CN101560384A - Europium-(trifluoroacetylacetone)3-1, 10-phenanthroline/silica core/shell nanocomposite fluorescent material - Google Patents
Europium-(trifluoroacetylacetone)3-1, 10-phenanthroline/silica core/shell nanocomposite fluorescent material Download PDFInfo
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- CN101560384A CN101560384A CNA2008101042665A CN200810104266A CN101560384A CN 101560384 A CN101560384 A CN 101560384A CN A2008101042665 A CNA2008101042665 A CN A2008101042665A CN 200810104266 A CN200810104266 A CN 200810104266A CN 101560384 A CN101560384 A CN 101560384A
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- tta
- phen
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- trifluoroacetylacetone
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Abstract
The invention relates to an Eu-(TTA)3-1,10-phen/SiO2 core/shell type nano composite fluorescent material belonging to the preparation field of composite fluorescent materials. TTA is used as a first ligand and phen is used as a second ligand to prepare Eu-(TTA)3phen ligand which is the novel photoluminescence material and is hydrolyzed under the function of base catalyst by TEOS, and a layer of SiO2 shell is formed on the surface of a rare-earth composition so as to obtain rare-earth ligand nano particles with stable fluorescence intensity. The invention has the advantages of simple preparation process, low cost of raw materials, reaction at normal temperature and low energy consumption. Because the SiO2 shell is separated from oxygen and water in the air, compared with the Eu-(TTA)3phen fluorescent material, the Eu-(TTA)3phen/SiO2 core/shell type nano composite fluorescent material has greatly improved stability under the ultraviolet irradiation, strengthened fluorescent emission intensity and better UV absorptivity.
Description
Technical field
The invention belongs to the composite fluorescent material preparation field, a kind of europium-(trifluoroacetylacetone) particularly is provided
3-1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline/silica core/core-shell type nanometer composite fluorescent material of 10-.
Background technology
Rare earth element has unique 4f out-shell electron layer structure, light, electricity, magnetic property, the especially rare earth element that its compound shows many excellences have general element incomparable spectroscopic properties, so the application of rare earth luminescent material is especially noticeable.Now, the rare earth luminous whole solid luminescence field that almost related to.Rare earth luminescent material is widely used in illumination, shows and detects three big fields, great industrial production and consumption market scale have been formed, and expanding to other emerging technology fields, and rare earth compound function and application Study on Technology is the important topic of 21 century chemistry.In recent years, rare earth organic complex more and more causes people's extensive concern owing to have the high advantage of luminous intensity, and its applied research is very active.Yet there is the problem of stability difference in rare earth organic fluorescent materials as embedded photoluminescent material, and its fluorescent emission intensity can weaken gradually under UV-irradiation, until the forfeiture fluorescence property.Short duration of service as anti-counterfeiting mark, be difficult to play permanent false proof purpose.Need try every possible means to be improved.For overcoming the above problems, be first part with trifluoroacetylacetone (TTA), phenanthroline (phen) is that second part prepares Eu (TTA)
3This photoluminescent material of phen title complex afterwards by tetraethoxy (TEOS) hydrolysis under the alkaline catalysts effect, forms one deck SiO on the rare earth compounding surface
2Shell is to obtain the stable rare earth compounding nano particle of fluorescence intensity.
Summary of the invention
The object of the present invention is to provide a kind of europium-(trifluoroacetylacetone)
3-1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline/silica core/core-shell type nanometer composite fluorescent material of 10-has solved Eu (TTA)
3This rare earth organic complex embedded photoluminescent material of phen stability is poor, and its fluorescent emission intensity can weaken gradually under UV-irradiation, until the problem of forfeiture fluorescence property.Its preparation method technology is simple, and the prices of raw and semifnished materials are cheap, reaction at normal temperatures, and energy consumption is extremely low.Because SiO
2Shell has completely cut off airborne oxygen and water, than Eu (TTA)
3The phen fluorescent material, Eu (TTA)
3Phen/SiO
2Core/shell type nano-composite fluorescent material its stability under uviolizing improves greatly, and fluorescent emission intensity also has enhancing, and better uv absorption property is arranged.
Technical scheme of the present invention is to be first part with trifluoroacetylacetone (TTA) at first, 1, and the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-(phen) is second part, with europium chloride (EuCl
36H
2O) provide central ion Eu
3+Preparation Eu (TTA)
3Phen is then with Eu (TTA)
3Phen and tetraethoxy (TEOS) are dispersed in the ethanol, and under the catalysis of ammoniacal liquor, teos hydrolysis generates silicon-dioxide, with Eu (TTA)
3Phen is nuclear, and coated with silica is in Eu (TTA)
3The phen surface generates Eu (TTA)
3Phen/SiO
2The core/shell type nano-composite fluorescent material.Its processing step is as follows:
Step (a): preparation Eu (TTA)
3Phen rare earth organic complex embedded photoluminescent material
Take by weighing the crystal and the 3mmol organic ligand trifluoroacetylacetone of 1mmol europium chloride, these two kinds of materials are dissolved in the ethanolic soln of 30mL jointly, can filter if any insoluble impurity.Constantly in above-mentioned solution, add the 3mmol triethylamine under the stirring condition then.Constantly adding 1mmol second ligand 1 under the stirring condition at last, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-has white precipitate and generates.Constantly stir the filter cake that uses husky plate funnel suction filtration precipitation to obtain after for some time and be the product rare earth compounding.For the unreacting material that adheres in the washes clean product, the rare earth compounding that generates can be used ethanol or water washing several times, suction filtration then, drying for standby.
Step (b): preparation generates Eu (TTA)
3Phen/SiO
2Composite fluorescent material
Measure the 100mL dehydrated alcohol, 0.5g Eu (TTA)
3Phen and 1.1mL tetraethoxy are in beaker, and ultrasonic concussion 20min makes to mix, as solution A; Accurately measure 2mL ammoniacal liquor in addition, 0.25mL deionized water and 50mL dehydrated alcohol are in beaker, and ultrasonic concussion 20min mixes it, as solution B.Under continuous stirring condition, slowly solution B is added drop-wise in the solution A, drip and finish back continuation stirring 12h.The suction filtration precipitation, dry 1h under 120 ℃.Obtain europium-(trifluoroacetylacetone)
3-1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline/silica core/core-shell type nanometer composite fluorescent material of 10-.
Compared with prior art, the invention has the advantages that:
Preparation method's technology is simple, and the prices of raw and semifnished materials are cheap, reaction at normal temperatures, and energy consumption is extremely low.Because SiO
2Shell has completely cut off airborne oxygen and water, than Eu (TTA)
3The phen fluorescent material, Eu (TTA)
3Phen/SiO
2Core/shell type nano-composite fluorescent material its stability under uviolizing improves greatly, and fluorescent emission intensity also has enhancing, and better uv absorption property is arranged.
Description of drawings
Fig. 1 is Eu (TTA)
3Phen/SiO
2The transmission electron microscope photo.
Fig. 2 is Eu (TTA)
3Phen and Eu (TTA)
3Phen/SiO
2Fluorescence emission spectrum.
Fig. 3 is Eu (TTA)
3Phen and Eu (TTA)
3Phen/SiO
2Uv drs spectrum.
Fig. 4 is Eu (TTA)
3Phen and Eu (TTA)
3Phen/SiO
2Infrared spectra.
Fig. 5 is Eu (TTA)
3Phen and Eu (TTA)
3Phen/SiO
2The fluorescence spectrum and the time dependent curve of fluorescence intensity level of strong emission place.
Embodiment
At first, take by weighing the crystal and the 3mmol organic ligand trifluoroacetylacetone of 1mmol europium chloride, these two kinds of materials are dissolved in the ethanolic soln of 30mL jointly, can filter if any insoluble impurity.Constantly in above-mentioned solution, add the 3mmol triethylamine under the stirring condition then.Constantly adding 1mmol second ligand 1 under the stirring condition at last, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-has white precipitate and generates.Constantly stir the filter cake that uses husky plate funnel suction filtration precipitation to obtain after for some time and be the product rare earth compounding.For the unreacting material that adheres in the washes clean product, the rare earth compounding that generates can be used ethanol or water washing several times, suction filtration then, drying for standby.
Measure the 100mL dehydrated alcohol, 0.5g Eu (TTA)
3Phen and 1.1mL tetraethoxy are in beaker, and ultrasonic concussion 20min makes to mix, as solution A; Accurately measure 2mL ammoniacal liquor in addition, 0.25mL deionized water and 50mL dehydrated alcohol are in beaker, and ultrasonic concussion 20min mixes it, as solution B.Under continuous stirring condition, slowly solution B is added drop-wise in the solution A, drip and finish back continuation stirring 12h.The suction filtration precipitation, dry 1h under 120 ℃.Obtain europium-(trifluoroacetylacetone)
3-1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline/silica core/core-shell type nanometer composite fluorescent material of 10-.
Use JEOL JSM-2010 type transmission electron microscope to Eu (TTA)
3Phen/SiO
2Pattern characterize, the result as shown in Figure 1, Eu (TTA)
3Phen/SiO
2Be the nanometer particle of shell-nuclear shape, Eu (TTA)
3Phen is coated in the silicon-dioxide, and its diameter is less than 100nm.Because the silicon-dioxide that generates dissolves in ammoniacal liquor, its surperficial electric double layer is gone to pot and cause reunion.
Use the F-4500 fluorescence spectrophotometer to Eu (TTA)
3Phen and Eu (TTA)
3Phen/SiO
2Fluorescence emission spectrum characterize excitation wavelength 380nm, slit 2nm, useful range 575nm-650nm.The result as shown in Figure 2, Eu (TTA)
3Phen/SiO
2The fluorescence emission spectral intensity be greater than not the Eu (TTA) that coats
3Phen.
Use 725 type ultraviolet-visible pectrophotometers to Eu (TTA)
3Phen/SiO
2And Eu (TTA)
3The uv drs spectrum of phen characterizes useful range 200nm-500nm.The result as shown in Figure 3, than Eu (TTA)
3Phen, Eu (TTA)
3Phen/SiO
2Reflectivity in the near ultraviolet region obviously reduces, and to ultraviolet maximum absorption band generation blue shift, illustrates that its specific absorption to UV-light improves, and uv absorption property has clear improvement before not coating.
Use Nlcolet-210 type Fourier infrared spectrograph to Eu (TTA)
3Phen/SiO
2And Eu (TTA)
3The infrared spectra of phen characterizes, useful range 400cm
-1-4000cm
-1The result as shown in Figure 4, Eu (TTA)
3Each vibration absorption peak is at Eu (TTA) in the infrared spectrum of phen
3Phen/SiO
2Infrared spectra in all occur, and at Eu (TTA)
3Phen/SiO
2Infrared spectra in Si has appearred
2The characteristic peak of O, wherein 472cm
-1Be the flexural vibration peak of Si-O-Si key, 1080cm
-1(broad peak) is the symmetrical stretching vibration peak of Si-O-Si, and this has proved Eu in the product (TTA)
3Phen and Si
2The existence of O, except that time other chemical bond infrared absorption peak does not appear, prove SiO
2At Eu (TTA)
3The phen surface coats for physics, with Eu (TTA)
3Chemical reaction does not take place between the phen.
Use the F-4500 fluorescence spectrophotometer respectively to Eu (TTA)
3Phen and Eu (TTA)
3Phen/SiO
2Carry out fluorescence intensity stability and characterize, under the ultraviolet prolonged exposure of wavelength 380nm, measured the fluorescence emission spectrum of a material every five minutes, note the fluorescence intensity level of locating in the strongest emission (611.4nm), obtain Eu (TTA) respectively
3Phen and Eu (TTA)
3Phen/SiO
2At the time dependent curve of fluorescence intensity level of strong emission place.The result as shown in Figure 5, along with the prolonged exposure of UV-light, Eu (TTA)
3The fluorescent emission intensity of phen weakens gradually, and Eu (TTA)
3Phen/SiO
2Fluorescent emission intensity then almost remain unchanged.This explanation is owing to completely cut off airborne oxygen and water, and the fluorescent stability of product is than Eu (TTA)
3Phen has significant improvement.
Claims (1)
1. europium-(trifluoroacetylacetone)
3-1,10-phenanthroline/silica core/core-shell type nanometer composite fluorescent material.It is characterized in that reacting and carry out as follows:
Step (a): preparation Eu (TTA)
3Phen rare earth organic complex embedded photoluminescent material
Take by weighing the crystal and the 3mmol organic ligand trifluoroacetylacetone of 1mmol europium chloride, these two kinds of materials are dissolved in the ethanolic soln of 30mL jointly, can filter if any insoluble impurity.Constantly in above-mentioned solution, add the 3mmol triethylamine under the stirring condition then.Constantly adding 1mmol second ligand 1 under the stirring condition at last, the 10-phenanthroline has white precipitate and generates.Constantly stir the filter cake that uses husky plate funnel suction filtration precipitation to obtain after for some time and be the product rare earth compounding.For the unreacting material that adheres in the washes clean product, the rare earth compounding that generates can be used ethanol or water washing several times, suction filtration then, drying for standby.
Step (b): preparation generates Eu (TTA)
3Phen/SiO
2Composite fluorescent material
Measure the 100mL dehydrated alcohol, 0.5g Eu (TTA)
3Phen and 1.1mL tetraethoxy are in beaker, and ultrasonic concussion 20min makes to mix, as solution A; Accurately measure 2mL ammoniacal liquor in addition, 0.25mL deionized water and 50mL dehydrated alcohol are in beaker, and ultrasonic concussion 20min mixes it, as solution B.Under continuous stirring condition, slowly solution B is added drop-wise in the solution A, drip and finish back continuation stirring 12h.The suction filtration precipitation, dry 1h under 120 ℃.Obtain europium-(trifluoroacetylacetone)
3-1,10-phenanthroline/silica core/core-shell type nanometer composite fluorescent material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101042665A CN101560384A (en) | 2008-04-18 | 2008-04-18 | Europium-(trifluoroacetylacetone)3-1, 10-phenanthroline/silica core/shell nanocomposite fluorescent material |
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|---|---|---|---|
| CNA2008101042665A CN101560384A (en) | 2008-04-18 | 2008-04-18 | Europium-(trifluoroacetylacetone)3-1, 10-phenanthroline/silica core/shell nanocomposite fluorescent material |
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| CN102592716A (en) * | 2011-09-23 | 2012-07-18 | 长春理工大学 | Magnetic and optical dual-function coaxial nano cable and preparation method thereof |
| CN105801608A (en) * | 2016-04-15 | 2016-07-27 | 阜阳师范学院 | Novel rare earth europium complex and preparation method thereof |
| CN106190103A (en) * | 2016-06-30 | 2016-12-07 | 武汉工程大学 | Hydrophobic silica rare earth nano fluorescent material and preparation method thereof |
| CN106243835A (en) * | 2015-07-20 | 2016-12-21 | 广东壮丽彩印股份有限公司 | A kind of aqueous rare earth compounding complex microsphere fluorescent ink and preparation technology thereof |
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| CN107384375A (en) * | 2017-07-21 | 2017-11-24 | 洛阳师范学院 | A kind of rare earth luminous silicon dioxide hybrid materials and its preparation method and application |
| CN109504366A (en) * | 2019-01-07 | 2019-03-22 | 青岛大学 | A kind of rare-earth complex cladding nano-hollow SiO2With cladded type rare-earth complex and preparation method thereof |
| CN110734760A (en) * | 2018-07-19 | 2020-01-31 | 阜阳师范学院 | rare earth europium composite fluorescent material using sodium acetate as matrix and preparation method thereof |
| 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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| CN102592716B (en) * | 2011-09-23 | 2014-06-11 | 长春理工大学 | Magnetic and optical dual-function coaxial nano cable and preparation method thereof |
| CN102592716A (en) * | 2011-09-23 | 2012-07-18 | 长春理工大学 | Magnetic and optical dual-function coaxial nano cable and preparation method thereof |
| CN106243835A (en) * | 2015-07-20 | 2016-12-21 | 广东壮丽彩印股份有限公司 | A kind of aqueous rare earth compounding complex microsphere fluorescent ink and preparation technology thereof |
| CN105801608A (en) * | 2016-04-15 | 2016-07-27 | 阜阳师范学院 | Novel rare earth europium complex and preparation method thereof |
| CN106190103A (en) * | 2016-06-30 | 2016-12-07 | 武汉工程大学 | Hydrophobic silica rare earth nano fluorescent material and preparation method thereof |
| CN106190103B (en) * | 2016-06-30 | 2018-08-03 | 武汉工程大学 | Hydrophobic silica rare earth nano fluorescent material and preparation method thereof |
| CN106350057B (en) * | 2016-08-18 | 2018-11-20 | 青岛大学 | A kind of preparation method of fluorescence nano hybrid particle |
| CN106350057A (en) * | 2016-08-18 | 2017-01-25 | 青岛大学 | Preparation method of fluorescent hybrid nanoparticles |
| CN107384375A (en) * | 2017-07-21 | 2017-11-24 | 洛阳师范学院 | A kind of rare earth luminous silicon dioxide hybrid materials and its preparation method and application |
| CN107384375B (en) * | 2017-07-21 | 2019-09-03 | 洛阳师范学院 | A kind of rare earth luminous silicon dioxide hybrid materials and its preparation method and application |
| CN110734760A (en) * | 2018-07-19 | 2020-01-31 | 阜阳师范学院 | rare earth europium composite fluorescent material using sodium acetate as matrix and preparation method thereof |
| 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 |
| CN109504366A (en) * | 2019-01-07 | 2019-03-22 | 青岛大学 | A kind of rare-earth complex cladding nano-hollow SiO2With cladded type rare-earth complex and preparation method thereof |
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Open date: 20091021 |