CN102718255A - Preparation method of titanium dioxide hollow nano structure - Google Patents
Preparation method of titanium dioxide hollow nano structure Download PDFInfo
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- CN102718255A CN102718255A CN2012102023530A CN201210202353A CN102718255A CN 102718255 A CN102718255 A CN 102718255A CN 2012102023530 A CN2012102023530 A CN 2012102023530A CN 201210202353 A CN201210202353 A CN 201210202353A CN 102718255 A CN102718255 A CN 102718255A
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Abstract
The invention relates to nano titanium dioxide, particularly a preparation method of titanium dioxide hollow nano structures. According to the invention, ammonium fluotitanate ((NH4)2TiF6) is used as a precursor, silicon dioxide (SiO2) microspheres are used as a template, and the concentration of the ammonium fluotitanate ((NH4)2TiF6), the hydrothermal time and the silicon dioxide (SiO2) size are regulated to control the size of the hollow microspheres and the thickness of the shell. Thus, under relatively low temperature conditions, the titanium dioxide SiO2 hollow nano microsphere structures of which the sizes and the structures have high isotonicity can be massively synthesized, thereby solving the problem of overwide size distribution range in the past silicon dioxide synthesis process. The method provided by the invention is simple and easy to control, has the advantage of low cost, is suitable for industrial production, and can control the size of the reaction product through reaction conditions.
Description
Technical field
The present invention relates to nano titanium oxide, particularly, is the hollow nanostructured preparation method of a kind of titanium oxide.
Background technology
Because the nano material of nucleocapsid structure is boundless in the application prospect in fields such as catalysis, chromatography, bioactive agents protection, wastewater treatment, macromole slow-releasing system, makes controlled preparation nuclear shell structure nano material become the focus of research; Titanium oxide (TiO
2) be a kind of more multi-functional meticulous inorganic materials of studying; Also be important pottery, semi-conductor and catalytic material, be widely used in fields such as coating, dielectric materials, printing ink, papermaking because of it has particular performances such as good weather resisteant, chemical resistance, higher chemicalstability, nontoxicity, photosensitivity again; In recent years, because titanium oxide (TiO
2) the multiphase photocatalysis interaction energy effectively the organic pollutant in the big G&W is degraded to carbonic acid gas, water and mineral acid fully; Both there be not secondary pollution; Sun power capable of using again is a kind ofly to meet the Sustainable development needs, and has the sewage and the air handling new technology of broad prospect of application; Titanium oxide is because its nontoxic, high chemicalstability, low cost, thereby used the section's material as core-shell particles and hollow structure widely; Though have diverse ways to prepare the titanium dioxide hollow ball material of many types, exist technical process complicated, be difficult for problems such as expanded reproduction, quality product have much room for improvement; Present existing compound method mainly is through template, comprises hard template (for example, inorganic metal and polymeric colloid particle) and soft template (for example, the molecular tempiate of tensio-active agent and polymkeric substance), and does not have template; Hard template method forms nucleocapsid structure and tiny balloon on the template particles surface through self-assembly method or sol-gel method layer by layer usually, and the former complex process need relate to the polyelectrolyte that repeatedly uses band xenogenesis electric charge; And sol-gel method is difficult to the generating rate of controlled oxidation titanium nano particle, can cause a large amount of gatherings of offspring, influences the dispersiveness of microballoon; No template is synthetic then to be to make nucleocapsid structure or tiny balloon through hydro-thermal or one step of solvent-thermal method, though this method technology is simple, quick, it is wide to be difficult to overcome the product distribution of sizes, the shortcoming that impurity is more; Therefore, the contriver seeks low cost always, simple effective method is prepared titanium oxide hollow Nano micro-sphere structure.
Summary of the invention
The object of the present invention is to provide a kind of titanium oxide hollow nanostructured and preparation method thereof; This method can solve the problem of hollow nanostructured pattern of titanium oxide and distribution of sizes; The hollow nanostructured size ratio of the titanium oxide for preparing is more even, and particle size distribution range is between 100 ~ 400nm.
Above-mentioned purpose realizes through following technical scheme: with ammonium titanium fluoride ((NH
4)
2TiF
6) be precursor, with silicon-dioxide (SiO
2) microballoon is template, through regulating ammonium titanium fluoride ((NH
4)
2TiF
6) concentration, hydro-thermal time and silicon-dioxide (SiO
2) size control the size of tiny balloon and the thickness of shell, thereby under low relatively temperature condition, it is hollow nanostructured with tropism's titanium oxide that synthetic in a large number size and structure all have height.
Particularly, comprise the steps:
(1) with even particle size distribution, median size is silica dioxide granule adding the ammonium titanium fluoride ((NH of 85 ~ 95nm
4)
2TiF
6) in the aqueous solution; Silicon-dioxide is 1:2-1:4 with the ratio of the amount of substance of ammonium titanium fluoride;
(2) above-mentioned solution stirring is even, 60-80 ℃ of insulation 6 ~ 24h;
(3) will stir the product of accomplishing and clean the suction filtration collection with zero(ppm) water or ethanol;
(4) product of collecting is dry;
(5) product is calcined 2h down at 450 ~ 550 ℃, promptly obtain titanium oxide hollow Nano micro-sphere structure.
Described ammonium titanium fluoride ((NH
4)
2TiF
6) concentration of the aqueous solution is 0.02 ~ 0.08mol/L.
The inventive method technology is simple; With low cost, control the pattern of product through the restriction of spherical template, thereby under low relatively temperature condition; Having synthesized size and structure in a large number all has high hollow nanostructured with tropism's titanium oxide; The distribution of sizes scope in the synthesis of titanium dioxide microballoon process in the past of having solved is excessive, the problem of complex process, and the hollow nanostructured epigranular of the titanium oxide for preparing, average particle size range be 100 ~ 400nm.
Description of drawings
Fig. 1 is the ESEM picture of employed silica template ball among the present invention;
Fig. 2 is the ESEM picture of the spherical tio2 nano hollow structure of embodiment 1;
Fig. 3 is the x XRD X picture of the spherical tio2 nano hollow structure of embodiment 1;
Fig. 4 is the ESEM picture of the spherical tio2 nano hollow structure of embodiment 2;
Fig. 5 is the ESEM picture of the spherical tio2 nano hollow structure of embodiment 3;
Fig. 6 is the transmission electron microscope picture of the spherical tio2 nano hollow structure of embodiment 4.
Embodiment
Below further describe the present invention through embodiment; Can know by technological general knowledge; The present invention also can describe through other the scheme that does not break away from technical characterictic of the present invention, thus all within the scope of the present invention or the change that is equal in the scope of the invention all comprised by the present invention.
Embodiment 1:
With even particle size distribution, median size is that silicon-dioxide (like Fig. 1) particle of 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH
4)
2TiF
6) in the aqueous solution, silicon-dioxide is 1:2 with the ratio of the amount of substance of ammonium titanium fluoride; With the insulation 24h of above-mentioned solution at 60 ℃, product is cleaned suction filtration with zero(ppm) water or ethanol collect, with product dry 8h under 60 ℃ temperature, and then calcining 2h promptly obtains titanium oxide hollow Nano micro-sphere structure under 450 ℃.
Present embodiment product (titanium oxide hollow Nano micro-sphere structure) is carried out electron-microscope scanning to observe its microscopic appearance, and result's products therefrom particle diameter as shown in Figure 2 is about about 100nm; The present embodiment product is advanced the XRD test, and the result is corresponding with standard P DF card, and particulate component is pure titanium oxide, and is as shown in Figure 3.
Embodiment 2:
With even particle size distribution, median size is that silicon-dioxide (like Fig. 1) particle of 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH
4)
2TiF
6) in the aqueous solution, silicon-dioxide is 1:3 with the ratio of the amount of substance of ammonium titanium fluoride; Above-mentioned solution is incubated 6h under 80 ℃ condition, product is cleaned suction filtration with zero(ppm) water or ethanol collect, with product dry 8h under 60 ℃ temperature, and then calcining 2h promptly obtains titanium oxide hollow Nano micro-sphere structure under 500 ℃.
Present embodiment product (titanium oxide hollow Nano micro-sphere structure) is carried out electron-microscope scanning to observe its microscopic appearance, and result's products therefrom particle diameter as shown in Figure 4 is about about 105nm.
Embodiment 3:
With even particle size distribution, median size is that silicon-dioxide (like Fig. 1) particle of 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH
4)
2TiF
6) in the aqueous solution, silicon-dioxide is 1:4 with the ratio of the amount of substance of ammonium titanium fluoride; Above-mentioned solution at the following insulation of 70 ℃ condition 12h, is cleaned suction filtration with product with zero(ppm) water or ethanol and collects, and with product dry 8h under 60 ℃ temperature, and then calcining 2h promptly obtains titanium oxide hollow Nano micro-sphere structure under 550 ℃.
Present embodiment product (titanium oxide hollow Nano micro-sphere structure) is carried out sem test to observe its microscopic appearance, and the result is as shown in Figure 5, and the products therefrom particle diameter is about the ball-type structure about 300nm.
Embodiment 4:
With even particle size distribution, median size is that silicon-dioxide (like Fig. 1) particle of 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH
4)
2TiF
6) in the aqueous solution, silicon-dioxide is 1:2 with the ratio of the amount of substance of ammonium titanium fluoride; Above-mentioned solution is incubated 12h under 70 ℃ condition, product is cleaned suction filtration with zero(ppm) water or ethanol collect, with product dry 8h under 60 ℃ temperature, and then calcining 2h promptly obtains titanium oxide hollow Nano micro-sphere structure under 500 ℃.
Present embodiment product (titanium oxide hollow Nano micro-sphere structure) is carried out transmission electron microscope scanning to observe its microscopic appearance, and the result is as shown in Figure 6, and the products therefrom particle diameter is about the hollow ball-type structure about 350nm, and shell thickness is about 100nm.
Claims (3)
1. the preparation method that titanium oxide is hollow nanostructured is characterized in that comprising the steps:
(1) with even particle size distribution, median size is silica dioxide granule adding the ammonium titanium fluoride ((NH of 85 ~ 95nm
4)
2TiF
6) in the aqueous solution; Silicon-dioxide is 1:2-1:4 with the ratio of the amount of substance of ammonium titanium fluoride;
(2) above-mentioned solution stirring is even, 60-80 ℃ of insulation 6 ~ 24h;
(3) will stir the product of accomplishing and clean the suction filtration collection with zero(ppm) water or ethanol;
(4) product of collecting is dry;
(5) product is calcined 2h down at 450 ~ 550 ℃, promptly obtain titanium oxide hollow Nano micro-sphere structure.
2. the hollow nanostructured preparation method of a kind of titanium oxide as claimed in claim 1 is characterized in that: described ammonium titanium fluoride ((NH
4)
2TiF
6) concentration of the aqueous solution is 0.02 ~ 0.08mol/L.
3. the hollow nanostructured preparation method of a kind of titanium oxide as claimed in claim 1 is characterized in that: the particle size distribution range of said titanium oxide hollow Nano microballoon is between 100 ~ 400nm.
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| CN102718255B CN102718255B (en) | 2014-07-30 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269273A (en) * | 2014-09-28 | 2015-01-07 | 吉林大学 | TiO<2> of nano hollow spiky ball structure, preparation method and application in photo anode of solar cell |
| CN105347395A (en) * | 2015-12-05 | 2016-02-24 | 国家林业局竹子研究开发中心 | Method for preparing mesoporous TiO2 at indoor temperature |
| CN106082318A (en) * | 2016-05-26 | 2016-11-09 | 青海大学 | The preparation method of nano titanium oxide hollow ball |
| CN106848276A (en) * | 2017-04-19 | 2017-06-13 | 合肥工业大学 | A kind of titanium dioxide of core-shell structure cladding silicon lithium ion battery cathode material and preparation method thereof |
| CN107902693A (en) * | 2017-11-22 | 2018-04-13 | 陕西科技大学 | The method that one step hydrothermal template method prepares the hollow micro-nano structure TiO2 microballoons of bivalve layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638218A (en) * | 1986-06-26 | 1988-01-14 | Mitsubishi Metal Corp | Production of spherical titanium oxide powder |
-
2012
- 2012-06-19 CN CN201210202353.0A patent/CN102718255B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638218A (en) * | 1986-06-26 | 1988-01-14 | Mitsubishi Metal Corp | Production of spherical titanium oxide powder |
Non-Patent Citations (2)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20080915 刘雯 "多孔球形二氧化钛光催化材料的制备与表征" B020-296，正文33-34、45页 1-3 , 第09期 * |
| 刘雯: ""多孔球形二氧化钛光催化材料的制备与表征"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269273A (en) * | 2014-09-28 | 2015-01-07 | 吉林大学 | TiO<2> of nano hollow spiky ball structure, preparation method and application in photo anode of solar cell |
| CN105347395A (en) * | 2015-12-05 | 2016-02-24 | 国家林业局竹子研究开发中心 | Method for preparing mesoporous TiO2 at indoor temperature |
| CN106082318A (en) * | 2016-05-26 | 2016-11-09 | 青海大学 | The preparation method of nano titanium oxide hollow ball |
| CN106848276A (en) * | 2017-04-19 | 2017-06-13 | 合肥工业大学 | A kind of titanium dioxide of core-shell structure cladding silicon lithium ion battery cathode material and preparation method thereof |
| CN107902693A (en) * | 2017-11-22 | 2018-04-13 | 陕西科技大学 | The method that one step hydrothermal template method prepares the hollow micro-nano structure TiO2 microballoons of bivalve layer |
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| Publication number | Publication date |
|---|---|
| CN102718255B (en) | 2014-07-30 |
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