CN101575514B - Mesoporous rare earth phosphate fluophor and preparation method thereof - Google Patents
Mesoporous rare earth phosphate fluophor and preparation method thereof Download PDFInfo
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- CN101575514B CN101575514B CN200910052062A CN200910052062A CN101575514B CN 101575514 B CN101575514 B CN 101575514B CN 200910052062 A CN200910052062 A CN 200910052062A CN 200910052062 A CN200910052062 A CN 200910052062A CN 101575514 B CN101575514 B CN 101575514B
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Abstract
The invention discloses a mesoporous rare earth phosphate fluophor and a preparation method thereof, belonging to the field of multifunctional rare earth luminescent material. The method, which takes mesoporous silicon dioxide with an ordered pore channel structure as a hard template agent, comprises the steps of adding homogeneous solution of soluble rare-earth salts/rare earth fluophor material/strong phosphoric acid/concentrated nitric acid in the silicon dioxide pore channel, removing the nitric acid solvent through direct volatilization, thus precipitating the phosphate fluophor in the pore channel; further leading the rare earth phosphate fluophor to be cured in the mesoporous pore channel through high-temperature roasting treatment, removing the silicon dioxide hard template agent,thus obtaining the mesoporous rare earth phosphate fluophor. The mesoporous rare earth phosphate fluophor material has the characteristics of high degree of order, adjustable pore diameter and mesoporous structure, large specific surface area, pore diameter and pore volume and the like, with the specific surface area being 100-500m<2>/g, the pore diameter being 3-8nm, and the pore volume being 0.15-1.5cm<3>/g; and can be used as a novel absorbing and embedding material of medicaments.
Description
Technical field
The present invention relates to a kind of mesoporous rare earth phosphate fluophor and preparation method thereof, belong to the multifunctional rare-earth field of light emitting materials.
Background technology
(aperture is widely used at catalyzer, absorption, separation field because of its duct regular in order, very big specific surface area and pore volume 2～50nm) mesoporous material.REE has crucial application owing to its unique 4f electronics subgrade structure in fields such as light, electricity, magnetic devices; If we combine both; Synthesising mesoporous rare earth nano material such as mesoporous rare earth phosphate etc.; Then prepared mesoporous rare-earth material is having performances such as mesoporous excellent properties (as selecting shape selectivity, absorption etc.) and the distinctive light of rare earth, electricity, magnetic simultaneously, thereby this novel mesoporous rare-earth compound nano-material will be opened up new evolutionary path in fields such as new function material such as delivery of drug, porous photo luminescent devices, magnetic absorption and parting materials.
Since Mobil company synthesizing mesoporous silicon dioxide molecular sieve; The study on the synthesis of mesoporous material has been obtained huge progress; But the synthesizing of mesoporous material to containing rare earth compound mainly concentrates on loading type (Ce-MCM-41; Ce-MCM-48) or the preparation of codoped type rare earth compound, also only be confined to the report of their catalytic performance and to the application of these compounds containing rare earth mesoporous materials.
Recently; People try rare earth compound is combined with the means of mesoporous silica molecular sieve through grafting (graft) or back synthetic (post-synthesis doping), prepare performances such as organic and inorganic rare earth composite material that has porous character simultaneously and the light except that catalytic performance of further studying this complex mesoporous material, electricity, magnetic.Domestic Zhang Hongjie seminar like Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences, with the organic rare-earth ligand grafting to the surface of SBA-15 mesopore molecular sieve and test its luminescent properties.[the Piaoping Yang of Lin Jun researcher seminar of Changchun applied chemistry institute; Shanshan Huang; Deyan Kong, et al Inorg.Chem.2007,46; 3203] directly obtain multi-functional YVO4:Eu/SBA-15 material with synthetic YVO4:Eu through Pechini sol-gelprocess, then with this not only had the mesoporous material characteristics, but also the multifunctional material with optical property be applied to the absorption/sustained release of drug molecule.Up-conversion luminescence performance [Fan Zhang, Ying Wan, the Yifeng Shi that presoma has synthesized the rare earth La F:Ln nano wire display of mesoscopic structure and tested them is with fluorine-containing rare earth organism in the first seminar in Zhao of Fudan University east; Et al; Chem.Mater.2008,20,3778].
It should be noted that; At present mostly the rare earth mesoporous functional materials of report is to be employed in the organic molecule that contains rare earth on the mesoporous silica molecular sieve surface graft or codoped, back synthetic method preparation; Its weak point is that surface, the inner duct of molecular sieve is often covered by these organic molecules; The result causes mesoporous aperture to reduce, and pore volume reduces, thereby is unfavorable for the entering of bioactive molecule; The toxicity of organic molecule is also limiting the application of these rare earth materials in field of biology simultaneously.Pure rare earth compound (like RE phosphate and doping salt thereof etc.) has higher chemicalstability and bio-compatibility preferably, thereby is necessary to develop the multi-functional pure rare earth compound nano-material of the meso-hole structure with high pore volume.
Less relatively to the report of the synthetic mesoporous compound-material of pure rare earth at present; Though this pure rare earth compound become in the future probably have controllable light, the multifunctional material of electricity, magnetic: Mitsunori Yada [Y.Mitsunori; K.Hirohumi; I.Akira et al, Angew.Chem.Int.Ed.1999,38; 3506.] once made the synthetic rare earth mesoporous oxide material of stratiform of method of template, precipitation from homogeneous solution(PFHS) with anionic and characterized their magnetic behavior, but the thermostability of the rare earth mesoporous oxide compound of this stratiform is relatively poor.Michael A.Morris [M.L.Daniel, M.R.Kevin, M.A.Morris J.Mater.Chem.; 2002; 12,1207.] improve their research method, adopted neutral template to synthesize mesoporous rare-earth oxide; After 450 ℃ of following roastings, can keep structures of samples, but the order of sample is relatively poor.Domestic Wang Tong culture and education is awarded [T.Wang, L.Dai, Cloid and surfaces A:physicochemical and Engineering; Aspects, 2002,209; 65] once synthesized the mesoporous rare-earth yttrium oxide with AS, but the less stable of meso-hole structure.
The less reason of mesoporous rare-earth compound synthetic aspect report; Mainly be to synthesize relevant through directly doing template with tensio-active agent with the mesoporous rare-earth compound is difficult; Because rare earth compound is insoluble in water usually; Solubility product constant very little (Ksp～10-23 order of magnitude), its rare earth presoma was just separated out from solution with sedimentary form before also not with tensio-active agent generation organic and inorganic synergy; In addition, remove in the process of tensio-active agent, because the behavior of rare earth compound generation crystal also causes subsiding of mesopore orbit in roasting.Thereby with the difficult rare earth compound nano hole material that synthesizes structurally ordered and Heat stability is good of the method for soft template.
The hard mould agent method [R.Ryoo, S.H.Joo, S.Jun, J.Phys.Chem.B 1999,103, and 7743; 20; Michael Tiemann Chem.Mater.2008; 20,961] be to use a kind of method of mesoporous silica molecular sieve as synthetic other mesoporous materials of template (like mesoporous non-silicon oxide etc.), its principle is that non-silicon oxide presoma (normally the transition metal nitrate of solubility etc.) is packed in the duct of silica mesoporous zeolite; Further dry except that the back high-temperature roasting of desolvating, utilize the nitrate salt pyrolytic decomposition to obtain the transition metal oxide/silicon dioxide mixture.Remove hard template with hydrofluoric acid or strong caustic at last, promptly obtain the mesopore oxide nano material of ordered structure.
Because the high-sequential property of hard mould agent; Thereby resulting mesopore oxide also is high-sequential, adopts this method, can keep the structurally ordered property of mesopore oxide well; So a lot of mesopore oxides such as aluminum oxide, priorities such as nickel oxide are produced out through hard template method.
Because RE phosphate has quite high physical and chemical stability certain bio-compatibility is arranged again; Its block main body of making luminescent material commonly used; If RE phosphate is made poroid material, then institute's synthetic mesoporous rare earth phosphate nano material will not only have excellent photoluminescence performance, but also have mesoporous performance as having bigger specific surface area and pore volume etc.The rare earth compound of this vesicular structure can be used as the delivery of drug vehicle of a new generation, has bigger pore volume and the embedding medicinal molecule, and the while has luminosity again and can confirm the organism part (on-line monitoring) that the delivery of drug vehicle is arrived at any time.Thereby the rare earth compound of synthetic this meso-hole structure has very tempting application prospect at biology and nanosecond medical science field.Also rare-earth phosphate phosphor is not prepared at present the report of porous material.
Summary of the invention
The objective of the invention is in order to solve in the prior art; The preparation of mesoporous luminescent material depends on the meso-porous titanium dioxide silicon face and mixes or the grafting luminophore; Its result causes that the specific surface area of mesoporous luminescent material is low, pore volume and deficiency such as the aperture is little and luminophore is poisonous, thereby proposes a kind of mesoporous rare earth phosphate fluophor and preparation method thereof.
Know-why of the present invention
The mesoporous silicon oxide that the present invention uses orderly pore passage structure is the method for hard mould agent; Insert the homogeneous phase solution of soluble rare-earth salt/rare earth luminous body material/SPA/concentrated nitric acid in the silicon-dioxide duct; Remove the nitric acid solvent through direct volatilization, thereby phosphate fluophor is precipitated in the duct, further handle through high-temperature roasting; Make rare-earth phosphate phosphor in mesopore orbit, solidify, obtain rare earth mesoporous phosphate fluophor after removing the silicon dioxide hard template agent;
Simultaneously, in building-up process, add the rare earth ion of different luminosities (like red, green, blue etc.), the result will obtain having the mesoporous rare earth phosphate fluophor material of different luminescent properties.This mesoporous functional materials has porous character and luminescent properties simultaneously, and can substitute needs grafting or aftertreatment synthetic rare earth/silicon dioxide composite material usually, and method is simple and practical.Thereby has important development prospect in the delivery of drug direction of biomedicine field.
Technical scheme of the present invention
A kind of preparation method of mesoporous rare earth phosphate fluophor comprises that preparation process is following:
(1) configuration of rare-earth phosphate phosphor homogeneous phase solution
Is 1: 0.001～0.1 mixing with rare earth soluble salt matrix and rare earth luminous body material according to mol ratio, and joining concentration is 16mol.L
-1Concentrated nitric acid in, further this mixed solution being joined concentration is 14mol.L
-1SPA in be made into the rare-earth phosphate phosphor homogeneous phase solution;
Wherein soluble rare-earth salt, rare earth luminous body material, concentration are 14mol.L
-1SPA and concentration be 16mol.L
-1The mol ratio of concentrated nitric acid be 1: 0.001～0.1: 0.5～3.5: 0.05～2.0;
Described soluble rare-earth salt adopts rare earth nitrate or hydrochloride; Preferentially select rare earth nitrate for use;
Wherein rare earth nitrate is one or more mixtures in rare earth Yttrium trinitrate, Lanthanum trinitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Terbium trinitrate, the Dysprosium trinitrate;
Wherein rare earth luminous body material (Ln
3+) be Eu
3+(NO
3)
3, Tb
3+(NO
3)
3Or cerous nitrate Ce
3+(NO
3)
3In one or more mixture;
Be preferably rare earth Yttrium trinitrate and Lanthanum trinitrate, in final formed yttrium phosphate fluor homogeneous phase solution or the phosphoric acid lanthanum fluorescence body homogeneous phase solution, yttrium phosphate (YPO
4) or lanthanum orthophosphate (LaPO
4) and rare earth luminescent material (Ln
3+) molar concentration rate be YPO
4: Ln
3+=1: 0.001～0.1 or LaPO
4: Ln
3+=1: 0.001～0.1;
(2), the preparation of the liquid alkane dispersion liquid of mesoporous silicon dioxide hard template agent
The mesoporous silicon oxide template is distributed to the alkane dispersion liquid of forming the silica template agent in the liquid alkane, and the mesoporous silicon oxide template is 1: 15～100 with the mass ratio of liquid alkane;
It is the porous silica material of 2～50nm that the aperture is adopted in the mesoporous silicon dioxide hard template agent, like the SBA-15 of two-dimentional hexagonal (P6m) or the KIT-6 of three-dimensional cubic structure (Ia3d);
Wherein liquid alkane is a normal butane, Skellysolve A, normal hexane, normal heptane and octane or their mixture;
(3) preparation of rare-earth phosphate phosphor/silica composite
The rare-earth phosphate phosphor homogeneous phase solution that step (1) is obtained joins in the dispersion liquid of mesoporous silicon dioxide hard template agent of the liquid alkane that step (2) obtained; Wherein the rare-earth phosphate phosphor homogeneous phase solution is 1: 0.3～10 with the mass ratio of mesoporous silicon oxide; Stir simultaneously; The control mixing speed is 200～600r/min, evaporates into driedly fully until the nitric acid solvent, promptly gets rare-earth phosphate phosphor/silica composite;
Described RE phosphate homogeneous phase solution and mesoporous silicon dioxide hard template agent mass ratio be preferably 1: 0.5～and 4.
(4), RE phosphate/silica composite roasting
Between the rare-earth phosphate phosphor/silica composite roasting at high temperature that step (3) is obtained, 300～1300 ℃ of control maturing temperatures, roasting time is at 3～12h;
(5), remove the silicon dioxide hard template agent;
(a), after the reaction of step (4) rare-earth phosphate phosphor/silica composite roasting finishes, naturally cool to room temperature;
(b), after step (a) is cooled to room temperature, be 0.5～4mol.L with rare-earth phosphate phosphor/silica composite after the roasting and concentration
-1Sodium hydroxide solution mix by 1: 10～60.0 by mass volume ratio, slowly stir, controlled temperature is between 30～100 ℃, mixing speed is 200～600r r/min, the time is 20～120min, spinning then discards supernatant liquid; Or be 1～10% hydrofluoric acid solution with rare-earth phosphate phosphor/silica composite after the roasting and concentration by mass volume ratio be 1: 10～60.0 to mix; The control mixing speed is 200～600r/min; Churning time is 10～80min, and spinning then discards supernatant liquid;
(c), repeating step (b) 2～4 times to be to remove silica mesoporous zeolite, continues washing with deionized water at last and presents neutrality until the pH of filtrating, the solid product of gained is mesoporous rare earth phosphate fluophor of the present invention.
A kind of mesoporous rare earth phosphate fluophor
Mesoporous rare earth phosphate fluophor of the present invention, its specific surface area are 100～500m
2/ g, the aperture is 3～8nm, pore volume is 0.15～1.5cm
3/ g.
Technique effect of the present invention
Mesoporous rare earth phosphate fluophor of the present invention had not only had excellent photoluminescence performance, but also had had mesoporous performance as having bigger specific surface area and pore volume etc.The rare earth compound of this vesicular structure can be used as the delivery of drug vehicle of a new generation, has bigger pore volume and the embedding medicinal molecule, and the while has luminosity again and can confirm the organism part (on-line monitoring) that the delivery of drug vehicle is arrived at any time.Thereby the rare earth compound of synthetic this meso-hole structure has very tempting application prospect, the novel absorption and the embedded material of useful as drug at biology and nanosecond medical science field.
Description of drawings
Fig. 1, the little angle XRD figure spectrum of mesoporous silicon oxide SBA-15
Fig. 2, the little angle XRD figure spectrum of mesoporous silicon oxide KIT-6
Fig. 3, mesoporous silicon oxide KIT-6, YPO4:5%Eu/KIT-6 and mesoporous yttrium phosphate: europium (YPO
4: the 5%Eu) nitrogen adsorption of nano material-desorption curve
Fig. 4, mesoporous silicon oxide KIT-6, YPO4:5%Eu/KIT-6 and mesoporous yttrium phosphate: europium (YPO
4: the 5%Eu) pore size distribution curve of nano material
Fig. 5, mesoporous rare-earth YPO
4: 5% (mol) Eu
3+The photoluminescence performance collection of illustrative plates
Fig. 6, mesoporous rare-earth YPO
4: 3% (mol) Tb
3+The photoluminescence performance collection of illustrative plates
Fig. 7, mesoporous rare-earth YPO
4: 1% (mol) Ce
3+The photoluminescence performance collection of illustrative plates
Embodiment
Further specify the present invention through embodiment below, but do not limit the present invention.
The mesoporous silicon oxide SBA-15 of two dimension hexagonal and the mesoporous silicon oxide KIT-6 of three-dimensional cubic are respectively according to document synthetic (Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G.H.; Chmelka, B.F.; Stucky, G.D.Science 1998,279, and 548; Kleitz, F.; Choi, S.H.; Ryoo, R.Chem.Commun. (Cambridge, U.K.) 2003,2136.)
With fully stirring 30min in the 50ml normal hexane in the mesoporous silicon oxide KIT-6 dispersion of 2.0 grams, splash into gradually then the 2.18 gram Y (NO that are dissolved in the 5ml concentrated nitric acid in advance
3)
36H
2O, 0.067 gram Eu (NO
3)
36H
2O and 0.6 gram SPA homogeneous phase solution.Continue to stir, the control mixing speed is that 200～600r/min does to solvent evaporates, further in 100 ℃ of baking ovens, places 24h.With this rare earth yttrium phosphate: europium/KIT-6 mixture is put in the retort furnace, slowly is warmed up to 650 ℃, keeps stopping heating behind the 5h, takes out behind the naturally cooling.With 4% hydrofluoric acid 30ml stir process 15min, the control stirring velocity is 200～600r/min, further spinning; Discard supernatant liquid, repeat 3 times, continue washing with deionized water at last and present neutrality until the pH of filtrating to remove the mesoporous SiO 2 hard mould agent; Filter oven dry.Thereby obtain having the mesoporous YPO of three-dimensional cubic Ia3d structure
4: Eu
3+Mano-porous material.Mesoporous silicon oxide KIT-6, YPO4:5%Eu/KIT-6 and mesoporous yttrium phosphate: europium (YPO
4: 5%Eu) nitrogen adsorption of nano material-desorption Fig. 3 and pore size distribution curve are seen Fig. 4.
With fully stirring 1h in the 45ml normal hexane in the mesoporous silicon oxide SBA-15 dispersion of 1.0 grams, splash into gradually then the 1.1 gram Y (NO that are dissolved in the 5ml concentrated nitric acid in advance
3)
36H
2O, 0.035 gram Eu (NO
3)
36H
2O and 0.6 gram SPA homogeneous phase solution.Continue to stir, the control mixing speed is that 200～600r/min does to solvent evaporates, further in 100 ℃ of baking ovens, places 24h.With this rare earth yttrium phosphate: europium/KIT-6 mixture is put in the retort furnace, slowly is warmed up to 650 ℃, keeps stopping heating behind the 5h, takes out behind the naturally cooling.2mol.L with 40 ℃
-1NaOH40ml stir process 40min, stirring velocity is 200～600r/min, further spinning discards supernatant liquid, repeats 4 times to remove the mesoporous SiO 2 hard mould agent, continues washing with deionized water at last and presents neutrality until the pH of filtrating.Filter oven dry.Thereby obtain having the mesoporous YPO of two-dimentional hexagonal structure P6mm
4: 5%molEu
3+Mano-porous material.Pl-shows mesoporous YPO4:5%molEu
3+Nano material can red-emitting under the ultraviolet excitation of 395nm wavelength.The result sees accompanying drawing 5.
The mesoporous silicon oxide KIT-6 of 1.0 grams is scattered in fully stirs 1h in the normal hexane of 45ml, splash into the 1.1 gram Y (NO that are dissolved in the 5ml concentrated nitric acid in advance then gradually
3)
36H
2O, 0.068 gram Tb (NO
3)
36H
2O and 0.6 gram SPA homogeneous phase solution.Continue to stir, the control mixing speed is that 200～600r/min does to solvent evaporates, further in 100 ℃ of baking ovens, places 24h.With this rare earth yttrium phosphate: terbium/KIT-6 mixture is put in the retort furnace, slowly is warmed up to 650 ℃, keeps stopping heating behind the 5h, takes out behind the naturally cooling.With 3% hydrofluoric acid 40ml stir process 20min, the control stirring velocity is 200～600r/min.Further spinning discards supernatant liquid, repeats 3 times to remove the mesoporous SiO 2 hard mould agent, continues washing with deionized water at last and presents neutrality until the pH of filtrating, filters oven dry.Thereby obtain having the mesoporous YPO of three-dimensional cubic Ia3d structure
4: 5%molTb
3+Mano-porous material.Pl-shows mesoporous YPO
4: 5%molTb
3+Nano material can transmitting green light under the ultraviolet excitation of 235nm wavelength.See accompanying drawing 6.
With fully stirring 1h in the 45ml normal hexane in the mesoporous silicon oxide KIT-6 dispersion of 1.0 grams, splash into gradually then the 1.1 gram Y (NO that are dissolved in the 5ml concentrated nitric acid in advance
3)
36H
2O, 0.065 gram Ce (NO
3)
36H
2O and 0.6 gram SPA homogeneous phase solution.Continue to be stirred to solvent evaporates and do, further in 100 ℃ of baking ovens, place 24h.With this rare earth yttrium phosphate: cerium/KIT-6 mixture is put in the retort furnace, slowly is warmed up to 650 ℃, keeps stopping heating behind the 5h, takes out behind the naturally cooling.2mol.L with 80 ℃
-1Sodium hydroxide solution 40ml stir process 40min, the control stirring velocity is 200～600r/min, further spinning; Discard supernatant liquid, repeat 4 times, continue washing with deionized water at last and present neutrality until the pH of filtrating to remove the mesoporous SiO 2 hard mould agent; Filter oven dry.Thereby obtain having the mesoporous YPO of three-dimensional cubic Ia3d structure
4: 5%molCe
3+Mano-porous material.Pl-shows mesoporous YPO
4: 5%molCe
3+Nano material can be launched blue light under the ultraviolet excitation of 302nm wavelength.See accompanying drawing 7.
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. the preparation method of a mesoporous rare earth phosphate fluophor is characterized in that comprising being prepared as follows step:
(1) configuration of rare-earth phosphate phosphor homogeneous phase solution
With soluble ree salt matrix and rare earth luminous body material Ln
3+According to mol ratio is 1: 0.001～0.1 mixing, and joining concentration is 16mol.L
-1Concentrated nitric acid in, further this mixed solution being joined concentration is 14mol.L
-1SPA in be made into the rare-earth phosphate phosphor homogeneous phase solution;
Wherein soluble rare-earth salt, rare earth luminous body material Ln
3+, concentration is 14mol.L
-1SPA and 16mol.L
-1The mol ratio of concentrated nitric acid is 1: 0.001～0.1: 0.5～3.5: 1.0～10.0;
Described soluble rare-earth salt adopts rare earth nitrate or hydrochloride;
Wherein rare earth nitrate is one or more mixtures in Yttrium trinitrate, Lanthanum trinitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Terbium trinitrate, the Dysprosium trinitrate;
Wherein rare earth luminous body material Ln
3+Be europium nitrate Eu (NO
3)
3, Terbium trinitrate Tb (NO
3)
3Or cerous nitrate Ce (NO
3)
3In one or more mixture;
(2), the preparation of the liquid alkane dispersion liquid of mesoporous silicon dioxide hard template agent
The mesoporous silicon oxide template is distributed to the alkane dispersion liquid of forming the silica template agent in the liquid alkane, and the mesoporous silicon oxide template is 1: 15～100 with the mass ratio of liquid alkane;
Mesoporous silicon dioxide hard template agent employing aperture is that the porous silica material of 2～50nm is the SBA-15 of two-dimentional hexagonal (P6m) or the KIT-6 of three-dimensional cubic structure (Ia3d);
Wherein liquid alkane is a normal butane, Skellysolve A, normal hexane, normal heptane and octane or their mixture;
(3) preparation of rare-earth phosphate phosphor/silica composite
The rare-earth phosphate phosphor homogeneous phase solution that step (1) is obtained joins in the liquid alkane dispersion liquid of the mesoporous silicon dioxide hard template agent that step (2) obtained; Wherein the rare-earth phosphate phosphor homogeneous phase solution is 1: 0.3～10 with the mass ratio of mesoporous silicon oxide; Stir simultaneously; The control mixing speed is 200～600r/min, evaporates into driedly fully until solvent, promptly gets rare-earth phosphate phosphor/silica composite;
(4), rare-earth phosphate phosphor/silica composite roasting
Between the rare-earth phosphate phosphor/silica composite roasting at high temperature that step (3) is obtained, 300～1300 ℃ of control maturing temperatures, roasting time is at 3～12h;
(5), remove the silicon dioxide hard template agent;
(a), after the reaction of step (4) rare-earth phosphate phosphor/silica composite roasting finishes, naturally cool to room temperature;
(b), after step (a) is cooled to room temperature, be 0.5～4mol.L with rare-earth phosphate phosphor/silica composite after the roasting and concentration
-1Sodium hydroxide solution be that the mass volume ratio of g/ml is 1: 10～60.0 to mix by unit, slowly stir, controlled temperature is between 30～100 ℃; Mixing speed is 200～600r/min; Time is 20～120min, and spinning then discards supernatant liquid; Or be 1～10% hydrofluoric acid solution with rare-earth phosphate phosphor/silica composite after the roasting and concentration by unit be that the mass volume ratio of g/ml is 1: 10～60.0 to mix; The control mixing speed is 200～600r/min; Churning time is 10～80min; Spinning then discards supernatant liquid;
(c), repeating step (b) 2～4 times to be to remove the silicon dioxide hard template agent, continues washing with deionized water at last and presents neutrality until the pH of filtrating, the solid product of gained is mesoporous rare earth phosphate fluophor.
2. the preparation method of a kind of mesoporous rare earth phosphate fluophor according to claim 1; It is characterized in that preferred rare earth nitrate is Yttrium trinitrate or Lanthanum trinitrate in the configuration of the rare-earth phosphate phosphor homogeneous phase solution described in the preparation process (1); In final formed yttrium phosphate fluor homogeneous phase solution or the phosphoric acid lanthanum fluorescence body homogeneous phase solution, yttrium phosphate YPO
4Or lanthanum orthophosphate LaPO
4With rare earth luminous body material Ln
3+Molar concentration rate be YPO
4: Ln
3+=1: 0.001～0.1 or LaPO
4: Ln
3+=1: 0.001～0.1.
3. the preparation method of a kind of mesoporous rare earth phosphate fluophor according to claim 1 is characterized in that rare-earth phosphate phosphor homogeneous phase solution described in the preparation process (3) and mesoporous silicon dioxide hard template agent mass ratio are 1: 0.5～4.
4. the preparation method of a kind of mesoporous rare earth phosphate fluophor according to claim 1 is characterized in that the mesoporous rare earth phosphate fluophor specific surface area that is obtained is 100～500m
2/ g, the aperture is 3～8nm, pore volume is 0.15～1.5cm
3/ g.
5. the preparation method of a kind of mesoporous rare earth phosphate fluophor according to claim 1, the absorption and the embedded material of the mesoporous rare earth phosphate fluophor useful as drug that it is characterized in that being obtained.
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| CN111019641B (en) * | 2019-12-31 | 2024-01-05 | 河北北方学院 | Preparation method of luminescent material based on rare earth phosphate |
| CN113292990B (en) * | 2021-05-11 | 2022-08-16 | 昆明理工大学 | Method for preparing silicon dioxide-based composite fluorescent material by terbium and cerium doped yellow phosphorus furnace slag |
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| EP1108772A2 (en) * | 1999-12-16 | 2001-06-20 | Kasei Optonix, Ltd. | Rare earth phosphate, its production process and rare earth phosphate phosphor |
| US7270793B2 (en) * | 2003-12-17 | 2007-09-18 | Patent-Treuhand-Gesellschaft Fuer Elektrische Gluehlampen Mbh | Process for producing a phosphate of the lanthanoids, and phosphate produced thereby |
| CN1907858A (en) * | 2005-08-03 | 2007-02-07 | 北京有色金属研究总院 | Process for preparing rare earth phosphate |
| CN101172639A (en) * | 2007-11-21 | 2008-05-07 | 上海应用技术学院 | Method of producing mesoporous rare-earth oxide |
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