 * |
| 铕(111)多核配合物的形成及其荧光增强效应 刘德文，闫爱华，吴爱萍，发光学报，第20卷第3期 1999 * |
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