CN103803643A - Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof - Google Patents
Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof Download PDFInfo
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- CN103803643A CN103803643A CN201410072201.2A CN201410072201A CN103803643A CN 103803643 A CN103803643 A CN 103803643A CN 201410072201 A CN201410072201 A CN 201410072201A CN 103803643 A CN103803643 A CN 103803643A
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Abstract
The invention provides monodisperse mesoporous hollow nano spherical titanium dioxide and a preparation method thereof. Composite nano-spheres (PS@TiO2@SiO2) are synthesized through multilayer packaging, and then the monodisperse mesoporous hollow nano spherical titanium dioxide is obtained through high-temperature calcination treatment and sodium hydroxide solution treatment. According to the preparation method disclosed by the invention, polystyrene (PS) spherules are used as a template, the obtained composite microspheres can remove the PS template through high-temperature calcination, the silicon dioxide covering on the outer side of titanium dioxide can prevent the titanium dioxide from agglomeration during calcination and can prevent the spherules from being damaged during calcination at the same time; and moreover, the silicon dioxide layer at the outermost layer can be removed by using a sodium hydroxide solution. The preparation method is simple and is suitable for large-scale production.
Description
Technical field
The invention belongs to polymerizing microballoons preparation field, be specifically related to the preparation method of the spherical titanium dioxide of a kind of monodisperse mesoporous hollow Nano.
Background technology
Recent years, outstanding along with the worsening shortages of Mineral resources and environmental problem, how utilizing new forms of energy, reducing environmental pollution is the problem that every country is needed solution badly.Since TiO has been delivered at Nature in two scholar's Hashimoto Herens (Hashimoto) He Teng island clear (Fujishima) of Tokyo Univ Japan in 1972
2electrode can brine electrolysis under visible ray after, optically catalytic TiO 2 mechanism probe into and apply the heat subject that becomes investigators.Through the research of decades, titanium dioxide is considered to have most the conductor oxidate of using value, and its application relates to sensor, photonic crystal, energy storage device and photocatalyst etc.
Under illumination condition, titanium dioxide can produce electronics and the hole with redox ability, the surface of catalyzer is transferred in electronics and hole, electronics and cavity energy are water and carbonic acid gas the organic substance decomposing that is adsorbed on titanium dioxide surface, compare with other catalyzer, optically catalytic TiO 2 activity is high, and chemical stability is good, low toxicity.Based on these features, titanium dioxide becomes ideal catalyst of photocatalytic degradation water pollutant.
Although the catalytic activity of titanium dioxide is high, but titanium dioxide can only utilize the UV-light in sunlight, and electronics and hole-recombination speed that titanium dioxide produces are fast, therefore in order to improve the utilization ratio of titanium dioxide hole and electronics, a lot of researchers are template with silicon-dioxide or PS bead, at the outside of bead cladding titanium dioxide, and then calcining, make to be transformed into by unformed titanium dioxide the hollow titanium dioxide of anatase octahedrite, improved the specific surface area of reaction.In high-temperature calcination process, although titanium dioxide is transformed into the titanium dioxide of anatase octahedrite, but due to high-temperature calcination, cause the bonding between titanium dioxide bead, can not produce monodispersed titanium dioxide bead, reduce the area of catalysis, therefore the invention provides a kind of preparation method of monodisperse mesoporous hollow Nano titanium dioxide ball, prepared monodispersed hollow Nano titanium dioxide ball.
Summary of the invention
The object of the invention is to easily bond for titanium dioxide bead in prior art, spherical titanium dioxide of a kind of monodisperse mesoporous hollow Nano and preparation method thereof is provided.The present invention is after the coated layer of silicon dioxide in the outside of titanium dioxide, and then calcine in retort furnace, not only make unformed titanium dioxide be transformed into the titanium dioxide of anatase octahedrite, make kernel polystyrene sphere decompose simultaneously and obtain hollow ball, by sodium hydroxide, outer field silicon dioxide layer corrosion is removed again afterwards, obtained the spherical titanium dioxide of hollow Nano that monodispersity is good.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for the spherical titanium dioxide of monodisperse mesoporous hollow Nano, take styrene monomer as raw material, take Potassium Persulphate as initiator, makes the pipe/polyhenylethylene nano bead of surface band negative charge; Then the mixing solutions that drips tetrabutyl titanate and ethanol, obtains polystyrene-TiO
2composite pellets; Add tetraethyl orthosilicate at composite pellets surface coated silica; Finally in retort furnace, polystyrene is removed in high-temperature calcination, and centrifuge washing is removed silicon-dioxide and made monodisperse mesoporous hollow Nano titanium dioxide ball.
Specifically comprise the following steps:
(1) preparation of pipe/polyhenylethylene nano bead:
Under room temperature, add deionized water, styrene monomer in the there-necked flask of 250mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 20～40min, is increased to 50～90 ℃ gradually by temperature; Initiator potassium persulfate is dissolved in deionized water, is heated to 50～90 ℃, add in there-necked flask disposable this solution; Continue reaction 22～26h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene-TiO
2the preparation of composite pellets:
Polystyrene sphere and dehydrated alcohol are joined in the there-necked flask of 250mL and stir 20～40min, add after ammoniacal liquor and hydroxypropylcellulose, stir 20～40min; Then slowly drip the mixing solutions of tetrabutyl titanate and ethanol, reaction 0.5～1.5h, obtains polystyrene-TiO
2composite pellets;
(3) composite pellets surface coated silica
(2) gained composite pellets is scattered in the Polyvinylpyrolidone (PVP) aqueous solution to hold over night, centrifugal; Centrifugal gained solid is scattered in the ethanol and water mixed solution preparing in proportion, adds ammoniacal liquor and tetraethyl orthosilicate, reaction 2～6h, centrifugally obtains the composite pellets that surface is coated with silicon oxide;
(4) remove polystyrene
The composite pellets that gained is coated with silicon oxide high-temperature calcination in retort furnace, removes polystyrene; (5) remove silicon-dioxide shell
The hollow ball that calcining is obtained adds in sodium hydroxide solution and reacts, and centrifuge washing, except decapsidate, obtains hollow monodispersed mesoporous TiO 2 bead.
In described step (1), the volume ratio of deionized water and styrene monomer is 10:0.5～1.5, and the quality of initiator is 0.2～0.4% of styrene monomer quality.
In described step (2), polystyrene sphere consumption is 0.01～0.03% of dehydrated alcohol quality, ammonia volume is 0.2～0.4% of dehydrated alcohol quality, tetrabutyl titanate consumption is 0.3～0.7% of dehydrated alcohol quality, and hydroxypropylcellulose consumption is 0.01～0.03% of dehydrated alcohol quality.
In described step (3), in the Polyvinylpyrolidone (PVP) aqueous solution, the massfraction of Polyvinylpyrolidone (PVP) is 0.24%, the mass ratio of composite pellets and Polyvinylpyrolidone (PVP) is 1:1, in the mixing solutions of dehydrated alcohol and water: the volume ratio of dehydrated alcohol and deionized water is 10:2～4, ammonia concn used is 26%wt, in ammoniacal liquor and mixing solutions, the volume ratio of deionized water is 1～2:7, and the volume ratio of ammoniacal liquor and tetraethyl orthosilicate is 1.24:0.31 ~ 0.4.
High-temperature calcination in described step (4): temperature is 450～550 ℃, and calcination time is 2～4h.
In described step (5), the concentration of sodium hydroxide is 2～3mol/L, and the reaction times is 2～4h.
The spherical titanium dioxide of monodisperse mesoporous hollow Nano that a kind of preparation method as above makes.
Advantage in the present invention is: take polystyrene sphere as kernel, at the outside of titanium dioxide coated silica layer, can directly remove polystyrene by high-temperature calcination, simultaneously because the existence of silicon dioxide layer is difficult for bonding between bead; And silicon-dioxide can be removed with sodium hydroxide corrosion, obtain the hollow Nano titanium dioxide bead that monodispersity is good.
Accompanying drawing explanation
Fig. 1 is the TEM figure of embodiment 1 gained hollow ball;
Fig. 2 is the TEM figure of embodiment 2 gained hollow balls;
Fig. 3 is the TEM figure of embodiment 3 gained hollow balls;
Fig. 4 is the TEM figure of embodiment 4 gained hollow balls;
Fig. 5 is the XRD figure of embodiment 5-7 gained hollow ball, and a is the XRD figure of embodiment 5 gained hollow balls, and b is the XRD figure of embodiment 6 gained hollow balls, and c is the XRD figure of embodiment 7 gained hollow balls.
Embodiment
With specific embodiment, the present invention will be further described below, but protection scope of the present invention is not limited to this
embodiment 1
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains PS bead;
(2) PS bead surface cladding titanium dioxide (PS@TiO
2)
0.024gPS bead and 10mL dehydrated alcohol join in the there-necked flask of 250mL and stir 30min, add ammoniacal liquor and the 0.024g hydroxypropylcellulose (HPC) of 0.3mL to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, obtains PS@TiO
2bead;
(3) remove PS bead
By gained bead (PS@TiO
2) in retort furnace, 500 ℃ of high-temperature calcination 3h remove PS bead, leave outer wall;
embodiment 2
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene sphere surface cladding titanium dioxide (PS@TiO
2)
0.024g PS bead and 10mL dehydrated alcohol are joined in the there-necked flask of 250mL and stir 30min, add 0.3mL ammoniacal liquor and 0.024g hydroxypropylcellulose (HPC) to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, the centrifugal PS@TiO that obtains
2bead.
(3) the outside coated silica of titanium dioxide (PS@TiO
2@SiO
2)
(2) gained composite pellets is scattered in to hold over night in the deionized water that 10ml contains 0.024g Polyvinylpyrolidone (PVP) (PVP), then centrifugal; Centrifugal gained solid is scattered in to the mixing solutions of 30mL ethanol and 8.6mL deionized water, then adds 1.24mL ammoniacal liquor and 0.31mL tetraethyl orthosilicate reaction 4h, the centrifugal composite pellets that obtains;
(4) remove PS bead
By gained bead (PS@TiO
2@SiO
2) in retort furnace, 500 ℃ of high-temperature calcination 3h remove PS bead, leave outer wall;
(5) remove silicon-dioxide shell
By calcine hollow ball add in 2.5mol/L sodium hydroxide solution and react 3h, centrifuge washing,, except decapsidate, obtains monodispersed meso-porous hollow nano titanium dioxide ball.
embodiment 3
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene sphere surface cladding titanium dioxide (PS@TiO
2)
0.024g PS bead and 10mL dehydrated alcohol are joined in the there-necked flask of 250mL and stir 30min, add 0.3mL ammoniacal liquor and 0.024g hydroxypropylcellulose (HPC) to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, the centrifugal PS@TiO that obtains
2bead.
(3) the outside coated silica of titanium dioxide (PS@TiO
2@SiO
2)
(2) gained composite pellets is scattered in to hold over night in the deionized water that 10ml contains 0.024g Polyvinylpyrolidone (PVP) (PVP), then centrifugal; Centrifugal gained all solids is scattered in to the mixing solutions of 30mL ethanol and 8.6mL deionized water, then adds 1.24mL ammoniacal liquor and 0.36mL tetraethyl orthosilicate reaction 4h, the centrifugal composite pellets that obtains;
(4) remove PS bead
By gained bead (PS@TiO
2@SiO
2) in retort furnace, 500 ℃ of high-temperature calcination 3h remove PS bead, leave outer wall;
(5) remove silicon-dioxide shell
By calcine hollow ball add in 2.5mol/L sodium hydroxide solution and react 3h, centrifuge washing,, except decapsidate, obtains monodispersed meso-porous hollow nano titanium dioxide ball.
embodiment 4
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene sphere surface cladding titanium dioxide (PS@TiO
2)
0.024g PS bead and 10mL dehydrated alcohol are joined in the there-necked flask of 250mL and stir 30min, add 0.3mL ammoniacal liquor and 0.024g hydroxypropylcellulose (HPC) to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, the centrifugal PS@TiO that obtains
2bead.
(3) the outside coated silica of titanium dioxide (PS@TiO
2@SiO
2)
(2) gained composite pellets is scattered in to hold over night in the deionized water that 10mL contains 0.024g Polyvinylpyrolidone (PVP) (PVP), then centrifugal; Centrifugal gained all solids is scattered in to the mixing solutions of 30mL ethanol and 8.6mL deionized water, then adds 1.24mL ammoniacal liquor and 0.40mL tetraethyl orthosilicate reaction 4h, the centrifugal composite pellets that obtains;
(4) remove PS bead
By gained bead (PS@TiO
2@SiO
2) in retort furnace, 500 ℃ of high-temperature calcination 3h remove PS bead, leave outer wall;
(5) remove silicon-dioxide shell
By calcine hollow ball add in 2.5mol/L sodium hydroxide solution and react 3h, centrifuge washing,, except decapsidate, obtains monodispersed meso-porous hollow nano titanium dioxide ball
embodiment 5
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene sphere surface cladding titanium dioxide (PS@TiO
2)
0.024g PS bead and 10mL dehydrated alcohol are joined in the there-necked flask of 250mL and stir 30min, add 0.3mL ammoniacal liquor and 0.024g hydroxypropylcellulose (HPC) to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, the centrifugal PS@TiO that obtains
2bead.
(3) the outside coated silica of titanium dioxide (PS@TiO
2@SiO
2)
(2) gained composite pellets is scattered in to hold over night in the deionized water that 10ml contains 0.024g Polyvinylpyrolidone (PVP) (PVP), then centrifugal; Centrifugal gained all solids is scattered in to the mixing solutions of 30mL ethanol and 8.6mL deionized water, then adds 1.24mL ammoniacal liquor and 0.36mL tetraethyl orthosilicate reaction 4h, the centrifugal composite pellets that obtains;
(4) remove PS bead
By gained bead (PS@TiO
2@SiO
2) in retort furnace, 500 ℃ of high-temperature calcination 2h remove PS bead, leave outer wall;
(5) remove silicon-dioxide shell
By calcine hollow ball add in 2.5mol/L sodium hydroxide solution and react 3h, centrifuge washing,, except decapsidate, obtains monodispersed meso-porous hollow nano titanium dioxide ball.
embodiment 6
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene sphere surface cladding titanium dioxide (PS@TiO
2)
0.024g PS bead and 10mL dehydrated alcohol are joined in the there-necked flask of 250mL and stir 30min, add 0.3mL ammoniacal liquor and 0.024g hydroxypropylcellulose (HPC) to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, the centrifugal PS@TiO that obtains
2bead.
(3) the outside coated silica of titanium dioxide (PS@TiO
2@SiO
2)
(2) gained composite pellets is scattered in to hold over night in the deionized water that 10ml contains 0.024g Polyvinylpyrolidone (PVP) (PVP), then centrifugal; Centrifugal gained all solids is scattered in to the mixing solutions of 30mL ethanol and 8.6mL deionized water, then adds 1.24mL ammoniacal liquor and 0.36mL tetraethyl orthosilicate reaction 4h, the centrifugal composite pellets that obtains;
(4) remove PS bead
By gained bead (PS@TiO
2@SiO
2) in retort furnace, 500 ℃ of high-temperature calcination 3h remove PS bead, leave outer wall;
(5) remove silicon-dioxide shell
By calcine hollow ball add in 2.5mol/L sodium hydroxide solution and react 3h, centrifuge washing,, except decapsidate, obtains monodispersed meso-porous hollow nano titanium dioxide ball.
embodiment 7
(1) preparation of polystyrene (PS) nanometer bead
Under room temperature, add the deionized water of 90mL in the there-necked flask of 250mL, then add the styrene monomer of 9mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 30min, is increased to 70 ℃ gradually by temperature; 0.3g initiator potassium persulfate (KPS) is dissolved in 10mL deionized water, is heated to 70 ℃, add in there-necked flask disposable this solution, under the environment of logical nitrogen and 70 ℃, react 24h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene sphere surface cladding titanium dioxide (PS@TiO
2)
0.024g PS bead and 10mL dehydrated alcohol are joined in the there-necked flask of 250mL and stir 30min, add 0.3mL ammoniacal liquor and 0.024g hydroxypropylcellulose (HPC) to stir 30min, then slowly drip tetrabutyl titanate and the 20mL ethanol of 0.5mL, reaction 1h, the centrifugal PS@TiO that obtains
2bead.
(3) the outside coated silica of titanium dioxide (PS@TiO
2@SiO
2)
(2) gained composite pellets is scattered in to hold over night in the deionized water that 10ml contains 0.024g Polyvinylpyrolidone (PVP) (PVP), then centrifugal; Centrifugal gained all solids is scattered in to the mixing solutions of 30mL ethanol and 8.6mL deionized water, then adds 1.24mL ammoniacal liquor and 0.36mL tetraethyl orthosilicate reaction 4h, the centrifugal composite pellets that obtains;
(4) remove PS bead
By gained bead (PS@TiO
2@SiO
2) in retort furnace, 500 ℃ of high-temperature calcination 4h remove PS bead, leave outer wall;
(5) remove silicon-dioxide shell
By calcine hollow ball add in 2.5mol/L sodium hydroxide solution and react 3h, centrifuge washing,, except decapsidate, obtains monodispersed meso-porous hollow nano titanium dioxide ball.
The amount difference of embodiment 1-embodiment 4 tetraethyl orthosilicate used, can find out the monodispersity difference of the hollow titanium dioxide ball of gained from TEM, embodiment 1 does not use coated with silica bead, and titanium dioxide bonding in calcination process, so the bead finally obtaining adheres to each other.The amount of the tetraethyl orthosilicate that embodiment 2 drips is few, that bead is completely not coated, and part titanium dioxide bonding in calcination process, so monodispersity is poor.In embodiment 3 and embodiment 4, silicon-dioxide is better bead cladding ratio, and the bead monodispersity obtaining is relatively good.So the amount of the tetraethyl orthosilicate adding is extremely important.
The calcination time difference of embodiment 5-embodiment 7 in retort furnace, from XRD figure, the titanium dioxide crystal form of the different gained of calcination time is anatase octahedrite, but the grain size of calcining 2h gained is 18.7nm, calcining 3h gained grain size is 16.5nm, calcining 4h gained grain size is 17.6nm, so calcination time is 2h-4h.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (8)
1. a preparation method for the spherical titanium dioxide of monodisperse mesoporous hollow Nano, is characterized in that: take styrene monomer as raw material, take Potassium Persulphate as initiator, make the pipe/polyhenylethylene nano bead of surface band negative charge; Then the mixing solutions that drips tetrabutyl titanate and ethanol, obtains polystyrene-TiO
2composite pellets; Then add tetraethyl orthosilicate at composite pellets surface coated silica; Finally in retort furnace, polystyrene is removed in high-temperature calcination, and through sodium hydroxide solution corrode silicon dioxide, centrifuge washing makes the spherical titanium dioxide of monodisperse mesoporous hollow Nano.
2. the preparation method of the spherical titanium dioxide of monodisperse mesoporous hollow Nano according to claim 1, is characterized in that: specifically comprise the following steps:
(1) preparation of pipe/polyhenylethylene nano bead:
Under room temperature, add deionized water, styrene monomer in the there-necked flask of 250mL, logical nitrogen is got rid of the air in bottle, and magnetic agitation 20～40min, is increased to 50～90 ℃ gradually by temperature; Initiator potassium persulfate is dissolved in deionized water, is heated to 50～90 ℃, add in there-necked flask disposable this solution; Continue reaction 22～26h, centrifugal drying obtains polystyrene sphere;
(2) polystyrene-TiO
2the preparation of composite pellets:
Polystyrene sphere and dehydrated alcohol are joined in the there-necked flask of 250mL and stir 20～40min, add after ammoniacal liquor and hydroxypropylcellulose, stir 20～40min; Then slowly drip the mixing solutions of tetrabutyl titanate and ethanol, reaction 0.5～1.5h, obtains polystyrene-TiO
2composite pellets;
(3) composite pellets surface coated silica
(2) gained composite pellets is scattered in the Polyvinylpyrolidone (PVP) aqueous solution to hold over night, centrifugal; Centrifugal gained solid is scattered in the mixing solutions of ethanol and deionized water, then adds ammoniacal liquor and tetraethyl orthosilicate, reaction 2～6h, centrifugally obtains the composite pellets that surface is coated with silicon oxide;
(4) remove polystyrene
The composite pellets that gained is coated with silicon oxide high-temperature calcination in retort furnace, removes polystyrene; (5) remove silicon-dioxide shell
The hollow ball that calcining is obtained adds in sodium hydroxide solution and reacts, and centrifuge washing, except decapsidate, obtains hollow monodispersed mesoporous TiO 2 bead.
3. the preparation method of the spherical titanium dioxide of monodisperse mesoporous hollow Nano according to claim 2, it is characterized in that: in described step (1), the volume ratio of deionized water and styrene monomer is 10:0.5～1.5, and the quality of initiator is 0.2～0.4% of styrene monomer quality.
4. the preparation method of the spherical titanium dioxide of monodisperse mesoporous hollow Nano according to claim 2, it is characterized in that: in described step (2), polystyrene sphere consumption is 0.01～0.03% of dehydrated alcohol quality, ammonia volume is 0.2～0.4% of dehydrated alcohol quality, tetrabutyl titanate consumption is 0.3～0.7% of dehydrated alcohol quality, and hydroxypropylcellulose consumption is 0.01～0.03% of dehydrated alcohol quality.
5. the preparation method of the spherical titanium dioxide of monodisperse mesoporous hollow Nano according to claim 2, it is characterized in that: in described step (3), in the Polyvinylpyrolidone (PVP) aqueous solution, the massfraction of Polyvinylpyrolidone (PVP) is 0.24%, the mass ratio of composite pellets and Polyvinylpyrolidone (PVP) is 1:1, in the mixing solutions of dehydrated alcohol and water: the volume ratio of dehydrated alcohol and deionized water is 10:2～4, ammonia concn used is 26%wt, in ammoniacal liquor and mixing solutions, the volume ratio of deionized water is 1～2:7, the volume ratio of ammoniacal liquor and tetraethyl orthosilicate is 1.24:0.31 ~ 0.4.
6. the preparation method of the spherical titanium dioxide of monodisperse mesoporous hollow Nano according to claim 2, is characterized in that: high-temperature calcination in described step (4): temperature is 450～550 ℃, and calcination time is 2～4h.
7. the preparation method of the spherical titanium dioxide of monodisperse mesoporous hollow Nano according to claim 2, is characterized in that: in described step (5), the concentration of sodium hydroxide is 2～3mol/L, and the reaction times is 2～4h.
8. the spherical titanium dioxide of monodisperse mesoporous hollow Nano that preparation method as claimed in claim 1 or 2 makes.
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