CN106221692A - A kind of preparation method of monodisperse silica fluorescent microsphere - Google Patents
A kind of preparation method of monodisperse silica fluorescent microsphere Download PDFInfo
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Abstract
The present invention discloses chemical composition of a kind of monodisperse silica fluorescent microsphere and preparation method thereof.The chemical general formula of this fluorescent microsphere is SiO2@SiO2:Ln(L)3, wherein, SiO2Representing the silicon dioxide of fluorescent microsphere main part, Ln is denoted as the thulium of the centre of luminescence, and L is denoted as strengthening the organic ligand of fluorescence property.The preparation method of this fluorescent microsphere is that organic ligand sensitized fluorescence strengthens the colloidal sol seed law, is i.e. with silicon dioxide as nucleus of the seed, using silica-doped rare earth compounding as surface cover.Preparation method of the present invention is simple, and sphericity, monodispersity, stability and the luminescent properties of gained silica fluorescent microsphere is all preferable, and this fluorescent microsphere is with a wide range of applications at aspects such as photoelectric material, fluorescent labeling, drug targetings.
Description
Technical field
The present invention is to utilize a kind of monodisperse silica fluorescence of organic ligand sensitized fluorescence enhancing-colloidal sol seed law preparation
Microsphere, is i.e. with silicon dioxide as core, prepares single dispersing dioxy using silica-doped rare earth compounding as surface cover
SiClx fluorescent microsphere, belongs to fluorescent material preparation field.
Background technology
Monodisperse silica microspheres because its mechanical strength is high, good stability and the easy feature such as dispersion in a solvent,
And it is widely used in chromatographic column filler, coating, additive etc..Meanwhile, silicon dioxide microsphere also has avirulence, high biology is lived
The advantage such as property, hydrophilic, the easy functionalization of surface silanol group, therefore suffer from the biggest application at catalyst, biology, medical domain
It is worth.In order to realize more being widely applied of silicon dioxide microsphere, give its fluorescent functional, silica fluorescent can be prepared micro-
Ball.Fluorescent microsphere, can be as label at composite microcosmic owing to having stable structure and efficient luminous efficiency
The fields such as detection, biological detection imaging, medicine carrying and DNA detection play an important role.Compared to traditional organic fluorescence
Molecule, the emission spectrum of rare earth ion is symmetrical and narrow width, is difficult to photobleaching, and fluorescence lifetime is long, luminosity not with
Matrix material and change, so obtaining paying close attention to the most widely and studying.Therefore, the rare earth with silicon dioxide as substrate
Doping fluorescent microsphere can as signal tracer or fluorescence molecule composite microcosmic detection, life analysis science and
The fields such as medicine targeting research play a significant role.
Major part rare earth ion itself will not be luminous, part rare earth when at the ultraviolet light of certain wavelength or radiation of visible light
Ion can send characteristic fluorescence, and ratio is if launching the Eu of red fluorescence3+, the Tb of green fluorescence3+And the Ce of blue-fluorescence3+
And Eu2+Deng.It is largely focused at present about the research of silica fluorescent microsphere and rare earth ion is directly entrained in titanium dioxide
In silicon microsphere, such as, Yen-Ming Liu etc. prepare Eu by sol-gel microemulsion method3+The silica fluorescent of doping
Microsphere also analyzes different reaction conditions impact (the Sol-Gel Sci Technol on product morphology and monodispersity
(2012) 63:36-44).But, there is the defect that luminous intensity is low, the luminescence of composite to be strengthened in single rare earth ion
Intensity is necessary for increasing the doping of rare earth ion, and this adds the cost of composite to a certain extent and affects titanium dioxide
Silicon itself structure and performance.Numerous studies show, after rare earth ion forms coordination compound with organic ligand, its fluorescence is strong
Degree can be obviously enhanced.Therefore, for fluorescence property to be obtained preferable monodisperse silica fluorescent microsphere, rare earth can be coordinated
Thing is compound in silicon dioxide microsphere.At present, by main with the method that silicon dioxide forms composite fluorescence microsphere for rare earth compounding
Including reverse microemulsion process, sol-gel process, modification etc..Qin Pinzhu etc. utilize reverse microemulsion process to be prepared for Eu
(TTA)3Phen is core, and TEOS base catalysis condition hydrolyzes the long-term durability luminous nano granule that silicon dioxide the is shell (China obtained
Patent of invention, CN101362944 A).But, reverse microemulsion process is more suitably applied to the preparation of superfine nano granule, prepares
Fluorescent microsphere easily reunite, and its cost is high, and organic principle is difficult to remove, is easily affected by factors such as experiment conditions.Pottery
Foundation etc. use sol-gel process, have prepared with a series of different rare earth compounding nanometers as core, with silicon dioxide as shell
Composite (Chinese invention patent, CN102153576 A).Mingguang Yu et al. uses polyvinylpyrrolidone conduct
Rare earth compounding Eu (DBM)3Phen surfactant, utilizes hydrolysis under tetraethyl orthosilicate base catalysis to be prepared for coated with silica
The ball shaped nano composite of rare earth compounding, this composite launches strong redness under 350nm excitation source irradiates
Fluorescence (Journal of Materials Science & Technology, 2013 (9): 801 805).Traditional colloidal sol-
Although gel method can obtain the preferable product of sphericity, but due to rare earth compounding reunite and its pattern scrambling with
And clad silica surface has highly active silicone hydroxyl so that the fluorescent microsphere monodispersity obtained is poor, necessarily
The homogeneity distribution of particle diameter relatively difficult to achieve in degree, and the rare earth compounding interpolation that the composite obtained by cladding is needed
Measure more.Daojun Zhang etc. at silicon dioxide microsphere surface grafting rare earth compounding, are prepared for tool by modification
There are green and the red fluorescent microspheres (J. Phys. Chem. C 2010,114,12505 12510) of stronger luminous intensity.
But, modification can consume the silicone hydroxyl on fluorescent microsphere surface, thus reduces surface activity and the life of fluorescent microsphere
The thing compatibility.
Therefore, in order to prepare that sphericity and monodispersity be good, uniform particle sizes and the excellent fluorescent microsphere of luminescent properties,
This patent quasi-step matrix organic ligand sensitized fluorescence enhancement techniques, uses the colloidal sol seed law to prepare silica fluorescent microsphere.Colloidal sol
The seed law be utilize monodispersity micelle as seed, then by the method for physics or chemistry in the surface of the seed continued growth two
Silicon oxide, the advantage of the method can be by producing seed amount and controls microspherulite diameter.At present, more existing document report is logical
Cross the colloidal sol seed law to prepare silica fluorescent microsphere.Wherein, Michiel J. A. de Dood et al. by the seed law with
And acid catalyzed process is prepared for a diameter of 194nmEr3+The SiO of doping2Fluorescent material (Chemistry of materials, 2002,
14 (7): 2849-2853.).Lina Gong et al. uses Eu3+For the centre of luminescence, prepared in acid catalysis by the colloidal sol seed law
Go out SiO2@SiO2: Eu3+Single dispersing red fluorescent microspheres (Optical Materials, 2014,37:583-588).Therefore,
On the basis of the colloidal sol seed law, strengthen fluorescence property by introducing rare earth compounding sensitization, rare earth ion will be greatly improved
Luminescent quantum conversion efficiency, reduces rare earth addition, thus prepares and have good luminous performance and good sphericity, be uniformly dispersed
Silica fluorescent microsphere.
Summary of the invention
The present invention utilizes a kind of organic ligand sensitized fluorescence enhancing-colloidal sol seed law to prepare silica fluorescent microsphere, this
The chemical general formula planting fluorescent microsphere is SiO2@SiO2:Ln(L)3, wherein Ln represents rare earth elements europium (Eu), terbium (Tb), cerium (Ce)
In one, the sent fluorescence color of fluorescent microsphere prepared be respectively redness, yellow green, blueness；L represents organic ligand,
Mainly include the organic ligand of a series of beta-diketon class such as: 2-thenoyltrifluoroacetone (TTFA), trifluoroacetylacetone (TFA)
(TFA), dibenzoyl methane (DBM), acetylacetone,2,4-pentanedione (AcAc), benzoyl acetone (BA), benzoyltrifluoroacetone (BFA), β-
Naphthoyl trifluoroacetone (β-NTA).
The invention provides silica fluorescent method for preparing microsphere, specifically include following steps:
Step (a): prepare rare earth compounding Ln (L)3
Weigh Eu (NO respectively3)3、Tb(NO3)3、Ce(NO3)3Crystal is dissolved in 95% dehydrated alcohol and is formulated as a solution, separately takes organic
Ligand L or triethylamine are dissolved in 95% dehydrated alcohol and are formulated as b solution, until completely dissolved, by a under conditions of being stirred continuously
Solution dropwise instills in b solution, and in whole course of reaction, the pH value being regulated whole reaction system by triethylamine is maintained
Between 6.5-7.0.After reaction terminates, filter, wash, be dried to obtain rare earth compounding Ln (L)3。
Step (b): preparation SiO2@SiO2: Ln(L)3Fluorescent microsphere
Measure the distilled water of certain volume, dehydrated alcohol, ammonia respectively in beaker, sonic oscillation its make mix homogeneously, obtain c
Solution, under conditions of being stirred continuously, accurately measures the tetraethyl orthosilicate (TEOS) of certain volume, is slowly added in c solution anti-
D solution should be obtained the regular hour；Separately measure the dehydrated alcohol of certain volume, distilled water, ammonia in beaker, sonic oscillation its
Make mix homogeneously, obtain e solution, e solution is disposably poured in d solution react a period of time obtain f solution；Weigh certain matter
The rare earth compounding Ln (L) of step (a) gained of amount3, and be dissolved in acetone obtaining g solution, under the conditions of sonic oscillation
With microsyringe, g solution is slowly added in f solution, after reaction a period of time, is slowly added dropwise the TEOS of certain volume again,
Obtain sol product after reaction, then through being centrifuged, wash, being dried, finally obtain SiO2@SiO2: Ln(L)3Fluorescent microsphere.
Advantages of the present invention:
(1) present invention utilizes the colloidal sol seed law to prepare silica fluorescent microsphere, and its preparation technology is simple, the most just can
Complete reaction；
(2) in the present invention in preparing silica fluorescent microsphere introduce rare earth compounding strengthen luminescent properties, reduce rare earth from
Sub-doping, the most cost-effective；
(3) present invention is prepared the sphericity of gained silica fluorescent microsphere, monodispersity, stability and luminescent properties equal
Preferably, this fluorescent microsphere is with a wide range of applications at aspects such as photoelectric material, fluorescent labeling, drug targetings.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the monodisperse silica fluorescent microsphere A of the embodiment of the present invention 1.
Fig. 2 is the excitation and emission spectra figure of the monodisperse silica fluorescent microsphere A of the embodiment of the present invention 1.
Detailed description of the invention
The present invention can further illustrate in conjunction with the embodiments
Embodiment 1
Weigh 1mmolEu (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately takes 3mmol DBM, 3mmol
Triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously, a is molten
Liquid dropwise instills in b solution, and in whole course of reaction, the pH value being regulated whole reaction system by triethylamine maintains 6.5-
Between 7.0, stirring 1h after, sucking filtration, wash, be dried, obtain light yellow solid powder.
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min so that it is mixed
Close uniformly, as c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution,
D solution is obtained after reaction 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, Under Ultrasonic Vibration
Swing 5min, as e solution, e solution disposably poured into reaction 20min in d solution and obtains f solution,；Weigh 0.09g rare earth to join
Compound is dissolved in 2mL acetone soln and obtains g solution, with microsyringe, g solution is slowly added into f under the conditions of sonic oscillation
In solution, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, wash
Wash, be dried, finally obtain SiO2@SiO2: Eu(DBM)3Fluorescent microsphere A, testing its microsphere average diameter is 100-500nm, swashs
Sending out wavelength is 285nm, and a length of 614nm of transmitted wave belongs to emitting red light.
Embodiment 2
Weigh 1mmolEu (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately take 3mmol TTFA,
3mmol triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously
Dropwise being instilled by a solution in b solution, in whole course of reaction, the pH value being regulated whole reaction system by triethylamine is maintained
Between 6.5-7.0, stirring 1h after, sucking filtration, wash, be dried, obtain white solid powder.
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min, make mixing
Uniformly, as c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution, instead
D solution is obtained after answering 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, sonic oscillation
5min, as e solution, disposably pours e solution reaction 20min in d solution into and obtains f solution,；Weigh 0.09g rare earth to coordinate
Thing is dissolved in 2mL acetone soln and obtains g solution, with microsyringe, g solution is slowly added into f molten under the conditions of sonic oscillation
In liquid, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, washing,
It is dried, finally obtains SiO2@SiO2: Eu(TTFA)3Fluorescent microsphere B, testing its microsphere average diameter is 100-500nm, excites
Wavelength is 254nm, a length of 612nm of transmitted wave, belongs to emitting red light.
Embodiment 3
Weigh 1mmolEu (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately takes 3mmol TFA, 3mmol
Triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously, a is molten
Liquid dropwise instills in b solution, and in whole course of reaction, the pH value being regulated whole reaction system by triethylamine maintains 6.5-
Between 7.0, stirring 1h after, sucking filtration, wash, be dried, obtain rare earth compounding.
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min, make mixing
Uniformly, as c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution, instead
D solution is obtained after answering 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, sonic oscillation
5min, as e solution, disposably pours e solution reaction 20min in d solution into and obtains f solution,；Weigh 0.09g rare earth to coordinate
Thing is dissolved in 2mLDMF solution and obtains g solution, with microsyringe, g solution is slowly added into f molten under the conditions of sonic oscillation
In liquid, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, washing,
It is dried, finally obtains SiO2@SiO2: Eu(TFA)3Fluorescent microsphere C, testing its microsphere average diameter is 100-500nm, excitation wave
A length of 340nm, a length of 617nm of transmitted wave, belong to emitting red light.
Embodiment 4
Weigh 1mmolEu (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately take 3mmol AcAc,
3mmol triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously
Dropwise being instilled by a solution in b solution, in whole course of reaction, the pH value being regulated whole reaction system by triethylamine is maintained
Between 6.5-7.0, stirring 1h after, sucking filtration, wash, be dried, obtain rare earth compounding.
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min, make mixing
Uniformly, as c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution, instead
D solution is obtained after answering 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, sonic oscillation
5min, as e solution, disposably pours e solution reaction 20min in d solution into and obtains f solution,；Weigh 0.09g rare earth to coordinate
Thing is dissolved in 2mLDMF solution and obtains g solution, with microsyringe, g solution is slowly added into f molten under the conditions of sonic oscillation
In liquid, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, washing,
It is dried, finally obtains SiO2@SiO2: Eu(AcAc)3Fluorescent microsphere D, testing its microsphere average diameter is 100-500nm, excites
Wavelength is 320nm, a length of 615nm of transmitted wave, belongs to emitting red light.
Embodiment 5
Weigh 1mmolEu (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately takes 3mmol BFA, 3mmol
Triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously, a is molten
Liquid dropwise instills in b solution, and in whole course of reaction, the pH value being regulated whole reaction system by triethylamine maintains 6.5-
Between 7.0, stirring 1h after, sucking filtration, wash, be dried, obtain rare earth compounding.
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min, make mixing
Uniformly, as c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution, instead
D solution is obtained after answering 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, sonic oscillation
5min, as e solution, disposably pours e solution reaction 20min in d solution into and obtains f solution,；Weigh 0.09g rare earth to coordinate
Thing is dissolved in 2mLDMF solution and obtains g solution, with microsyringe, g solution is slowly added into f molten under the conditions of sonic oscillation
In liquid, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, wash
Wash, be dried, finally obtain SiO2@SiO2: Eu(BFA)3Fluorescent microsphere E, testing its microsphere average diameter is 100-500nm, swashs
Sending out wavelength is 340nm, and a length of 620nm of transmitted wave belongs to emitting red light.
Embodiment 6
Weigh 1mmolTb (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately take 3mmol AcAc,
3mmol triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously
Dropwise being instilled by a solution in b solution, in whole course of reaction, the pH value being regulated whole reaction system by triethylamine is maintained
Between 6.5-7.0, stirring 1h after, sucking filtration, wash, be dried, obtain rare earth compounding.
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min, make mixing
Uniformly, as c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution, instead
D solution is obtained after answering 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, sonic oscillation
5min, as e solution, disposably pours e solution reaction 20min in d solution into and obtains f solution,；Weigh 0.09g rare earth to coordinate
Thing is dissolved in 2mLDMF solution and obtains g solution, with microsyringe, g solution is slowly added into f molten under the conditions of sonic oscillation
In liquid, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, washing,
It is dried, finally obtains SiO2@SiO2: Tb(AcAc)3Fluorescent microsphere F, testing its microsphere average diameter is 100-500nm, excites
Wavelength is 400nm, a length of 550nm of transmitted wave, belongs to green emitting.
Embodiment 7
Weigh 1mmol Ce (NO3)3Crystal is dissolved in 20mL95% dehydrated alcohol and is formulated as a solution, separately take 3mmol AcAc,
3mmol triethylamine is dissolved in 20mL 95% dehydrated alcohol and is formulated as b solution, until completely dissolved, under conditions of being stirred continuously
Dropwise being instilled by a solution in b solution, in whole course of reaction, the pH value being regulated whole reaction system by triethylamine is maintained
Between 6.5-7.0, stirring 1h after, sucking filtration, wash, be dried, obtain rare earth compounding
Measure 25mL distilled water, 65mL dehydrated alcohol, 7mL ammonia respectively in beaker, sonic oscillation 20min, make mix homogeneously,
As c solution, under conditions of being stirred continuously, measure 4mL tetraethyl orthosilicate (TEOS) and be slowly added in c solution, reaction
D solution is obtained after 30min；Another 18mL dehydrated alcohol, 8mL distilled water, the 2mL ammonia of measuring respectively in beaker, sonic oscillation
5min, as e solution, disposably pours e solution reaction 20min in d solution into and obtains f solution,；Weigh 0.09g rare earth to coordinate
Thing is dissolved in 2mLDMF solution and obtains g solution, with microsyringe, g solution is slowly added into f molten under the conditions of sonic oscillation
In liquid, continue after sonic oscillation 30min, be slowly added to 1mL TEOS, after reaction 2h, obtain sol product, more by centrifugation, washing,
It is dried, finally obtains SiO2@SiO2: Ce(AcAc)3Fluorescent microsphere G, testing its microsphere average diameter is 100-500nm, excites
Wavelength is 335nm, a length of 452nm of transmitted wave, belongs to blue-light-emitting.
Claims (2)
1. a monodisperse silica fluorescent microsphere, its chemical general formula is SiO2@SiO2: Ln(L)3, wherein Ln represents rare earth
Element, L represents organic ligand, prepares this silica fluorescent by the organic ligand sensitized fluorescence enhancing-colloidal sol seed law micro-
Specifically comprising the following steps that of ball
(1) rare earth compounding Ln (L) is first prepared3: with rare earth nitrate Ln (NO3)3It is that preparation of raw material becomes one with organic ligand L
Determine the ethanol solution of concentration, then rare earth ion ethanol solution is added dropwise in organic ligand ethanol solution, in certain pH
In the range of there is complexation reaction, then through filtering, obtaining rare earth compounding Ln (L) after drying3；
(2) SiO is then prepared2@SiO2: Ln(L)3Fluorescent microsphere: prepare silica seeds solution with teos hydrolysis,
Then by step (1) gained rare earth compounding Ln (L)3It is added thereto, again adds tetraethyl orthosilicate and be hydrolyzed reaction, finally
Through filtering, wash, obtaining monodispersed silica fluorescent microsphere after drying.
2. in the method for the silica fluorescent microsphere prepared as claimed in claim 1,
(1) one during Ln represents rare earth elements europium (Eu), terbium (Tb), cerium (Ce), L represents the organic ligand of beta-diketon class:
2-thenoyltrifluoroacetone (TTFA), trifluoroacetylacetone (TFA) (TFA), dibenzoyl methane (DBM), acetylacetone,2,4-pentanedione (AcAc),
Benzoyl acetone (BA), benzoyltrifluoroacetone (BFA), β-naphthoyl trifluoroacetone (β-NTA)；
(2) rare earth compounding Ln (L) is prepared3PH span of control be 6.5-8.5, its compound concentration is 0.01-0.2mol/L；Dilute
Soil coordination compound with the ratio range of the amount of the material again adding tetraethyl orthosilicate is: 0.3%≤n (Ln (L)3): n (TEOS)
≤5.0%。
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| CN107321313A (en) * | 2016-09-22 | 2017-11-07 | 武汉大学 | A kind of Surface porous core shell structure silica gel microball and its preparation method and application |
| 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 |
| CN110132918A (en) * | 2019-05-15 | 2019-08-16 | 四川大学 | The three-dimensional net structure characterizing method of functional stuffing in polymer composite foam 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 |
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| CN107321313B (en) * | 2016-09-22 | 2019-10-25 | 武汉大学 | A kind of Surface porous core-shell structure silica gel microball and its preparation method and application |
| 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 |
| 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 |
| CN110132918A (en) * | 2019-05-15 | 2019-08-16 | 四川大学 | The three-dimensional net structure characterizing method of functional stuffing in polymer composite foam material |
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| 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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