CN108329907A - Hard template sol-gal process prepares long-persistence luminous nano material - Google Patents
Hard template sol-gal process prepares long-persistence luminous nano material Download PDFInfo
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- CN108329907A CN108329907A CN201810260377.9A CN201810260377A CN108329907A CN 108329907 A CN108329907 A CN 108329907A CN 201810260377 A CN201810260377 A CN 201810260377A CN 108329907 A CN108329907 A CN 108329907A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7706—Aluminates
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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Abstract
The present invention provides a kind of hard template sol-gal process preparing long-persistence luminous nano material.This method can well solve the Sintering Problem that existing long-persistence luminous nano material generates in high-temperature burning process, facilitate large-scale production long-persistence nano material.Such long-persistence nano material has larger application value in biomedical sectors such as bioluminescence marker, the diagnosis of tumour luminescence imaging and optical dynamic therapies.This method is applied widely, can be widely applied to the long afterglow composite nano materials for preparing a variety of luminescent spectrums, is particularly suitable for preparing the high long-afterglow material of the synthesis temperatures such as silicate, aluminate, aluminosilicate, gallate.This method is mainly characterized by using nano particles such as silica cheap and easy to get, aluminium oxide, zirconium oxides as hard template, the long afterglow precursor sol raw material of liquid is adsorbed on hard mold plate surface, (hard template@gel moulds) structure is formed after desiccant gel, then it calcines under the high temperature conditions, obtains the long-persistence luminous nanometer material of (hard template@long-afterglow materials) nucleocapsid.
Description
Technical field
The invention belongs to long after glow luminous material field, relates generally to a kind of synthesizing long-persistence and shine composite nano materials
New method.In more detail, the present invention utilizes the high-temperature resistant nanos materials such as nano silicon dioxide, nano aluminium oxide, nano zircite
Material is hard template, and the long afterglow precursor sol raw material of liquid is adsorbed on hard mold plate surface, (hard template is formed after desiccant gel
Gel mould) structure, it then calcines under the high temperature conditions, obtains the long-persistence luminous of (hard template@long-afterglow materials) nucleocapsid
Nano material.
Background technology
Long-persistence luminous nano material has distinctive excitation long persistent luminescence characteristic in short-term.The material is received as novel light-emitting
Rice probe has larger practical application potentiality in biomedical sector.But no matter traditional alkaline-earth silicate, alkaline earth aluminate
Salt long-afterglow material or novel Cr3+ activate gallic acid salt material, it usually needs could be obtained by high-temperature calcination excellent
Long-persistence luminous property.So obtained product is typically the blocks of solid of height sintering, it is necessary to by cumbersome crushing, grind
Mill, classification can just obtain fine grained.Nevertheless, conventional method is still difficult to obtain nanometer production monodispersed, that pattern is regular
Product.Part research is successfully prepared for porous long-persistence nano material by mesoporous template, but due to the use of mesoporous mould
Plate loses thermal stability when more than 900 DEG C, deforms rapidly, is sintered, grows up into blocks of solid.So in more than 900 DEG C items
It is extremely difficult that long-persistence nano material monodispersed, that pattern is regular is largely prepared under part.Currently, both at home and abroad there is not yet
The relevant report of long-persistence nano material monodispersed, that pattern is regular is synthesized by hard template method.
Invention content
The object of the present invention is to provide a kind of new methods for producing monodisperse long-persistence nano material in enormous quantities.Work of the present invention
Skill is simple, is easy to mass produce.Regular, the size adjustable using long-persistence luminous appearance of nano material produced by the invention, production
Product hard aggregation-free, luminescent properties are excellent, are easy to large-scale production.Template in the present invention refers to utilizing heat safe nano oxygen
The nano materials such as SiClx, nano aluminium oxide, nano zircite are template, more than the larger specific surface area absorption length of nano-form
Brightness precursor sol raw material is formed the nucleocapsid of (nano-form@long afterglows precursor gel) by drying process, is forged by high temperature
Burning obtains long-persistence nano material.The hard template method mainly has there are four advantage：(1) size and shape of product can be by receiving
Rice template is adjusted and controls；(2) building-up process can be resistant to more than 900 DEG C or more high temperature, and product luminescent properties are excellent；
(3) the long-persistence nano material easily disperseed is directly obtained, is not required to subsequently grind；(4) production scale is from gram-grade to tonne can be random
Control.
The invention mainly comprises following basic steps：
1, prepare or directly buy high-temperature resistant nano template
This method is high-temperature resistant nano template using mono-dispersed nano silica, nano aluminium oxide, nano zircite etc.,
The grain size and pattern of product are adjusted by adjusting template size and pattern.Both the shape characteristic of the nano-form selected determines life
The microscopic appearance feature of the long-persistence nano material of production.High-temperature resistant nano templated synthesis technical maturity used, has much engaged in trade
Product, such as nano silicon dioxide, nano aluminium oxide, nano zircite etc. easily can be directly commercially available.
2, the precursor sol of long-persistence nano material is prepared
The element for constituting long-persistence nano material generally comprises various matrix elements, such as Ca, Mg, Sr, Ba, Zn, Cd, Ga,
Al, Y, Lu, Gd, Si, Ge, Sn, Ti etc., also various a small amount of doping are as the centre of luminescence or the codope of adjusting long afterglow qualities
Element, such as Li, Mn, Eu, Cr, Ce, Dy, Nd, Yb etc..Most of metallic element can be by dissolving corresponding nitrate, hydrochloric acid
Salt etc. obtains solution, Si and Ti elements can be by hydrolyzing corresponding organic ester, such as tetraethyl orthosilicate, titanium in acid condition
Sour four N-butyls etc., obtain colloidal sol.Citric acid, polyethylene glycol, boric acid, ammonium chloride etc. are added in solution to adjust metal ion
Solubility, colloidal sol viscosity etc..
3, (template@long afterglows gel) intermediate of nucleocapsid is prepared
High-temperature resistant nano template described in a certain amount of step (1) is added in step (2) described colloidal sol, filtering or
It centrifuges and removes remaining colloidal sol.The nano-form for having adsorbed colloidal sol is incubated at a certain temperature, is dry.Templating nanoparticles circle
Colloidal sol on face because moisture volatilization and gelation, obtain the nucleocapsid of (template@gels).
4, high-temperature calcination produces long-persistence nano material
The intermediate that step (3) obtains will be passed through, be put into high temperature furnace, as needed with corresponding air atmosphere, inertia
Atmosphere or protection of reducing atmosphere, through high-temperature calcination certain time, long-afterglow material is in high-temperature resistant nano template surface crystallization, production
Grow afterglow shell.After cooling, (template@long afterglows) composite nano materials of nucleocapsid are obtained.
Description of the drawings
Fig. 1 is SiO2@Zn2SiO4:The X ray diffracting spectrum of Yb, Mn long-persistence nano material.
Fig. 2 is SiO2@Zn2SiO4:The electron scanning micrograph of Yb, Mn long-persistence nano material.
Fig. 3 is SiO2@Zn2SiO4:The long-persistence luminous spectrum of Yb, Mn.
Fig. 4 is SiO2@Zn2SiO4:The long-persistence luminous attenuation curve of Yb, Mn at 510nm.
Specific implementation mode
As an example, we introduce it is a kind of using nano silicon oxide be high temperature resistant template prepare monodisperse green length more than
Brightness composite nano materials SiO2@Zn2SiO4:The specific implementation method of Yb, Mn.By a certain amount of zinc nitrate, ytterbium nitrate, manganese nitrate,
Citric acid is dissolved in 50mL water, and enriching salt acid for adjusting pH is 0~3, and tetraethyl orthosilicate is added under stirring condition, is added certain
Measure polyethylene glycol (Mw.400~10 000) adjust viscosity, control Zn/Si/Yb/Mn molar ratio be 2/1/0.02/0.005, one
Determine to obtain colloidal sol after stirring 1~24 hour at temperature.Amorphous silica nano particle 1g~10g of 50nm-5000nm
It is immersed in 50mL colloidal sols, stirs 1~24 hour, filter, dry 1 under the conditions of 30 DEG C~100 DEG C~for 24 hours, obtain (template@long
Twilight sunset gel) intermediate.Intermediate is put into Muffle furnace, under air atmosphere, 1min~48h is calcined at 900 DEG C~1300 DEG C
Afterwards, it after cooled to room temperature, takes out, it is SiO2@Zn2SiO4 to obtain loosely organized white powder:More than Yb, Mn green length
Brightness nano material.Due to calcination temperature height, silicon dioxide nano template is partly or entirely converted into quartzy phase two from unformed shape
Silica (Fig. 1), but still keep the original pattern of template and size (Fig. 2).SiO2@Zn2SiO4:Yb, Mn nano material are passed through
After 254nm ultraviolet lights, bright green long afterglow can be sent out and shine (Fig. 3,4).
Claims (6)
1. the template described in this patent refers to size in the heat safe silica of 10nm to 1um, aluminium oxide, zirconium oxide, alkaline earth
Silicate, alkaline earth aluminate, alkaline earth aluminates, one kind in the nano materials such as alkaline earth phosphate or mixture.
2. template according to claim 1, it is raw material that template, which refers to using the template described in claim 1, by template
It is immersed in the premise colloidal sol of long-afterglow material, using the adsorption long afterglow colloidal sol of template, after drying in template surface
It forms long afterglow premise gel film and obtains long-persistence luminous nano material by high-temperature calcination technique.
3. template according to claim 2, wherein the colloidal sol refers to metal ion, citric acid, ethylene glycol and its
The additive (such as polyethylene glycol, polyvinylpyrrolidone, the macromolecules such as starch) that he increases viscosity is dissolved in water the tool to be formed
There is the liquid dispersion of larger viscosity.
4. according to claim 3, wherein the metal ion refers to the solvable of the metallic element of composition long-afterglow material
Solve salt, such as Zn2SiO4:Zn2+ in Yb, Mn, Yb3+, Mn2+；SrAl2O4:Sr2+ in Eu, Dy, Al3+, Eu3+, Dy3+；
ZnGa2O4:Zn2+ in Cr, Ga3+, Cr3+.
5. according to claim 2, wherein the long-afterglow material refers to SrAl2O4:Eu,Dy；Sr2MgSi2O7:Eu,
Dy；Zn2SiO4:Yb,Mn；LiGa5O8:Cr；ZnXGayGezOx+1.5y+2z+1.5m:Crm；Y3AlxGa5-xO12:Cr,Ce
Deng to represent Eu2+ or Cr3+ be one kind or derivative in the long-afterglow material of the centre of luminescence.
6. according to claim 5, wherein the derivative refers to will be by the alkaline earth element in long-afterglow material molecular formula
Other diads are replaced by, Sr is completely or partially such as replaced by Ca, Mg, Ba, one or more of Zn, Cd etc.；By Al
Completely or partially it is replaced by Ga, In etc.；Y element is completely or partially replaced by La, Lu, Gd etc.；Increase micro codope member
Element, such as Eu, Yb, Er, Li, Sn, Ge, Dy, Ho, Nd etc..
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| CN201810260377.9A CN108329907A (en) | 2018-03-27 | 2018-03-27 | Hard template sol-gal process prepares long-persistence luminous nano material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229657A (en) * | 2019-04-26 | 2019-09-13 | 深圳科尔新材料科技有限公司 | The preparation method of long afterglow mechanoluminescence material |
| CN114369457A (en) * | 2021-12-09 | 2022-04-19 | 江西师范大学 | Preparation method of green long-afterglow luminescent material |
| CN115646551A (en) * | 2022-11-08 | 2023-01-31 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
| CN110229657B (en) * | 2019-04-26 | 2024-07-26 | 深圳科尔新材料科技有限公司 | Preparation method of long-afterglow luminescent material |
Citations (3)
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| CN102994074A (en) * | 2011-09-19 | 2013-03-27 | 中国科学院城市环境研究所 | Preparation of monodisperse porous long afterglow luminescent nano material by adopting template method |
| CN103074061A (en) * | 2013-01-04 | 2013-05-01 | 沈阳化工大学 | Synthetic method of rare earth nanometer nuclear shell spherical particle luminescent material |
| CN103261367A (en) * | 2010-12-14 | 2013-08-21 | 罗地亚管理公司 | Composition containing a core-hell aluminate, phosphor obtained from said composition, and preparation methods |
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2018
- 2018-03-27 CN CN201810260377.9A patent/CN108329907A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261367A (en) * | 2010-12-14 | 2013-08-21 | 罗地亚管理公司 | Composition containing a core-hell aluminate, phosphor obtained from said composition, and preparation methods |
| CN102994074A (en) * | 2011-09-19 | 2013-03-27 | 中国科学院城市环境研究所 | Preparation of monodisperse porous long afterglow luminescent nano material by adopting template method |
| CN103074061A (en) * | 2013-01-04 | 2013-05-01 | 沈阳化工大学 | Synthetic method of rare earth nanometer nuclear shell spherical particle luminescent material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229657A (en) * | 2019-04-26 | 2019-09-13 | 深圳科尔新材料科技有限公司 | The preparation method of long afterglow mechanoluminescence material |
| CN110229657B (en) * | 2019-04-26 | 2024-07-26 | 深圳科尔新材料科技有限公司 | Preparation method of long-afterglow luminescent material |
| CN114369457A (en) * | 2021-12-09 | 2022-04-19 | 江西师范大学 | Preparation method of green long-afterglow luminescent material |
| CN114369457B (en) * | 2021-12-09 | 2023-05-16 | 江西师范大学 | Preparation method of green long-afterglow luminescent material |
| CN115646551A (en) * | 2022-11-08 | 2023-01-31 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
| CN115646551B (en) * | 2022-11-08 | 2023-12-08 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
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