CN102502807A - White hollow titanium dioxide microsphere and preparation method thereof - Google Patents
White hollow titanium dioxide microsphere and preparation method thereof Download PDFInfo
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- CN102502807A CN102502807A CN2011103299346A CN201110329934A CN102502807A CN 102502807 A CN102502807 A CN 102502807A CN 2011103299346 A CN2011103299346 A CN 2011103299346A CN 201110329934 A CN201110329934 A CN 201110329934A CN 102502807 A CN102502807 A CN 102502807A
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Abstract
The invention relates to a white hollow titanium dioxide microsphere and a preparation method thereof. According to the invention, the particle size of the microsphere is 120-230 nm, and the relative density of the microsphere is 1.31-1.88g/cm<3>. The white hollow titanium dioxide microsphere is prepared from an organic matter copolymer microsphere utilized as a core and tetrabutyl titanate utilized as a precursor through static adsorption and a sol-gel reaction by freeze drying and high temperature roasting at air atmosphere. By using the preparation method provided by the invention, the defects in the traditional method are overcome; and an organic matter microsphere is used as a template so that the prepared white hollow titanium dioxide microsphere is regular in shape, uniform in size and easily controllable in particle size and thickness, and simultaneously the shell and hollow part of the hollow microsphere are different in refraction coefficients and good in light scattering properties due to the hollow structure. The white hollow titanium dioxide microsphere has the advantage of easily available raw materials and the preparation method has the advantage of simple preparation process.
Description
Technical field
The present invention relates to the technology of preparing of type material, prepared white hollow titanium dioxide microballoon sphere can be applicable to microcapsule electrophoresis showed, photochemical catalysis, fields such as dye sensitization solar battery.
Technical background
Along with the further deeply development of nanometer science and technology, people have proposed wider higher requirement to preparation, character, the application of nano material.Hollow microsphere is exactly a kind of new structural material.This structure can have many new capabilities that general particle can't obtain, and application prospect is widely arranged.The preparation difficulty of hollow microsphere is bigger, is difficult to directly obtain with general synthetic technology.Titanium oxide is that a kind of performance is good, and broad-spectrum inorganics can be used for catalyzer, dyestuff, a plurality of fields such as hydrogen storage material.Hollow titanium oxide has the advantage of hollow structure and titanium oxide concurrently, and its preparation becomes the focus of research.At present, the method for preparing the hollow nanoparticle is mainly template, and it is to prepare nuclear through other method earlier, is template with nuclear again, after its surface coats, obtains nucleocapsid structure, except that the structure that obtains hollow after the stoning.Template has significant limitation; Usually the template of preparation needs surface-treated or adds tensio-active agent to increase the reactive force between the nucleocapsid; Complex technical process and be difficult to adopt effective means that template is carried out complete coating, this has limited its application aspect demonstration.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of white hollow TiO 2 particles; It is simple that the present invention prepares process; Do not need extra surface-treated or tensio-active agent; And after adopting freeze-drying method process nuclear shell structure, shell structure can not destroyed in the template removal processes, keeps integrity preferably.Prepared hollow microsphere regular shape, size is even, and hollow structure is stable.The hollow microsphere of preparation is owing to its lower specific density, and advantages such as higher specific surface area can be used for the preparation of electrophoresis showed electrophoresis particle, catalyzer, fields such as dye sensitization solar battery.
The present invention provides a kind of preparation method of white hollow titanium dioxide microballoon sphere, and concrete technical scheme is following:
A kind of white hollow titanium dioxide microballoon sphere, microspherulite diameter is 120-230nm, specific density is 1.31-1.88g/cm
3With the organism copolymer microsphere is nuclear, is presoma with the butyl(tetra)titanate, and through electrostatic adsorption and solgel reaction, through lyophilize, high-temperature roasting is prepared from air atmosphere.
The preparation method of white hollow titanium dioxide microballoon sphere of the present invention; The organic copolymer microballoon is distributed to the solution that is prepared into 1.16g/L～2.33g/L in the absolute ethyl alcohol; 1.43～4.30 times the Vinylpyrrolidone polymer that adds the organic copolymer microspheres quality is a dispersion agent, is to prepare burden in 1: 4.3～1: 14.3 according to organic copolymer microspheres quality and butyl(tetra)titanate mass ratio;
(1) the organic copolymer microballoon is scattered in the absolute ethyl alcohol; Add Vinylpyrrolidone polymer, agitation condition adds butyl(tetra)titanate down fast, behind the reaction 120min; Spinning obtains white spheric organic copolymer microballoon/titanium dioxide core-shell composite particles after lyophilize;
(2) organic copolymer microballoon/titanium dioxide core-shell composite particles is placed air atmosphere,, obtain white hollow titanium dioxide microballoon sphere 500～900 ℃ of following roastings 3 hours.
Described organic copolymer microballoon is meant the multipolymer of TEB 3K and ethyl propenoate or the multipolymer of TEB 3K and Bing Xisuandingzhi.
Described maturing temperature is preferably 500～700 ℃.Said drying means is lyophilize.
The preparation method of white hollow titanium dioxide microballoon sphere provided by the invention can overcome the defective of traditional method.The present invention with the organic copolymer microballoon as template make the white hollow titanium dioxide microballoon sphere regular shape prepare, size evenly and particle diameter and thickness be easy to control; Hollow structure makes the shell of hollow microsphere have different refraction coefficients with hollow parts simultaneously, has good light scattering property.It is simple to the present invention be advantageous in that this legal system is equipped with process, and raw material is easy to get.
Description of drawings
The result that Fig. 1 observes under ESEM for the white hollow titanium dioxide microballoon sphere that adopts instance 2 to make.
Fig. 2 is the electrophoresis showed design sketch of the white hollow titanium dioxide microballoon sphere that adopts instance 2 and make.
Embodiment
Instance 1
1. the organic copolymer microballoon 0.07g with TEB 3K and ethyl propenoate is scattered in the 60mL absolute ethyl alcohol; Add the 0.10g Vinylpyrrolidone polymer; Agitation condition adds the 0.30g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. organic copolymer microballoon/titanium dioxide core-shell composite particles is placed air atmosphere, 500 ℃ of following roastings, obtain white hollow titanium dioxide microballoon sphere, size is even, is about 120nm, and specific density is 1.31g/cm
3
Instance 2
1. the organic copolymer microballoon 0.07g with TEB 3K and Bing Xisuandingzhi is scattered in the 60mL absolute ethyl alcohol; Add the 0.10g Vinylpyrrolidone polymer; Agitation condition adds the 0.50g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. with organic copolymer microballoon/titanium dioxide core-shell composite particles in air atmosphere, 500 ℃ of following roastings, obtain white hollow titanium dioxide microballoon sphere, size is even, is about 140nm, specific density is 1.38g/cm
3
Be illustrated in figure 1 as the scanning electron microscope diagram of the white hollow titanium dioxide microballoon sphere of instance 2 preparations; Fig. 2 is the electrophoresis showed design sketch of the white hollow titanium dioxide microballoon sphere of employing instance 2 preparations.
Instance 3
1. the organic copolymer microballoon 0.07g with TEB 3K and ethyl propenoate is scattered in the 60mL absolute ethyl alcohol; Add the 0.10g Vinylpyrrolidone polymer; Agitation condition adds the 0.50g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. with organic copolymer microballoon/titanium dioxide core-shell composite particles in air atmosphere, 700 ℃ of following roastings, obtain white hollow titanium dioxide microballoon sphere, size is even, is about 160nm, specific density is 1.62g/cm
3
Instance 4
1. the organic copolymer microballoon 0.07g with TEB 3K and Bing Xisuandingzhi is scattered in the 60mL absolute ethyl alcohol; Add the 0.10g Vinylpyrrolidone polymer; Agitation condition adds the 0.70g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. with organic copolymer microballoon/titanium dioxide core-shell composite particles in air atmosphere, 900 ℃ of following roastings, obtain white hollow titanium dioxide microballoon sphere, size is even, is about 180nm, specific density is 2.14g/cm
3
Instance 5
1. the organic copolymer microballoon 0.14g with TEB 3K and ethyl propenoate is scattered in the 120mL absolute ethyl alcohol; Add the 0.42g Vinylpyrrolidone polymer; Agitation condition adds the 1.00g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. with organic copolymer microballoon/titanium dioxide core-shell composite particles in air atmosphere, 500 ℃ of following roastings, obtain white hollow titanium oxide and close microballoon, size is even, is about 150nm, specific density is 1.47g/cm
3
Instance 6
1. the organic copolymer microballoon 0.21g with TEB 3K and Bing Xisuandingzhi is scattered in the 100mL absolute ethyl alcohol; Add the 0.30g Vinylpyrrolidone polymer; Agitation condition adds the 1.50g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. with organic copolymer microballoon/titanium dioxide core-shell composite particles in air atmosphere, 500 ℃ of following roastings, obtain white hollow titanium dioxide microballoon sphere, size is even, is about 210nm, specific density is 1.88g/cm
3
Instance 7
1. the organic copolymer microballoon 0.21g with TEB 3K and ethyl propenoate is scattered in the 120mL absolute ethyl alcohol; Add the 0.20g Vinylpyrrolidone polymer; Agitation condition adds the 1.50g butyl(tetra)titanate down fast; Reaction 120min, spinning obtains white spherical organic copolymer microballoon/titanium dioxide core-shell composite particles after the lyophilize.
2. with organic copolymer microballoon/titanium dioxide core-shell composite particles in air atmosphere, 700 ℃ of following roastings, obtain white hollow titanium dioxide microballoon sphere, size is even, is about 230nm, specific density is 1.43g/cm
3
The white hollow titanium dioxide microballoon sphere of above-mentioned preparation is dispersed in the electrophoresis liquid, and ball milling is after for some time, dispersion liquid carried out microcapsule coat, and can observe tangible electrophoresis after being prepared into little cupule spare then, realizes electrophoresis showed.
Claims (5)
1. a white hollow titanium dioxide microballoon sphere is characterized in that particle diameter 120～230nm, and specific density is 1.31～1.88g/cm
3With the organism copolymer microsphere is nuclear, is presoma with the butyl(tetra)titanate, and through electrostatic adsorption and solgel reaction, through lyophilize, high-temperature roasting is prepared from air atmosphere.
2. the preparation method of the described white hollow titanium dioxide microballoon sphere of claim 1; The organic copolymer microballoon is distributed to the solution that is prepared into 1.16g/L～2.33g/L in the absolute ethyl alcohol; 1.43～4.30 times the Vinylpyrrolidone polymer that adds the organic copolymer microspheres quality is a dispersion agent, is to prepare burden in 1: 4.3～1: 14.3 according to organic copolymer microspheres quality and butyl(tetra)titanate mass ratio;
(1) the organic copolymer microballoon is scattered in the absolute ethyl alcohol; Add Vinylpyrrolidone polymer, agitation condition adds butyl(tetra)titanate down fast, behind the reaction 120min; Spinning obtains white spheric organic copolymer microballoon/titanium dioxide core-shell composite particles after lyophilize;
(2) organic copolymer microballoon/titanium dioxide core-shell composite particles is placed air atmosphere,, obtain white hollow titanium dioxide microballoon sphere 500～900 ℃ of following roastings 3 hours.
3. the method for claim 1 is characterized in that described organic copolymer microballoon is meant the multipolymer of TEB 3K and ethyl propenoate or the multipolymer of TEB 3K and Bing Xisuandingzhi.
4. method as claimed in claim 2 is characterized in that described drying means refers to lyophilize.
5. the application of the white hollow titanium dioxide microballoon sphere of claim 1 is characterized in that being specially adapted to the preparation of white electrophoretic particles in the electrophoresis showed.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159257A (en) * | 2013-03-22 | 2013-06-19 | 中国石油天然气集团公司 | Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel |
| CN106223054A (en) * | 2016-08-03 | 2016-12-14 | 浙江汇锋新材料股份有限公司 | A kind of puggaree with endurance life and processing method thereof |
| CN108447688A (en) * | 2018-02-10 | 2018-08-24 | 深圳大图科创技术开发有限公司 | A kind of solar energy energy-saving central air conditioner |
| CN109133164A (en) * | 2018-11-15 | 2019-01-04 | 湖北天瓷电子材料有限公司 | A kind of high dispersiveness spherical titanium dioxide process |
| CN110589881A (en) * | 2018-06-13 | 2019-12-20 | 宁波新福钛白粉有限公司 | Preparation method of waxberry-shaped titanium dioxide/silicon dioxide composite structure particles |
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| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101210120A (en) * | 2007-12-25 | 2008-07-02 | 天津大学 | Hollow titanium dioxide white electrophoresis ion for electrophoresis displaying and preparing method thereof |
| CN101423249A (en) * | 2007-10-29 | 2009-05-06 | 中国科学院理化技术研究所 | Monodisperse pure rutile type or rutile type and anatase type composite phase titanic oxide hollow sub-micron ball and preparation method |
| CN101537349A (en) * | 2009-04-22 | 2009-09-23 | 东华大学 | Preparation of core/shell structural polystyrene/titanium dioxide composite photo catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101423249A (en) * | 2007-10-29 | 2009-05-06 | 中国科学院理化技术研究所 | Monodisperse pure rutile type or rutile type and anatase type composite phase titanic oxide hollow sub-micron ball and preparation method |
| CN101210120A (en) * | 2007-12-25 | 2008-07-02 | 天津大学 | Hollow titanium dioxide white electrophoresis ion for electrophoresis displaying and preparing method thereof |
| CN101537349A (en) * | 2009-04-22 | 2009-09-23 | 东华大学 | Preparation of core/shell structural polystyrene/titanium dioxide composite photo catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159257A (en) * | 2013-03-22 | 2013-06-19 | 中国石油天然气集团公司 | Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel |
| CN106223054A (en) * | 2016-08-03 | 2016-12-14 | 浙江汇锋新材料股份有限公司 | A kind of puggaree with endurance life and processing method thereof |
| CN108447688A (en) * | 2018-02-10 | 2018-08-24 | 深圳大图科创技术开发有限公司 | A kind of solar energy energy-saving central air conditioner |
| CN110589881A (en) * | 2018-06-13 | 2019-12-20 | 宁波新福钛白粉有限公司 | Preparation method of waxberry-shaped titanium dioxide/silicon dioxide composite structure particles |
| CN109133164A (en) * | 2018-11-15 | 2019-01-04 | 湖北天瓷电子材料有限公司 | A kind of high dispersiveness spherical titanium dioxide process |
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Application publication date: 20120620 |