CN102491415A - Preparation method of monodispersed anatase titanium dioxide nano porous microspheres - Google Patents
Preparation method of monodispersed anatase titanium dioxide nano porous microspheres Download PDFInfo
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- CN102491415A CN102491415A CN2011103971460A CN201110397146A CN102491415A CN 102491415 A CN102491415 A CN 102491415A CN 2011103971460 A CN2011103971460 A CN 2011103971460A CN 201110397146 A CN201110397146 A CN 201110397146A CN 102491415 A CN102491415 A CN 102491415A
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Abstract
The invention discloses a preparation method of monodispersed anatase titanium dioxide nano porous microspheres. The sizes of the obtained microspheres are adjustable in the range of 400-900 nanometers, are monodispersed and have rough surfaces, and the specific surface area exceeds 80 m<2>/g; and a single microsphere is formed by self-assembling small crystal grains of about 10 nanometers and has a typical graded structure, and the pore diameter is 12-20 nanometers. The preparation method comprises the following steps of: quickly hydrolyzing, polymerizing and self-assembling butyl titanate under the assistance of lauryl amine at the room temperature to form titanium dioxide microspheres of smooth surfaces and single sizes; and performing hydro-thermal treatment in a mixed solvent consisting of ethanol and water at the temperature of 150-180 DEG C for 15-20 hours to transform into monodispersed anatase titanium dioxide nano porous microspheres. A remarkable crystal face staggered growing phenomenon exists among small crystal grains in the obtained nano porous microspheres, so that quick transmission of electrons is facilitated; and the monodispersed anatase titanium dioxide nano porous microspheres can be taken as a photocatalyst, a photoelectrode material of a sensitized solar cell and a cathode material of a high-temperature lithium cell.
Description
Technical field
The invention belongs to electronic technology field, further relate to a kind of single preparation method who disperses anatase titania nanoporous microballoon in the nano material manufacturing technology field.The titanium dioxide microballoon sphere of the present invention preparation, can be directly as the light anode material use of photocatalyst or dye sensitization solar battery.
Background technology
Nano titanium oxide is nontoxic, weather-proof with it, chemical-resistant stability and high photoelectrochemistry reactive behavior and superhigh specific surface area, is widely used in fields such as new dye sensitization solar battery and photochemical catalysis.The high-specific surface area of this nano particle for dye adsorption and light induced electron hole right separate very necessary, thereby can improve the electricity conversion of battery and the photocatalysis efficiency of catalyzer.Simultaneously, because particle size is little, recovery difficult is big aspect the catalysis use, and a little less than particle mutually combined in battery, the loss of electrons that causes because of the crystal boundary scattering was big.
The patent " a kind of monodisperse titanium dioxide nanometer microballoons and preparation method thereof " (application number 201010127828.5, publication number CN 101830502A) of Zhejiang University's application discloses a kind of preparation method by a nanometer ball of string bunch monodisperse titanium dioxide microballoon that assembling forms.Sodium hydroxide solution is added titanium plate and ydrogen peroxide 50 reaction surplus solution afterwards, obtained titanium dioxide microballoon sphere in 20～64 hours, obtain the anatase titania microballoon through IX and high-temperature heat treatment in 120 ℃ of hydro-thermal reactions.The deficiency that this patented claim exists is: complicated process of preparation, raw material corrodibility are strong, are difficult to accomplish scale production.
The patent " preparation method of the monodisperse spherical mesoporous titanium oxide colloid particle that size and pattern are controlled " (application number 200610011885.0, publication number CN 101070184A) of Physical Chemistry Technology Inst., Chinese Academy of Sciences application provides the preparation method of the controlled monodisperse titanium dioxide colloidal solid of a kind of size, pattern.As template, swelling infiltration through solvent and follow-up thermal treatment are removed template and are obtained the mesoporous TiO 2 microballoon with polymer microballoon.The deficiency that this patented claim exists is: sacrifice template, material loss is big, and solvent is poisonous, and is big to environmental influence, and preparation process is complicated, and pore diameter range distributes wide, and the separation influence right to the light induced electron hole is big.
The patent " a kind of method for preparing anatase-TiO 2 porous microspheres " (application number 200910308991.9, publication number CN 101665268A) of Harbin Institute of Technology's application has proposed a kind of preparation method of anatase titania porous microsphere.With the sulfate dihydrate titanium is precursor, obtains the poriferous titanium dioxide microballoon through hydrothermal treatment consists, deposition, washing.The deficiency that this patented claim exists is: the hydrothermal treatment consists time is long, and energy consumption is bigger.
Summary of the invention
The present invention provides a kind of single preparation method who disperses anatase titania nanoporous microballoon in order to overcome the deficiency of above-mentioned prior art, products therefrom size homogeneous, adjustable, porous, and specific surface area is big.
The present invention includes following steps:
(1) under the room temperature laurylamine is dissolved in the ethanol that contains Repone K, mixes the back and add butyl(tetra)titanate, stirring, standing demix.
(2) remove the upper solution of step (1) gained layered system, take out lower floor's white precipitate, and use washing with alcohol, spinning repeatedly, drying at room temperature obtains titanium dioxide microballoon sphere.
(3) titanium dioxide microballoon sphere with step (2) is distributed in the mixed solvent of ethanol and water, adds ammoniacal liquor, stirs and transfers to contain and carry out hydro-thermal reaction in the teflon-lined autoclave pressure, and reaction finishes the back furnace cooling to room temperature.
(4) take out step (3) gained hydro-thermal reaction thing, use washing with alcohol, spinning repeatedly, drying at room temperature obtains monodispersed anatase titania nanoporous microballoon.
The present invention compared with prior art has the following advantages:
First; The present invention prepares the morphology control and the crystallization treatment of material and accomplishes step by step; Make precursor form spherical microballoon under the room temperature in auxiliary quick hydrolysis down, the polymerization self-assembly of tensio-active agent; Be converted into the anatase octahedrite porous microsphere through hydrothermal treatment consists then, wherein the basic configuration of microballoon remains unchanged in the hydrothermal treatment step.This morphology control and structural transformation are accomplished step by step is one of effective way of other ad hoc structure of preparation, specific morphology material.
The second, and the size adjustable of the nano titania porous microsphere that the present invention prepares (400nm～900nm), single dispersion, porous and high-specific surface area, surface irregularity, pore size are 12nm～20nm, specific surface area is all above 80m
2/ g, wherein pore size and specific surface area etc. are relevant with the hydrothermal crystallization process.
The 3rd; The resulting nano titania porous microsphere of the present invention has typical hierarchy; Single microballoon is that the little crystal grain self-assembly by a lot of particle diameter 9nm～14nm forms, and there is the staggered growth of tangible crystal face phenomenon in little intergranule, and this quick transmission for electronics is very necessary.
The 4th, the method technology that the present invention prepares the monodisperse titanium dioxide nanometer porous microsphere is simple, is easy to promote mass-producing and uses the solvent for use safety and environmental protection.
Description of drawings
Fig. 1 schema of the present invention;
The SEM figure of Fig. 2 embodiment of the invention 2 preparation titanium oxide amorphous microballoons;
The SEM figure of Fig. 3 embodiment of the invention 4 preparation anatase titania nanoporous microballoons;
Fig. 4 the present invention prepares the X-ray diffractogram of titanium dioxide microballoon sphere;
The TEM figure of Fig. 5 embodiment of the invention 4 preparation anatase titania nanoporous microballoons;
Fig. 6 embodiment of the invention 4 preparation titanium dioxide microballoon spheres are through the I-V curve of N719 dye sensitization gained solar cell.
Embodiment
1 couple of the present invention does further explain below in conjunction with accompanying drawing.
Step 1 is dissolved in laurylamine in the ethanol that contains Repone K under the room temperature, mixes the back and adds butyl(tetra)titanate, leaves standstill after stirring finishes and obtains layered system, and wherein, Repone K is the potassium chloride solution of concentration 0.1 mol, and consumption is 2～4mL; The concentration of laurylamine is 3g/l～5g/l; The concentration of butyl(tetra)titanate is 99%, and consumption is 15mL/l～25mL/.
Step 3 is distributed to the titanium dioxide microballoon sphere of step 2 in the mixed solvent of ethanol and water, adds ammoniacal liquor; Stir and transfer to contain and carry out hydro-thermal reaction in the teflon-lined autoclave pressure; Reaction finishes the back furnace cooling to room temperature, and wherein, the consumption of titanium dioxide microballoon sphere is 1g; The volume ratio of ethanol and water is 2 in the mixed solvent, and the total amount of solvent is 20mL; Ammonia concn is 28%, and consumption is 0～1mL; Hydrothermal temperature is 150 ℃～180 ℃, and the reaction times is 15h～20h.
The concrete embodiment of the present invention is following:
Embodiment 1
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 600mL; In the violent stirring process, adding 2mL concentration is the KCl solution of 0.1M, and adding 15mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, remove the upper solution of layered system, take out lower floor's white precipitate and continuous in washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 0mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 160 ℃ electronics baking oven to react 15 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 600mL; In the violent stirring process, adding 2mL concentration is the KCl solution of 0.1M, and adding 15mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, remove the upper solution of layered system, take out lower floor's white precipitate and continuous in washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 0.5mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 160 ℃ electronics baking oven to react 15 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
Embodiment 3
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 600mL; In the violent stirring process, adding 2mL concentration is the KCl solution of 0.1M, and adding 15mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, remove the upper solution of layered system, take out lower floor's white precipitate and continuous in washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 1mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 160 ℃ electronics baking oven to react 15 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 800mL; In the violent stirring process, adding 2mL concentration is the KCl solution of 0.1M, and adding 15mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, the upper strata clear solution is slowly outwelled, taken out lower floor's white precipitate and continuous in washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 0.5mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 160 ℃ electronics baking oven to react 15 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
Embodiment 5
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 1000mL; In the violent stirring process, adding 2mL concentration is the KCl solution of 0.1M, and adding 15mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, remove the upper solution of layered system, take out lower floor's white precipitate and continuous in washing with alcohol, spinning (centrifugal speed is 4000r/min) 3 times, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon; Again be distributed in the mixed solvent (20mL) of ethanol and water (volume ratio 2: 1); The strong aqua 0.5mL that adds concentration 28% transfers to after stirring and contains in the teflon-lined autoclave pressure, places 160 ℃ electronics baking oven reaction 15 hours; After reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning (centrifugal speed is 4000r/min) reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
Embodiment 6
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 800mL; In the violent stirring process, adding 2mL concentration is the KCl solution of 0.1M, and adding 15mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction trend towards balance, the obvious layering of system;
Secondly, remove the upper solution of layered system, take out lower floor's white precipitate and continuous in washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 0.5mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 160 ℃ electronics baking oven to react 18 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
Embodiment 7
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 800mL; In the violent stirring process, adding 3mL concentration is the KCl solution of 0.1M, and adding 20mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, remove the upper solution of layered system,, take out lower floor's white precipitate and continuous with washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 1mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 180 ℃ electronics baking oven to react 20 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
Embodiment 8
At first, at ambient temperature, the 5g laurylamine is dissolved in the ethanol of 800mL; In the violent stirring process, adding 4mL concentration is the KCl solution of 0.1M, and adding 25mL concentration is 99% butyl(tetra)titanate after mixing; It is muddy that solution becomes at once; Continue to stir 3-5 minute, sealing and standing makes reaction tend to balance system layering;
Secondly, remove the upper solution of layered system, take out lower floor's white precipitate and continuous in washing with alcohol, spinning, drying at room temperature obtains smooth surface, distribution of sizes homogeneous, amorphous TiO
2Microballoon;
Weighing 1g TiO
2Microballoon is distributed in the mixed solvent of 20mL ethanol and water again, adds strong aqua 0.5mL, transfers to after stirring to contain in the teflon-lined autoclave pressure, places 150 ℃ electronics baking oven to react 18 hours, and after reaction finished, furnace cooling was to room temperature;
Take out pressure reaction still, use washing with alcohol, spinning reaction product continuously, drying at room temperature can obtain monodispersed anatase titania nanoporous microballoon.
Fig. 2 is the SEM figure of embodiment 2 preparation titanium oxide amorphous microballoons.As can be seen from the figure, this microsphere features smooth surface, distribution of sizes homogeneous (700 ± 50nm), have good monodispersity.Fig. 3 is the SEM figure of embodiment 4 preparation anatase titania nanoporous microballoons.Can find out that by Fig. 3 the surface irregularity through the hydrothermal treatment consists microballoon has tangible hierarchy, and is converted into crystalline structure (shown in the XRD curve of Fig. 4).As can be seen from Figure 4 the diffraction peak of gained hydrothermal product belongs to anatase titania, and promptly products therefrom is the anatase titania microballoon.Fig. 5 is the TEM figure of embodiment 4 preparation anatase titania nanoporous microballoons.Can further find out by Fig. 5; Thus obtained microsphere is to form the hierarchy product by the little crystal grain self-assembly about size 10nm; There is the staggered growth of crystal face phenomenon each other in little crystal grain, and this is highly beneficial for photoelectronic quick transmission in the raising sensitization solar battery
Fig. 6 is the I-V curves of embodiment 4 preparation titanium dioxide microballoon spheres through N719 dye sensitization gained solar cell.Wherein, the electrodes use silk screen printing forms, effectively illuminating area 1cm
2, illumination condition is AM1.5.As can be seen from Figure 6; Compare with the basic sensitization solar battery of commercial titanium dioxide (P25) of same process preparation; The short-circuit photocurrent of gained titanium dioxide microballoon sphere base sensitization solar battery of the present invention obviously improves; Show that this grading structure material has higher specific surface area, is suitable for sensitization solar battery.
In sum, not only the size monodispersity is good for gained material of the present invention, and classifying porous, has high specific surface area, is suitable for the optoelectronic pole of sensitization solar battery and the negative material of high-performance lithium battery.
Claims (9)
1. a single preparation method who disperses anatase titania nanoporous microballoon is characterized in that, may further comprise the steps:
(1) under the room temperature laurylamine is dissolved in the ethanol that contains Repone K, mixes the back and add butyl(tetra)titanate, stirring, standing demix;
(2) remove the upper solution of step (1) gained layered system, take out lower floor's white precipitate, and use washing with alcohol, spinning repeatedly, drying at room temperature obtains titanium dioxide microballoon sphere;
(3) titanium dioxide microballoon sphere with step (2) is distributed in the mixed solvent of ethanol and water, adds ammoniacal liquor, stirs and transfers to contain and carry out hydro-thermal reaction in the teflon-lined autoclave pressure, and reaction finishes the back furnace cooling to room temperature;
(4) take out step (3) gained hydro-thermal reaction thing, use washing with alcohol, spinning repeatedly, drying at room temperature obtains monodispersed anatase titania nanoporous microballoon.
2. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the wherein said Repone K of step (1) is the potassium chloride solution of concentration 0.1 mol, and consumption is 2～4mL.
3. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the concentration of the described laurylamine of step (1) is 3g/l～5g/l.
4. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the concentration of the described butyl(tetra)titanate of step (1) is 99%, and consumption is 15mL/l～25mL/l.
5. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the consumption of the described titanium dioxide microballoon sphere of step (3) is 1g.
6. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the volume ratio of ethanol and water is 2 in the described mixed solvent of step (3), and the total amount of solvent is 20mL.
7. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the described ammonia concn of step (3) is 28%, and consumption is 0～1mL.
8. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the described hydrothermal temperature of step (3) is 150 ℃～180 ℃, and the reaction times is 15h～20h.
9. single preparation method who disperses anatase titania nanoporous microballoon according to claim 1, it is characterized in that: the rotating speed of step (3) and step (4) spinning is 4000r/min.
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| CN102718256A (en) * | 2012-06-23 | 2012-10-10 | 三峡大学 | Preparation method for titania microspheres with adjustable grain sizes |
| CN102774885A (en) * | 2012-07-20 | 2012-11-14 | 中国科学院等离子体物理研究所 | Porous submicron sphere, porous film electrode and preparation method and application in dye sensitized solar cells thereof |
| CN102795664A (en) * | 2012-08-10 | 2012-11-28 | 东华大学 | Preparation method of mesoporous titanium dioxide microballoons with controllable particle size |
| CN103739013A (en) * | 2014-01-07 | 2014-04-23 | 天津大学 | Porous spherical titanium dioxide with controllable diameter and preparation and application thereof |
| CN103771506A (en) * | 2013-12-24 | 2014-05-07 | 中国科学院合肥物质科学研究院 | Micro/nano hierarchical titanium dioxide microspheres as well as preparation method and application thereof |
| CN105688874A (en) * | 2016-03-11 | 2016-06-22 | 河北工业大学 | TiO2 nanopowder provided with graded pore structure and preparation method of TiO2 nanopowder |
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Cited By (10)
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| CN102718256A (en) * | 2012-06-23 | 2012-10-10 | 三峡大学 | Preparation method for titania microspheres with adjustable grain sizes |
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| CN102774885A (en) * | 2012-07-20 | 2012-11-14 | 中国科学院等离子体物理研究所 | Porous submicron sphere, porous film electrode and preparation method and application in dye sensitized solar cells thereof |
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| CN102795664B (en) * | 2012-08-10 | 2014-07-02 | 东华大学 | Preparation method of mesoporous titanium dioxide microballoons with controllable particle size |
| CN103771506A (en) * | 2013-12-24 | 2014-05-07 | 中国科学院合肥物质科学研究院 | Micro/nano hierarchical titanium dioxide microspheres as well as preparation method and application thereof |
| CN103771506B (en) * | 2013-12-24 | 2016-06-29 | 中国科学院合肥物质科学研究院 | Micro-/to receive hierarchy titanium dioxide microballoon sphere and preparation method thereof and application |
| CN103739013A (en) * | 2014-01-07 | 2014-04-23 | 天津大学 | Porous spherical titanium dioxide with controllable diameter and preparation and application thereof |
| CN105688874A (en) * | 2016-03-11 | 2016-06-22 | 河北工业大学 | TiO2 nanopowder provided with graded pore structure and preparation method of TiO2 nanopowder |
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Application publication date: 20120613 |