CN105315989B - A kind of red lanthanide fluorescent material and preparation method thereof - Google Patents
A kind of red lanthanide fluorescent material and preparation method thereof Download PDFInfo
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- CN105315989B CN105315989B CN201510837621.XA CN201510837621A CN105315989B CN 105315989 B CN105315989 B CN 105315989B CN 201510837621 A CN201510837621 A CN 201510837621A CN 105315989 B CN105315989 B CN 105315989B
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Abstract
The present invention relates to a kind of preparation method of red lanthanide fluorescent material, belong to field of light emitting materials.Using rare-earth europium as luminescent center ion, use that degree of rigidity is big, be conjugated o-methoxybenzoic acid of good performance for the first part, so that energy transmission effect is good, dentritic polyamidoamine with 3-D solid structure is Ligands.First part presses 3 with Ligands:0.5 mol ratio and the europium ion of trivalent coordinate, and are reacted in pH value is 6.5~7.5 95% ethanol solution, through the ageing of 4~5 hours, have synthesized solid-state red illuminating material.The luminous intensity of prepared material is 2.5 times of the two-element match without PAMAM under the conditions of same test be the ternary complex that phenanthroline makees Ligands under the conditions of same test 1.3 times.
Description
Technical field：
The invention belongs to field of light emitting materials, and in particular to a kind of red lanthanide organic-inorganic complex fluorescent material and its
Preparation method.
Background technology:
Rare earth ion various level structure and transition regime so that it is especially paid close attention in illumination field.In life
Many fields in, such as three-color fluorescent lamp, X-ray exposure paper, colorful display screen, white fluorescence all apply rare earth hair
Luminescent material.Rare earth embedded photoluminescent material is the focus of current international forward position research.In current red light material, there is stronger electricity
Lotus transfer characteristic and stronger π-π interactions, easily produce concentration quenching effect compared with relative superiority or inferiority in filminess or concentration, cause
Fluorescence quantum efficiency reduction does not light, it is necessary to further improve fluorescence intensity even.
Eu (III) complexs are as the excellent photic red illuminating material of a class, with efficient fluorescence quantum yield and list
The features such as color is good.One key point of synthesis Eu (III) complex is the design and optimization to part, passes through the change of part
To influence the luminous efficiency, stability and structure of complex, the change of part has far-reaching influence to luminous performance.Work as difference
Part introduce around luminescent center ion, the environment around it can be changed, and cause the symmetry of neighbouring electric field to change, directly
The fluorescence intensity of influence complex is connect, this has very big work to the fluorescence efficiency and fluorescent stability that improve rare earth organic complex
With.The first different parts is different on the fluorescence property influence of rare earth ternary complexes with Ligands.
The content of the invention：
It is an object of the invention to provide a kind of rare-earth red fluorescent material and preparation method thereof, the fluorescent material is marked in biology
The fields such as note, luminescence generated by light, anti-fake material have important application prospect.
A kind of rare-earth luminescent material, structural formula is as follows：
Wherein：M is that the methoxyl group in rare earth ion, formula can not be substituted for other groups, it is characterised in that described dilute
Earth metal element is Eu；The 1.0G structures of described pamam dendrimer molecule are：
The preparation process of the rare-earth luminescent material is as follows：
1) Europium chloride is dissolved in 95% ethanol solution and forms earth solution.
2) it is 1 by the mol ratio of europium ion, o-methoxybenzoic acid and 1.0G PAMAM：3：0.5 ratio, is weighed quantitative
O-methoxybenzoic acid and 1.0G PAMAM, be dissolved in respectively in 95% ethanol solution, two kinds of ligand solutions stirred
Mix down and be mixed to get part mixed liquor dropwise；
3) under agitation, Europium chloride solution is added drop-wise in part mixed liquor dropwise, there is Precipitation, pH is adjusted
Value, obtains a large amount of white precipitates, continues to stir, and stands overnight, dry the rare-earth luminescent material under centrifuge washing, then normal temperature.
Fluorescent material luminous intensity prepared by the present invention is the two-element match without PAMAM under the conditions of same test
2.5 times, be 1.3 times of the ternary complex that phenanthroline makees Ligands under the conditions of same test.
Europium is used for rare earth luminous ion, o-methoxybenzoic acid is the first part, the PAMAM in 1.0 generations (1.0G) is the
Two parts.PAMAM plays a part of the antenna and regulation level-density parameter degree of energy transmission, improves the luminous intensity of complex.
The complex that the present invention is designed, using o-methoxybenzoic acid as the first part, polyamide-amide dendrimer
(PAMAM) it is Ligands, it is contemplated that the conjugated system size and level-density parameter degree of molecule, it is also considered that the day of energy transmission
Line is acted on.The molecular rigidity of synthesized complex is big, and level-density parameter degree is high, and luminous efficiency is high；And water of coordination is reduced, reduce
The energy loss that O-H dither is brought in water, so as to further enhance the fluorescence intensity of complex.In the present invention,
PAMAM is high as the fluorescent material luminous intensity that Ligands are made, and material property is good, with good popularizing application prospect.
Advantages of the present invention：
(1) preparation condition of the rare-earth red fluorescent material is gentle, and room temperature reaction, method is simply controllable, manufacturing cycle compared with
It is short, it can be easily separated purifying.
(2) the Ligands PAMAM selected is organic dendrimer, with good bio-compatibility, environmental protection, tool
The antenna for having energy transmission is acted on, and Energy Efficient can be passed to central ion, and the complex material fluorescence intensity of preparation is high.
Brief description of the drawings
Accompanying drawing 1 and the fluorescent emission intensity comparison diagram that Fig. 2 is Different Complex.Shown in Fig. 1, a lines do second for PAMAM and matched somebody with somebody
The fluorescence intensity of the ternary complex of body, b lines are the fluorescence intensity of the two-element match without PAMAM, and a is 2.5 times of b.Fig. 2 institutes
Show, a lines are the fluorescence intensity for the ternary complex that PAMAM does Ligands, b lines are three first wifves that phenanthroline does Ligands
The fluorescence intensity of compound, a is 1.3 times of b.L represents o-methoxybenzoic acid in figure, and phen represents phenanthroline.
Embodiment:
Embodiment 1：
(1) Europium chloride for weighing 0.2583g is dissolved in 10ml 95% ethanol solution.
(2) stoichiometrically, 0.4565g o-methoxybenzoic acid is weighed, 95% absolute ethyl alcohol for being dissolved in 15ml is molten
In liquid.
(3) stoichiometrically, 0.2580g 1.0G PAMAM are weighed, are dissolved in 10ml 95% ethanol solution.
(4) under electromagnetic agitation, (2) resulting solution is added dropwise in (3) resulting solution, continues to stir 10min, must match somebody with somebody
Body mixed solution.
(5) alcohol sodium solution of configuration 10%.
(6) under the conditions of electromagnetic agitation, Europium chloride ethanol solution obtained by (1) is added drop-wise to (4) institute dropwise with 1 drop/s speed
Obtain in part mixed liquor, there is Precipitation.PH value is adjusted to 7 with 10% alcohol sodium solution, is now separated out from solution a large amount of white
Color is precipitated, and continues stirring reaction 5 hours.
(7) overnight, centrifuge washing, dry at normal temperatures white solid powder are stood.
(8) luminous intensity fluophotometer is monitored under the conditions of 700V voltages, 1.0/1.0nm slits.
Embodiment 2：
(1) Europium chloride for weighing 0.2583g is dissolved in 10ml 95% ethanol solution.
(2) stoichiometrically, 0.4565g o-methoxybenzoic acid is weighed, 95% absolute ethyl alcohol for being dissolved in 15ml is molten
In liquid.
(3) stoichiometrically, 0.1935g 1.0G PAMAM are weighed, are dissolved in 10ml 95% ethanol solution.
(4) under electromagnetic agitation, (2) resulting solution is added dropwise in (3) resulting solution, continues to stir 10min, must match somebody with somebody
Body mixed solution.
(5) alcohol sodium solution of configuration 10%.
(6) under the conditions of electromagnetic agitation, Europium chloride ethanol solution obtained by (1) is added drop-wise to (4) institute dropwise with 1 drop/s speed
Obtain in part mixed liquor, there is Precipitation.PH value is adjusted to 7 with 10% alcohol sodium solution, is now separated out from solution a large amount of white
Color is precipitated, and continues stirring reaction 5 hours.
(7) overnight, centrifuge washing, dry at normal temperatures white solid powder are stood.
(8) luminous intensity fluophotometer is monitored under the conditions of 700V voltages, 1.0/1.0nm slits.
Embodiment 3：
(1) Europium chloride for weighing 0.2583g is dissolved in 10ml 95% ethanol solution.
(2) stoichiometrically, 0.4565g o-methoxybenzoic acid is weighed, 95% absolute ethyl alcohol for being dissolved in 15ml is molten
In liquid.
(3) stoichiometrically, 0.3870g 1.0G PAMAM are weighed, are dissolved in 15ml 95% ethanol solution.
(4) under electromagnetic agitation, (2) resulting solution is added dropwise in (3) resulting solution, continues to stir 10min, must match somebody with somebody
Body mixed solution.
(5) alcohol sodium solution of configuration 10%.
(6) under the conditions of electromagnetic agitation, Europium chloride ethanol solution obtained by (1) is added drop-wise to (4) institute dropwise with 1 drop/s speed
Obtain in part mixed liquor, there is Precipitation.PH value is adjusted to 7 with 10% alcohol sodium solution, is now separated out from solution a large amount of white
Color is precipitated, and continues stirring reaction 5 hours.
(7) overnight, centrifuge washing, dry at normal temperatures white solid powder are stood.
(8) luminous intensity fluophotometer is monitored under the conditions of 700V voltages, 1.0/1.0nm slits.
Claims (3)
1. a kind of rare-earth luminescent material, structural formula is as follows：
Wherein：Light emitting ionic is that the methoxyl group in rare earth Eu, formula can not be substituted for other groups, described pamam dendrimer molecule
1.0G structure below figures, and can not replace；Component ratio is：Europium ion, o-methoxybenzoic acid and 1.0G PAMAM rub
You are than being 1：3：0.5
2. the preparation method of rare-earth luminescent material according to claim 1, it is characterised in that preparation process is as follows：
1) it is 1 by the mol ratio of europium ion, o-methoxybenzoic acid and 1.0G PAMAM：3：0.5 ratio, weighs quantitative neighbour
Methoxy benzoic acid and 1.0G PAMAM, are dissolved in 95% ethanol solution, respectively by two kinds of ligand solutions under agitation
Part mixed liquor is mixed to get dropwise；
2) under agitation, Europium chloride solution is added drop-wise in part mixed liquor dropwise, there is Precipitation, alcohol sodium solution is used
PH value is adjusted to 7, a large amount of white precipitates are obtained, continues to stir, overnight, dry the rare earth under centrifuge washing, then normal temperature is stood
Fluorescent material.
3. the preparation method of rare-earth luminescent material according to claim 2, it is characterised in that prepared fluorescent material lights
Intensity is 2.5 times of the two-element match without PAMAM under the conditions of same test, is phenanthroline work second under the conditions of same test
1.3 times of the ternary complex of part.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775981A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material |
| CN102816176A (en) * | 2012-08-15 | 2012-12-12 | 中国科学院西安光学精密机械研究所 | Preparation method and use of trivalent europium ternary complex liquid material |
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| FR2851565B1 (en) * | 2003-02-26 | 2005-04-01 | Commissariat Energie Atomique | DENDRIMERES PHOSPHORES, PROCESS FOR THEIR PREPARATION AND THEIR USE FOR THE EXTRACTION OF ACTINIDES AND LANTHANIDES |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775981A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material |
| CN102816176A (en) * | 2012-08-15 | 2012-12-12 | 中国科学院西安光学精密机械研究所 | Preparation method and use of trivalent europium ternary complex liquid material |
Non-Patent Citations (5)
| Title |
|---|
| Na Zhao等.Synthesis, crystal structure and properties of two ternary rare earth complexes with aromatic acid and 1,10-phenanthroline.《Journal of Alloys and Compounds》.2007,第463卷第338-342页. * |
| 杨佩佩.乙酰丙酮铽基荧光复合材料的制备及性能研究.《中国优秀硕士学位论文全文数据库（工程科技I辑）》.2013,第B020-43页. * |
| 牛贵平.稀土配合物掺杂聚合物复合材料的制备及性能研究.《中国优秀硕士学位论文全文数据库（工程科技I辑）》.2011,(第S2期),第B020-130页. * |
| 莫尊理等.PAMAM/乙酰丙酮铽复合物的制备及其性能研究.《西北师范大学学报（自然科学版）》.2011,第47卷第53-57页. * |
| 马瑞霞.铕芳香羧酸配合物的合成、晶体结构及发光性能研究.《中国优秀硕士学位论文全文数据库（工程科技I辑）》.2006,(第9期),第B014-173页. * |
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