CN1300258C - Process for preparing visible light absorbable titanium dioxide and its composite materials - Google Patents
Process for preparing visible light absorbable titanium dioxide and its composite materials Download PDFInfo
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- CN1300258C CN1300258C CNB2005100263050A CN200510026305A CN1300258C CN 1300258 C CN1300258 C CN 1300258C CN B2005100263050 A CNB2005100263050 A CN B2005100263050A CN 200510026305 A CN200510026305 A CN 200510026305A CN 1300258 C CN1300258 C CN 1300258C
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Abstract
The present invention provides a method for preparing titanium dioxide and a composite material of the titanium dioxide. The method comprises the following steps: through a sol-gel method or a hydrosol-gel method, the titanium dioxide is obtained; then, tetrahydrofuran is added in a titanium dioxide solution; the obtained titanium dioxide is compounded with an inorganic matter or / and a polymer. The titanium dioxide and the composite material of the titanium dioxide which are prepared by the method of the present invention is capable of both super powerful ultraviolet light absorption and strong visible light absorption. The material can be applied to photoelectric conversion equipment, photocatalysts, biosensors and other relevant fields.
Description
Technical field
The invention relates to the method that a kind of preparation has the titanium dioxide and the matrix material thereof of visible absorption
Background technology
The titanium dioxide semiconductor material is owing to have higher refractive index, very strong ultraviolet absorption, and excellent photoelectricity conversion performance and photocatalysis performance etc. are so more and more cause people's extensive studies interest.The ability that the photoelectricity conversion of titanium dioxide and photo-catalysis capability depend primarily on its light absorbing energy.In order to increase the surface-area of material, thereby increase light absorbing ability, often need titanium dioxide is made little particle to nano-grade size.The nanoparticle of the various crystal formations of common titanium dioxide (anatase octahedrite, rutile etc.) all is transparent at visible region, and strong absorption is only just arranged in the ultraviolet region.But in solar spectrum, ultraviolet content is very low, main concentration of energy is in visible region, therefore a kind of key problem in technology that improves titanic oxide material photoelectricity conversion performance and photocatalysis performance that generally believes at present is the energy bandwidth that reduces titanium dioxide, and the absorption spectrum of expanding titanium dioxide is to the visible region.
In order to prepare titanic oxide material with visible light activity, ion doping, ion implantation and dye sensitization etc. all is the comparison effective means, but do not appear in the newspapers up to now by the research of titanium dioxide nanocrystalline being carried out shape control introducing visible absorption, existing shape Control Study does not make titanic oxide material have visible light activity yet.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with titanium dioxide and matrix material thereof of visible absorption.
The Application Areas that the purpose of this invention is to provide above-mentioned titanium dioxide and matrix material thereof.
Preparation method with titanic oxide material of visible absorption of the present invention is:
(1) TiO 2 precursor prepares titania solution by sol-gel processing or non-aqueous sol-gel method;
(2) add tetrahydrofuran (THF) in the solution for preparing, the mol ratio that adds tetrahydrofuran (THF) and titanium dioxide is 0.001～1000, and is dry or moist as required then;
(3) above-mentioned titanium dioxide and other inorganic materials, polymer materials is compound, make binary or trielement composite material.
The presoma of above-mentioned titanium dioxide is titanic acid ester or titaniferous halogenide.
The content of above-mentioned titanium dioxide in the binary matrix material is 0.1～99.9wt%.
The content of above-mentioned titanium dioxide, inorganic materials, polymer materials trielement composite material is:
Titanium dioxide: 10～80wt%,
Inorganic materials: 10～80wt%,
Polymer materials: 10～80wt%.
Binary or the ternary complex that contains titanium dioxide of the present invention obtains by directly being mixed with.
Binary or the ternary complex that contains titanium dioxide of the present invention prepares by sol-gel processing.
Binary or the ternary complex that contains titanium dioxide of the present invention prepares by non-aqueous sol-gel method.
After titanium dioxide or its composite inorganic thing and polymer monomer directly mixed when binary that contains titanium dioxide of the present invention or ternary complex prepared, prepare by monomer polymerization.
Titanium dioxide or its composite inorganic thing and polymer materials mixed when binary that contains titanium dioxide of the present invention or ternary complex prepared, and added compound making behind silane coupling agent or the titanate coupling agent again.
Titanium dioxide or its composite inorganic thing and polymer monomer mixed when binary that contains titanium dioxide of the present invention or ternary complex prepared, and added silane coupling agent or titanate coupling agent again, carried out monomer polymerization then and prepared.
Used TiO 2 precursor is titanic acid ester or other titanium-containing compound in the above-mentioned preparation process, and wherein the structure of titanic acid ester is Ti (OR)
4, wherein R is the alkanes group; Other titanium-containing compound is mainly the halogenide of titanium, as titanium tetrachloride etc., but does not get rid of other titanium-containing compound.
Silane coupling agent and titanate coupling agent used in the above-mentioned preparation process are existing commercially available commodity.
Other inorganics among the present invention is mainly silicon oxide, aluminum oxide, zirconium white and zinc oxide etc., but do not get rid of other inorganic materials, in the middle of them one or more presoma can with TiO 2 precursor generation colloidal sol-gel reaction or non-aqueous sol-gel reaction.
The present invention carries out shape control by adding tetrahydrofuran (THF) to titanium dioxide nanocrystalline and matrix material thereof, reduce titanium dioxide energy bandwidth, widen its spectral absorption, preparation all has photoelectricity conversion capability and catalytic activity under UV-light and visible light titanium dioxide and matrix material thereof.The titanium dioxide that the present invention proposes and the matrix material of titanium dioxide thereof also have good visible absorption except keeping splendid ultraviolet absorption performance, can improve its electricity conversion and photocatalysis performance greatly.
Embodiment
Embodiment 1
The 20g isopropyl titanate is dissolved in the 30g methyl alcohol, adds 20g acetic acid and 4.5g distilled water, room temperature reaction 2 hours, add the 1g tetrahydrofuran (THF) then, the back of filming is at 700 ℃ of thermal treatments 10 hours, the titanium dioxide film that obtains having visible absorption.
Embodiment 2
The 1g tetraethoxy is dissolved in the 50g ethanol, adds 0.7g 5% hydrochloric acid soln then and also at room temperature reacted 2 hours, obtain silicon dioxide gel.The 1200g tetrabutyl titanate is joined in the 2000g ethanol, add silicon dioxide gel then, room temperature reaction 2 hours adds 2g tetrahydrofuran (THF), the titanium oxide inorganic complex sol that obtains having visible absorption in this solution.
Embodiment 3
In 1g titanium tetrachloride solution 3000g ethanol, add the 1000g aluminum isopropylate then, room temperature reaction is after 5 hours, the tetrahydrofuran solution that adds 10g 5% polymethylmethacrylate, stir after 5 minutes 100 ℃ of vacuum-treat 10 hours, the composite titania material that obtains having visible absorption.
Embodiment 4
Add 0.1g silane coupling agent (KH570) in the titanium oxide inorganic complex sol in 1g embodiment 2, room temperature reaction 1 hour, the tetrahydrofuran solution and the 0.8g initiator A IBN that add 1000g 20% butyl methacrylate then, 70 ℃ were reacted 10 hours, film, obtain having the composite titania material of visible absorption.
Embodiment 5
In the ethanolic soln of 500g 40% tetraethoxy, add 150g 5% hydrochloric acid, stirring reaction adds the ethanolic soln of 5g 40% titanium tetrachloride again under the room temperature after 2 hours, with reaction under the above-mentioned system room temperature 5 hours, add the 50g tetrahydrofuran (THF), the postlyophilization that stirs, the titanium oxide inorganic composite powder that obtains having visible absorption.
Embodiment illustrated and that discuss is only used for demonstrating use known for inventor best mode of the present invention to those skilled in the art in this specification sheets.Any content in the specification sheets all can not be thought limiting the scope of the invention.Can make amendment and do not exceed scope of the present invention above embodiment, by above explanation, implementing the inventive method be conspicuous for those skilled in the art.Therefore, should be appreciated that in the scope of claims and equivalent thereof, can implement the present invention in the mode different with above specific descriptions.
Claims (10)
1. preparation method with titanic oxide material of visible absorption is characterized in that:
(1) TiO 2 precursor prepares titania solution by sol-gel method or non-aqueous sol-gel method;
(2) add tetrahydrofuran (THF) in the solution for preparing, the mol ratio that adds tetrahydrofuran (THF) and titanium dioxide is 0.001～1000, and is dry or moist as required then;
(3) above-mentioned titanium dioxide and other inorganic materials, polymer materials is compound, make binary or trielement composite material.
2. preparation method according to claim 1, the presoma that it is characterized in that titanium dioxide is titanic acid ester or titaniferous halogenide.
3. preparation method according to claim 1 is characterized in that the content of titanium dioxide in the binary matrix material is 0.1～99.9wt%.
4. preparation method according to claim 1 is characterized in that the content of titanium dioxide, inorganic materials, polymer materials trielement composite material is:
Titanium dioxide: 10～80wt%
Inorganic materials: 10～g0wt%
Polymer materials: 10～80wt%.
5. according to claim 1,3 or 4 described preparation methods, it is characterized in that the binary or the ternary complex that contain titanium dioxide obtain by directly being mixed with.
6. according to claim 1,3 or 4 described preparation methods, it is characterized in that the binary or the ternary complex that contain titanium dioxide prepare by sol-gel method.
7. according to claim 1,3 or 4 described preparation methods, it is characterized in that the binary or the ternary complex that contain titanium dioxide prepare by non-aqueous sol-gel method.
8. according to claim 1,3 or 4 described preparation methods, titanium dioxide or its composite inorganic thing and polymer monomer directly mix when it is characterized in that containing the binary of titanium dioxide or ternary complex and preparing, and prepare by monomer polymerization.
9. according to claim 1,3 or 4 described preparation methods, titanium dioxide or its composite inorganic thing and polymer materials mix when it is characterized in that containing the binary of titanium dioxide or ternary complex and preparing, and add compound preparing behind silane coupling agent or the titanate coupling agent again.
10. according to claim 1,3 or 4 described preparation methods, titanium dioxide or its composite inorganic thing and polymer monomer mix when it is characterized in that containing the binary of titanium dioxide or ternary complex and preparing, add silane coupling agent or titanate coupling agent again, carry out monomer polymerization then and prepare.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100263050A CN1300258C (en) | 2005-05-30 | 2005-05-30 | Process for preparing visible light absorbable titanium dioxide and its composite materials |
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| CNB2005100263050A CN1300258C (en) | 2005-05-30 | 2005-05-30 | Process for preparing visible light absorbable titanium dioxide and its composite materials |
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| CN1699478A CN1699478A (en) | 2005-11-23 |
| CN1300258C true CN1300258C (en) | 2007-02-14 |
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| CNB2005100263050A Expired - Fee Related CN1300258C (en) | 2005-05-30 | 2005-05-30 | Process for preparing visible light absorbable titanium dioxide and its composite materials |
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| CN109491174B (en) * | 2018-11-19 | 2020-09-04 | 浙江精一新材料科技有限公司 | Inorganic-organic hybrid core-shell nanorod and light valve with same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405214A (en) * | 2002-11-08 | 2003-03-26 | 清华大学 | Method for preparing visible light catalytic degraded plastic |
| CN1587325A (en) * | 2004-08-05 | 2005-03-02 | 复旦大学 | High stability high transparency rutile type nano titanium dioxide slurry and its dispersively preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405214A (en) * | 2002-11-08 | 2003-03-26 | 清华大学 | Method for preparing visible light catalytic degraded plastic |
| CN1587325A (en) * | 2004-08-05 | 2005-03-02 | 复旦大学 | High stability high transparency rutile type nano titanium dioxide slurry and its dispersively preparing method |
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