CN101892053A - Silicon dioxide-rare earth phosphate core-shell structure fluorescent material and preparation method thereof - Google Patents
Silicon dioxide-rare earth phosphate core-shell structure fluorescent material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicon dioxide-rare earth phosphate core-shell structure fluorescent material and a preparation method thereof. The fluorescent material is prepared by dissolving La2O3, Tb(NO3)3.6H2O and Ce(NO3)3.6H2O in dilute nitric acid respectively to prepare rare earth ionic solutions; preparing a mixed rare earth ionic solution in proportions; dissolving sodium tripolyphosphate in water to prepare a sodium tripolyphosphate solution; adding the mixed rare earth ionic solution into the sodium tripolyphosphate solution dropwise, and stirring to obtain a mixed solution for preparing a shell material; adding SiO2 spherical particles as a core material into the mixed solution for preparing a shell material; and after reaction, collecting the silicon dioxide-rare earth phosphate core-shell structure fluorescent material by cooling, filtering, washing and vacuum drying. The silicon dioxide-rare earth phosphate core-shell structure spherical flourescent material has the advantages of regular form, low cost and simple preparation process, is suitable for batch production, and has an important application value for lighting industry.
Description
Technical field
The present invention relates to a kind of rare earth compound fluorescent material, particularly relate to silicon dioxide-rare earth phosphate core-shell structured fluorescence material and preparation method thereof.
Background technology
Because receptivity is strong, the turnover ratio height has very strong emission in the visible region, and physicochemical property are stable, and rare-earth luminescent material has now become the propping material in photoelectric component, illumination, exhibited light field.In rare-earth luminescent material, the RE phosphate fluorescent material gets most of the attention, and this type of material most important applications is exactly the luminescent material as electricity-saving lamp.China is first big producing country of energy-conservation lamp phosphor at present, day by day the contradiction between rare earth element consumption of Zeng Jiaing and the limited rare-earth mineral reserves is outstanding day by day, how to adopt appropriate means reduce effectively the RE phosphate fluorescent material synthetic cost, improve its product performance, reduce rare earth element dosage, improve the utilization ratio of rare earth resources, just become the urgent and important problem that luminouslighting material field is faced.
Preparation nucleocapsid structure material is an important means being adopted of synthesizing new fluorescent material in recent years.Owing to have and be easy to be made into spherical monodisperse particles, advantages such as particle diameter is controlled easily, and is synthetic with low cost, silicon-dioxide are usually used in the preparation of core-shell structured fluorescence particulate, as employing silicon-dioxide such as Liu Guixia and Hong Guangyan is the inner core layer material, the synthetic SiO that obtained
2-Y
2O
3: the Eu nucleocapsid structure has also prepared Y on this basis
2O
3: the empty ball of Eu red fluorescence powder, Liu, G..; Hong, G., Synthesis ofSiO
2/ Y
2O
3: Eu core-shell materials and hollow spheres, JOURNAL OF SOLIDSTATE CHEMISTRY, 2005,178 (5): 1647-1651.Liu, G.; Hong, G.; Dong, X.; Wang, J., Synthesis of Y
2O
3: Eu
3+Hollow Spheres using silica as templates, JOURNAL OF RARE EARTHS, 2007,25 (4): 407-411., employing sol-gel methodes such as Yu have prepared SiO
2-YVO
4: Eu
3+, Yu, M.; Lin, J., Fang, J., Silica spheres coated withYVO
4: Eu
3+Layers via sol-gel process:a simple method to obtain sphericalcore-shell phosphors, CHEMISTRY OF MATERIALS, 2005,17 (7): 1783-1791, Lin etc. have synthesized SiO
2-Y
0.9Eu
0.1BO
3Particle, Lin, C.; Kong, D.; Liu X., Wang, H.; Yu, M.; Lin, J., Monodisperse and core-shell-structured SiO
2@YBO
3: Eu
3+Sphericalparticles:synthesis and characterization, INORGANIC CHEMISTRY, 2007,46 (7): 2674-2681, Chang etc. have prepared (Y
2O
3: Eu
3+)-SiO
2-YVO
4: Eu
3+Multilayered structure.Chang, M.; Tie S., Fabrication of novel luminor Y
2O
3: Eu
3+@SiO
2@YVO
4: Eu
3+Withcore/shell heteronanostructure, NANOTECHNOLOGY, 2008,19 (7): 075711.1-075711.7, though at present existing a lot of be that the nucleocapsid structure luminescent material of kernel sees bibliographical information with silicon-dioxide, with important RE phosphate green emitting phosphor [LnPO
4(Ln=La:Ce, Tb)] relevant work is considerably less, has only Yu etc. at present about preparing SiO with the Pechini sol-gel method
2-LnPO
4(Ln=La:Ce, report Tb).Yu, M.; Wang, H.; Lin, C.; Li, G.; Lin, J., Sol-gel synthesis and photoluminescence properties of spherical SiO
2/ LaPO
4: Ce
3+/ Tb
3+Particles with a core-shell structure, NANOTECHNOLOGY, 2006,17 (13): 3245-3252, but its LnPO of material that adopts this method to prepare
4Shell is thinner, can only form the RE phosphate deposition of 60nm at every turn, if obtain that luminous better the material that shell is thicker then must repeatedly deposit, operate comparatively loaded down with trivial detailsly, and the while has also increased synthetic cost to a certain extent.If can adopt cheap preparing spherical SiO 2 is inner stratum nucleare, and the homogeneous precipitation method that adopts easy handling simultaneously is at the thicker LnPO of its surperficial disposable coating
4Stratum nucleare then can obtain the regular nucleocapsid structure spheroidal particle fluorescent material of pattern, because internal layer does not contain expensive rare earth element, so synthetic cost can be reduced effectively.This method preparation is simple, and is with low cost, easy handling, and product appearance be regular sphere, preferablyly is used in the high-quality display device Bang, J.; Abboudi, M.; Abrams, B.; Holloway, P.H., Combustion synthesis of Eu-, Tb-and Tm-doped Ln
2O
2S (Ln=Y, La, Gd) phosphors, JOURNAL OF LUMINESCENCE, 2004,106 (3-4): 177-185, the dispersion treatment of carrying out the later stage and be coated with when screen effect also can be better.This method is fit to commercial scale production, has using value for the luminouslighting industry.
Summary of the invention
The objective of the invention is in order to overcome existing RE phosphate green emitting phosphor material produce cost costliness, the regular inadequately shortcoming of pattern, propose a kind of prepare simple, with low cost, pattern is regular, silicon dioxide-rare earth phosphate core-shell structured fluorescence material that can commercial scale production and preparation method thereof.
According to technical scheme provided by the invention, silicon dioxide-rare earth phosphate core-shell structured fluorescence material comprises stratum nucleare and shell, and described shell is the LnPO of green light
4Fluorescent material, LnPO
4=LaPO
4: Ce, Tb; Stratum nucleare is SiO
2Spherical granular material.
Earlier with La
2O
3, Tb (NO
3)
36H
2O, Ce (NO
3)
36H
2O is dissolved in respectively in rare nitric acid, is mixed with rare-earth ion solution; Press La again
3+: Ce
3+: Tb
3+Mol ratio is to be mixed with mixed rare earth ionic solution in 0.60: 0.27: 0.13～0.55: 0.30: 0.15, gets tripoly phosphate sodium STPP, and it is soluble in water, uses the salt acid for adjusting pH value, is mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.125～0.175mol/L; By mixed rare earth ionic solution and sodium tripolyphosphate solution mol ratio is 1: 1～1: 1.4, and mixed rare earth ionic solution is dropwise added in the above-mentioned tripolyphosphate sodium water solution, stirs, and obtains preparing the mixing solutions of shell material; Will be as the SiO of stratum nucleare material
2Spheroidal particle is inserted in the mixing solutions of shell material of above-mentioned preparation, SiO in this mixing solutions
2With rare earth ion total amount mol ratio be 1: 0.4～1: 2, under 90 ℃～100 ℃, react the synthetic suspension liquid that obtains containing silicon dioxide-rare earth phosphate core-shell structured fluorescence material of the method by precipitation from homogeneous solution (PFHS), heterogeneous nucleation.After reaction finishes,, collect after the vacuum-drying and obtain silicon dioxide-rare earth phosphate core-shell structured fluorescence material through cooling, filtration, washing.
Described SiO
2Be non-luminous spherical granular material; Described LnPO
4Fluorescent material for green light; Described stratum nucleare SiO
2The spherical granular material diameter is: 200nm～2 μ m, described silicon dioxide-rare earth phosphate core-shell structured fluorescence granular material diameter is: 600nm～12 μ m.
The present invention relates to a kind of silicon dioxide-rare earth phosphate core-shell structured fluorescence preparation methods, adopt following processing step:
1, preparation rare-earth ion solution: earlier respectively with 0.04～0.30mol La
2O
3, 0.08～0.60molTb (NO
3)
36H
2O, 0.08～0.60mol Ce (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L 0.01mol/L, is mixed with the rare-earth ion solution that volumetric molar concentration is 0.08～0.60mol/L;
2, preparation mixed rare earth ionic solution: get the rare-earth ion solution of above-mentioned preparation, press La
3+: Ce
3+: Tb
3+Mol ratio is 0.60: 0.27: 0.13～0.55: 0.30: 0.15, is mixed with mixed rare earth ionic solution, and with salt acid for adjusting pH value to 2.5～3.5, the pH value is measured by accurate pH test paper, obtains mixed rare earth ionic solution;
3, preparation sodium tripolyphosphate solution: get tripoly phosphate sodium STPP 0.125～0.175mol, it is dissolved in 975～985mL water, successively the pH value of solution value is adjusted to 2.5～3.5 with 6mol/L and 1mol/L hydrochloric acid, with the solution constant volume is 1L, is mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.125～0.175mol/L;
4, continuing under the condition of stirring, the tripoly phosphate sodium STPP mol ratio is 1: 1～1: 1.4 a ratio in going on foot with the above-mentioned the 3rd in the above-mentioned second step mixed rare earth ionic solution middle-weight rare earths total ion concentration, mixed rare earth ionic solution with above-mentioned second step, dropwise add in the tripolyphosphate sodium water solution in above-mentioned the 3rd step, rate of addition is 1 droplet/second, stir, obtain preparing the mixing solutions of shell material;
5, get SiO
2Spherical granular material is inserted it in mixing solutions of above-mentioned the 4th step preparation shell material SiO in the 5th step solution
2The mol ratio of spherical granular material and rare earth ion total amount is 1: 0.4～1: 2.When keeping stirring, place 90 ℃～100 ℃ following sustained reaction 3～5h, at this moment LnPO
4Crystal forms in solution and with SiO
2Be nucleus growth, final LnPO
4Crystal is with SiO
2Coat and form shell fully, thereby obtain containing the suspension liquid of silicon dioxide-rare earth phosphate core-shell structured fluorescence material.
6, after reaction finishes, system is cooled to room temperature, goes out throw out with the filtering with microporous membrane of 0.22 μ m, the gained throw out with deionized water wash 4～5 times after, place more than 30 ℃ of dry 12h of vacuum drying oven, obtain silicon dioxide-rare earth phosphate core-shell structured fluorescence material.
The preparation method of the fluorescence granular material of nucleocapsid structure provided by the invention dropwise adds mixed rare earth ionic solution in the tripolyphosphate sodium water solution, adds the SiO as kernel again
2Spheroidal particle, under the certain reaction condition, tripoly phosphate sodium STPP progressively after the hydrolysis formed phosphate anion combine with rare earth ion in the solution, with SiO
2Spheroidal particle is that core growth forms LnPO
4Shell; Through cooling, filtration, washing, collect the fluorescence granular material that obtains the silicon dioxide-rare earth phosphate nucleocapsid structure after the vacuum-drying.
The spherical fluorescent grain of the silicon dioxide-rare earth phosphate nucleocapsid structure of the present invention's preparation can send green fluorescence when being subjected to ultraviolet excitation.The position at peak and relative intensity and pure LnPO in its fluorescent emission collection of illustrative plates
4The emission collection of illustrative plates meet fully.
The spherical fluorescence granular material of the silicon dioxide-rare earth phosphate of nucleocapsid structure provided by the invention, the pattern rule, with low cost, preparation technology is simple, is suitable for producing in batches, has significant application value for the luminouslighting industry.
Description of drawings
Fig. 1, scanning electron microscope photograph (a) are the SiO as kernel
2Particle; (b) be the SiO behind the formation nucleocapsid structure
2-LnPO
4Fluorescent grain.
Fig. 2, transmission electron microscope photograph (a) are the SiO as kernel
2Particle; (b) be the SiO behind the formation nucleocapsid structure
2-LnPO
4Fluorescent grain.
Fig. 3, as the SiO of kernel
2Particle and SiO
2-LnPO
4The contrast of core-shell structured fluorescence particulate X-ray diffractogram.
Fig. 4, UV-light (λ=272nm) excite down, SiO
2-LnPO
4Core-shell structured fluorescence particulate fluorescence emission spectrogram.
Embodiment
Embodiment 1 the present invention relates to a kind of silicon dioxide-rare earth phosphate core-shell structured fluorescence preparation methods, adopts following processing step:
1, respectively with 0.17molLa
2O
3, 0.34mol Tb (NO
3)
36H
2O, 0.34molCe (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L 0.01mol/L, is mixed with the rare-earth ion solution that volumetric molar concentration is 0.34mol/L;
2, get the rare-earth ion solution that the above-mentioned the first step is prepared, press La
3+: Ce
3+: Tb
3+Mol ratio 0.58: 0.28: 0.14 is mixed with mixed rare earth ionic solution 30mL, and the mixed rare earth ionic solution middle-weight rare earths ionic total amount that is made into is 2.5mmol, wherein La
3+, Ce
3+, Tb
3+Amount of substance be respectively 1.45mmol, 0.70mmol, 0.35mmol.And with salt acid for adjusting pH value to 3.0, the pH value is measured by accurate pH test paper.
3, taking by weighing tripoly phosphate sodium STPP 0.150mol, it is dissolved in the 980mL water, successively with 6mol/L and 1mol/L hydrochloric acid the pH value of solution value is adjusted to 2.5, is 1L with the solution constant volume, is mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.150mol/L.The pH value is measured by accurate pH test paper.
4, get the sodium tripolyphosphate solution 20mL in above-mentioned the 3rd step, continue to stir with magnetic stirring apparatus, stirring velocity is 300 rev/mins, the mixed rare earth ionic solution that dropwise adds above-mentioned second step, rate of addition is 1 droplet/second, obtain the mixing solutions of the preparation shell material of clear this moment, and wherein rare earth ion total amount and tripoly phosphate sodium STPP mol ratio are 1: 1.2.In dripping the process of mixed rare earth ionic solution, be the hydrochloric acid soln pH value of regulator solution at any time of 0.1mol/L with concentration, it is remained on about 3.0.The pH value is measured by accurate pH test paper.
5, take by weighing the kernel SiO that diameter is about 900nm
2Spherical granular material 2.5mmol inserts it in mixing solutions of preparation shell material of clear in above-mentioned the 4th step SiO in the 5th step mixing solutions
2With the mol ratio of rare earth ion total amount be 1: 2; Keep stirring with magnetic stirring apparatus, stirring velocity is 300 rev/mins, and the mixing solutions that the 5th step was obtained places 95 ℃ of following sustained reaction 4h, obtains containing SiO
2-LnPO
4The suspension liquid of core-shell particle.
6, after reaction finishes, system is cooled to room temperature, leaves standstill about 10min, filtering with microporous membrane with 0.22 μ m goes out throw out, deionized water wash 4～5 times of gained throw out place the gained precipitation more than 30 ℃ of vacuum drying oven dried overnight 12h, make SiO
2-LnPO
4Core-shell structured fluorescence granular material.
7, with scanning electron microscope (S-4800, HIT) and transmission electron microscope (JEM-2100, Japanese JEOL company) to SiO as kernel
2Particle and SiO
2-LnPO
4The core-shell structured fluorescence particle has carried out surface topography analysis (seeing accompanying drawing one, accompanying drawing two), and the result shows the SiO as inner nuclear material
2Monodispersity is good, and particle surface is smooth smooth; Form SiO
2-LnPO
4Behind the nucleocapsid structure, particle surface is no longer smooth, and particle size obviously increases SiO
2-LnPO
4The size of core-shell particle is about 1.5 μ m.Analyzed formation SiO with X-ray diffractometer (D8 Advance, German Bruker company)
2-LnPO
4Particulate phase composite before and after the nucleocapsid structure, (seeing accompanying drawing three) result show, behind the formation nucleocapsid structure, the SiO of internal layer
2Substantially coated fully, its corresponding diffraction peak intensity descends greatly.Meanwhile, at SiO
2-LnPO
4Occurred new diffraction peak in the X-ray diffractogram of core-shell particle, their position is just in time corresponding to the LnPO of shell
4This explanation has formed SiO really
2-LnPO
4Nucleocapsid structure.Ultraviolet excitation (under the λ=272nm), with spectrophotofluorometer (RF-5301, day island proper Tianjin company) to SiO
2And SiO
2-LnPO
4The core-shell structured fluorescence particle has carried out the mensuration (seeing accompanying drawing four) of fluorescence emission spectrum, and the result shows, pure SiO
2Do not produce fluorescent emission, and after forming nucleocapsid structure, then produced tangible fluorescent emission, the gained spectrogram is typical LnPO
4Fluorescence emission spectrum, spectrogram are mainly by four Tb
3+Transition emission peak (450-650nm) and one be positioned at the ultraviolet region and belong to Ce
3+The more weak emission peak of d-F transition form.This result has further confirmed SiO
2-LnPO
4The core-shell structured fluorescence particulate forms.
Embodiment 2
1, respectively with 0.04molLa
2O
3, 0.08mol Tb (NO
3)
36H
2O, 0.08molCe (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L 0.01mol/L, is mixed with the rare-earth ion solution that volumetric molar concentration is 0.08mol/L;
2, get the rare-earth ion solution that the above-mentioned the first step is prepared, press La
3+: Ce
3+: Tb
3+Mol ratio 0.60: 0.27: 0.13 is mixed with mixed rare earth ionic solution 30mL, and the mixed rare earth ionic solution middle-weight rare earths ionic total amount that is made into is 2.5mmol, wherein La
3+, Ce
3+, Tb
3+Amount of substance be respectively 1.5mmol, 0.675mmol, 0.325mmol.And with salt acid for adjusting pH value to 2.5, the pH value is measured by accurate pH test paper.
3, taking by weighing tripoly phosphate sodium STPP 0.125mol, it is dissolved in the 975mL water, successively with 6mol/L and 1mol/L hydrochloric acid the pH value of solution value is adjusted to 2.5, is 1L with the solution constant volume, is mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.125mol/L.The pH value is measured by accurate pH test paper.
4, get the sodium tripolyphosphate solution 20mL in above-mentioned the 3rd step, continue to stir with magnetic stirring apparatus, stirring velocity is 300 rev/mins, the mixed rare earth ionic solution that dropwise adds above-mentioned second step, rate of addition is 1 droplet/second, obtain the mixing solutions of the preparation shell material of clear this moment, and wherein rare earth ion total amount and tripoly phosphate sodium STPP mol ratio are 1: 1.In dripping the process of mixed rare earth ionic solution, be the hydrochloric acid soln pH value of regulator solution at any time of 0.1mol/L with concentration, it is remained on about 2.5.The pH value is measured by accurate pH test paper.
5, take by weighing the kernel SiO that diameter is about 200nm
2Spherical granular material 6.25mmol inserts it in mixing solutions of preparation shell material of clear in above-mentioned the 4th step SiO in the 5th step mixing solutions
2With the mol ratio of rare earth ion total amount be 1: 2; Keep stirring with magnetic stirring apparatus, stirring velocity is 300 rev/mins, and the mixing solutions that the 5th step was obtained places 90 ℃ of following sustained reaction 3h, obtains containing SiO
2-LnPO
4The suspension liquid of core-shell particle,
6, after reaction finishes, system is cooled to room temperature, leaves standstill about 10min, filtering with microporous membrane with 0.22 μ m goes out throw out, deionized water wash 4～5 times of gained throw out place the gained precipitation more than 30 ℃ of vacuum drying oven dried overnight 12h, make SiO
2-LnPO
4Core-shell structured fluorescence granular material.
7, to forming SiO
2-LnPO
4Particulate surface topography, phase composite and photoluminescent property carry out analyzing and testing before and after the nucleocapsid structure, and method is identical with the 7th step among the embodiment 1.
Embodiment 3
1, respectively with 0.30molLa
2O
3, 0.60mol Tb (NO
3)
36H
2O, 0.60molCe (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L 0.01mol/L, is mixed with the rare-earth ion solution that volumetric molar concentration is 0.60mol/L;
2, get the rare-earth ion solution that the above-mentioned the first step is prepared, press La
3+: Ce
3+: Tb
3+Mol ratio 0.55: 0.30: 0.15 is mixed with mixed rare earth ionic solution 30mL, and the mixed rare earth ionic solution middle-weight rare earths ionic total amount that is made into is 2.5mmol, wherein La
3+, Ce
3+, Tb
3+Amount of substance be respectively 1.375mmol, 0.21mmol, 0.375mmol.And with salt acid for adjusting pH value to 3.5, the pH value is measured by accurate pH test paper.
3, taking by weighing tripoly phosphate sodium STPP 0.175mol, it is dissolved in the 985mL water, successively with 6mol/L and 1mol/L hydrochloric acid the pH value of solution value is adjusted to 2.5, is 1L with the solution constant volume, is mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.175mol/L.The pH value is measured by accurate pH test paper.
4, get the sodium tripolyphosphate solution 20mL in above-mentioned the 3rd step, continue to stir with magnetic stirring apparatus, stirring velocity is 300 rev/mins, the mixed rare earth ionic solution that dropwise adds above-mentioned second step, rate of addition is 1 droplet/second, obtain the mixing solutions of the preparation shell material of clear this moment, and wherein rare earth ion total amount and tripoly phosphate sodium STPP mol ratio are 1: 1.4.In dripping the process of mixed rare earth ionic solution, be the hydrochloric acid soln pH value of regulator solution at any time of 0.1mol/L with concentration, it is remained on about 3.5.The pH value is measured by accurate pH test paper.
5, take by weighing the kernel SiO that diameter is about 2 μ m
2Spherical granular material 1.25mmol inserts it in mixing solutions of preparation shell material of clear in above-mentioned the 4th step SiO in the 5th step mixing solutions
2With the mol ratio of rare earth ion total amount be 1: 2; Keep stirring with magnetic stirring apparatus, stirring velocity is 300 rev/mins, and the mixing solutions that the 5th step was obtained places 100 ℃ of following sustained reaction 5h, obtains containing SiO
2-LnPO
4The suspension liquid of core-shell particle.
6, after reaction finishes, system is cooled to room temperature, leaves standstill about 10min, filtering with microporous membrane with 0.22 μ m goes out throw out, deionized water wash 4～5 times of gained throw out place the gained precipitation more than 30 ℃ of vacuum drying oven dried overnight 12h, make SiO
2-LnPO
4Core-shell structured fluorescence granular material.
7, to forming SiO
2-LnPO
4Particulate surface topography, phase composite and photoluminescent property carry out analyzing and testing before and after the nucleocapsid structure, and method is identical with the 7th step among the embodiment 1.
Claims (5)
1. silicon dioxide-rare earth phosphate core-shell structured fluorescence material and preparation method thereof, it is characterized in that: comprise stratum nucleare and shell, described shell is the LnPO of green light
4Fluorescent material, LnPO
4=LaPO
4: Ce, Tb; Stratum nucleare comprises SiO
2Spherical granular material;
Earlier with La
2O
3, Tb (NO
3)
36H
2O, Ce (NO
3)
36H
2O is dissolved in respectively in rare nitric acid, is mixed with rare-earth ion solution; Press La again
3+: Ce
3+: Tb
3+Mol ratio was mixed with mixed rare earth ionic solution in 0.60: 0.27: 0.13～0.55: 0.30: 0.15; It is soluble in water to get tripoly phosphate sodium STPP, successively uses the salt acid for adjusting pH value, is mixed with sodium tripolyphosphate solution; By rare earth ion total amount in the mixed rare earth ionic solution and tripoly phosphate sodium STPP mol ratio is 1: 1～1: 1.4, and mixed rare earth ionic solution is dropwise added in the above-mentioned tripolyphosphate sodium water solution, stirs the mixing solutions that obtains preparing the shell material; Will be as the SiO of stratum nucleare material
2Spheroidal particle is inserted in the mixing solutions of above-mentioned preparation shell material, SiO in the resulting mixing solutions
2With the mol ratio of rare earth ion total amount be 1: 0.4～1: 2, under 90 ℃～100 ℃, react, this moment LnPO
4Crystal forms in solution and with SiO
2Be nucleus growth, final LnPO
4Crystal is with SiO
2Coat and form shell fully, thereby obtain containing the suspension liquid of silicon dioxide-rare earth phosphate core-shell structured fluorescence material; After reaction finishes,, collect after the vacuum-drying and obtain silicon dioxide-rare earth phosphate core-shell structured fluorescence material through cooling, filtration, washing.
2. silicon dioxide-rare earth phosphate core-shell structured fluorescence preparation methods as claimed in claim 1, adopt following processing step:
(1), preparation rare-earth ion solution: earlier respectively with 0.04～0.30molLa
2O
3, 0.08～0.60molTb (NO
3)
36H
2O, 0.08～0.60mol Ce (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L 0.01mol/L, is mixed with volumetric molar concentration to be: the rare-earth ion solution of 0.08～0.60mol/L;
(2), preparation mixed rare earth ionic solution: get the rare-earth ion solution of above-mentioned preparation, press La
3+: Ce
3+: Tb
3+Mol ratio 0.60: 0.27: 0.13～0.55: 0.30: 0.15 is mixed with mixed rare earth ionic solution, is mixed with mixed rare earth ionic solution, with salt acid for adjusting pH value to 2.5～3.5, obtains mixed rare earth ionic solution;
(3), preparation sodium tripolyphosphate solution: get tripoly phosphate sodium STPP 0.125～0.175mol, it is dissolved in 975～985mL water, successively the pH value of solution value is adjusted to 2.5～3.5 with 6mol/L and 1mol/L hydrochloric acid, with the solution constant volume is 1L, is mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.125～0.175mol/L;
(4), continuing under the condition of stirring, the tripoly phosphate sodium STPP mol ratio is 1: 1～1: 1.4 a ratio in going on foot with the above-mentioned the 3rd in the above-mentioned second step mixed rare earth ionic solution middle-weight rare earths total ion concentration, mixed rare earth ionic solution with above-mentioned second step, dropwise add in the tripolyphosphate sodium water solution in above-mentioned the 3rd step, rate of addition is 1 droplet/second, stir, obtain preparing the mixing solutions of shell material;
(5), with SiO
2Insert in the mixing solutions of above-mentioned the 4th step preparation shell material, in the 5th step mixing solutions as the SiO of kernel
2The mol ratio of spherical granular material and rare earth ion total amount is 1: O.4～1: 2, when keeping stirring, place 90 ℃～100 ℃ following sustained reaction 3～5h, obtain containing SiO
2-LnPO
4The suspension liquid of core-shell particle;
(6), after reaction finishes, contain SiO in will the above-mentioned the 5th going on foot
2-LnPO
4The suspension liquid of core-shell particle is cooled to room temperature, go out throw out with the filtering with microporous membrane of μ m O.22, behind the gained throw out usefulness deionized water wash 4～5 times, place more than 30 ℃ of dry 12h of vacuum drying oven, obtain silicon dioxide-rare earth phosphate core-shell structured fluorescence material.
3. silicon dioxide-rare earth phosphate core-shell structured fluorescence preparation methods as claimed in claim 2 is characterized in that: described SiO
2Be non-luminous spherical granular material; Described SiO
2The spherical granular material diameter is: 200nm～2 μ m.
4. silicon dioxide-rare earth phosphate core-shell structured fluorescence preparation methods as claimed in claim 2 is characterized in that: described LnPO
4Fluorescent material for green light.
5. silicon dioxide-rare earth phosphate core-shell structured fluorescence preparation methods as claimed in claim 2, it is characterized in that: the diameter of described silicon dioxide-rare earth phosphate core-shell structured fluorescence granular material is: 600nm～12 μ m.
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Cited By (10)
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| CN103642497A (en) * | 2013-12-11 | 2014-03-19 | 江南大学 | Preparation method of nano rare earth phosphate fluorescent material LnPO4 |
| CN104650913A (en) * | 2013-11-22 | 2015-05-27 | 江南大学 | Preparation method of nanometer fluorescent material |
| CN104694123A (en) * | 2013-12-09 | 2015-06-10 | 江南大学 | Soft template hydrothermal preparation method of nano rare earth phosphate |
| CN104694124A (en) * | 2013-12-10 | 2015-06-10 | 江南大学 | Aluminium oxide-rare earth phosphate core-shell structured fluorescent material and preparation method thereof |
| CN105885840A (en) * | 2014-12-18 | 2016-08-24 | 江南大学 | PEG (polyethylene glycol) compound system hydrothermal preparation method of nano green phosphor |
| CN105885841A (en) * | 2014-12-18 | 2016-08-24 | 江南大学 | Preparation method of PEG (polyethylene glycol) composite system of nano fluorescent material |
| CN109158062A (en) * | 2018-09-19 | 2019-01-08 | 新疆维吾尔自治区产品质量监督检验研究院 | Silicon dioxide colloid compound rare-earth core-shell type microballoon and preparation method thereof |
| CN111019641A (en) * | 2019-12-31 | 2020-04-17 | 河北北方学院 | Preparation method of rare earth phosphate-based luminescent material |
| CN112176720A (en) * | 2020-09-28 | 2021-01-05 | 安徽瑜合警用装备有限公司 | Photoluminescent finishing agent based on silica microspheres, preparation method and application thereof |
| CN112618390A (en) * | 2020-11-26 | 2021-04-09 | 中山大学 | Silicon dioxide/rare earth oxide light conversion composite material and preparation method thereof |
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| CN104650913A (en) * | 2013-11-22 | 2015-05-27 | 江南大学 | Preparation method of nanometer fluorescent material |
| CN104694123A (en) * | 2013-12-09 | 2015-06-10 | 江南大学 | Soft template hydrothermal preparation method of nano rare earth phosphate |
| CN104694124B (en) * | 2013-12-10 | 2016-09-07 | 江南大学 | Alumina-rare earth phosphate core-shell structured fluorescence material and preparation method thereof |
| CN104694124A (en) * | 2013-12-10 | 2015-06-10 | 江南大学 | Aluminium oxide-rare earth phosphate core-shell structured fluorescent material and preparation method thereof |
| CN103642497A (en) * | 2013-12-11 | 2014-03-19 | 江南大学 | Preparation method of nano rare earth phosphate fluorescent material LnPO4 |
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| CN105885841A (en) * | 2014-12-18 | 2016-08-24 | 江南大学 | Preparation method of PEG (polyethylene glycol) composite system of nano fluorescent material |
| CN109158062A (en) * | 2018-09-19 | 2019-01-08 | 新疆维吾尔自治区产品质量监督检验研究院 | Silicon dioxide colloid compound rare-earth core-shell type microballoon and preparation method thereof |
| CN109158062B (en) * | 2018-09-19 | 2021-08-03 | 新疆维吾尔自治区产品质量监督检验研究院 | Silicon dioxide colloid composite rare earth core-shell microsphere and preparation method thereof |
| CN111019641A (en) * | 2019-12-31 | 2020-04-17 | 河北北方学院 | Preparation method of rare earth phosphate-based luminescent material |
| CN111019641B (en) * | 2019-12-31 | 2024-01-05 | 河北北方学院 | Preparation method of luminescent material based on rare earth phosphate |
| CN112176720A (en) * | 2020-09-28 | 2021-01-05 | 安徽瑜合警用装备有限公司 | Photoluminescent finishing agent based on silica microspheres, preparation method and application thereof |
| CN112618390A (en) * | 2020-11-26 | 2021-04-09 | 中山大学 | Silicon dioxide/rare earth oxide light conversion composite material and preparation method thereof |
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