CN101555037A - Method for preparing hollow titanium dioxide nano-sphere - Google Patents
Method for preparing hollow titanium dioxide nano-sphere Download PDFInfo
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- CN101555037A CN101555037A CNA200910098714XA CN200910098714A CN101555037A CN 101555037 A CN101555037 A CN 101555037A CN A200910098714X A CNA200910098714X A CN A200910098714XA CN 200910098714 A CN200910098714 A CN 200910098714A CN 101555037 A CN101555037 A CN 101555037A
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- titanium dioxide
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- dioxide nano
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Abstract
The invention discloses a method for preparing a hollow titanium dioxide nano-sphere, which comprises the steps of dissolving fluoroborate in de-ionized water, adding titanium trichloride and hydrogen peroxide under continuous mixing to obtain clarified solution, putting the clarified solution in a stainless steel reaction kettle with a poly-tetrafluoroethylene internal lining, sealing the solution, putting the solution in a baking oven with the temperature of 160 DEG C to 200 DEG C to preserve temperature for 10 to 16 hours, cooling the solution to room temperature, repeatedly washing and centrifugation-separating the obtained precipitation and de-ionized water, and then obtaining the hollow titanium dioxide nano-sphere by drying for 12 to 24 hours at the temperature of 80 to 100 DEG C. The method has simple process, low cost and friendly environment and is suitable for mass production; the obtained product is expected to be used in files of catalysts, dye-sensitized solar cell materials, lithium-ion electrode materials and the like.
Description
Technical field
The present invention relates to preparation of nanomaterials, relate in particular to a kind of preparation method of hollow titanium dioxide nano-sphere.
Background technology
Titanium dioxide (TiO
2) be a kind of important semiconductor material.Because it has high electricity conversion, highlight catalytic active, Stability Analysis of Structures, characteristics such as nontoxic, TiO
2Be widely used for modern science and technology fields such as photoelectrocatalysis, sun power utilization, pigment, transmitter, lithium ion battery.Similar with other nano materials, TiO
2Factor such as pattern, particle diameter, crystalline phase composition, defect and impurity for its photoelectric property important influence.Preparation has the TiO of unique pattern
2Nano material is significant for its photoelectric properties of further raising.With common low-dimensional TiO
2The nano material difference, three-dimensional hollow TiO
2Nano material often has better permeability, bigger specific surface area, lower density and the light utilization efficiency of Geng Gao, and the cavity at its center can be used as the generation that " nano-reactor " holds and promote chemical reaction.Therefore, prepare three-dimensional hollow TiO
2Nano material becomes the research focus that more and more receives publicity.Some relevant three-dimensional hollow TiO have been arranged at present
2The report of nano material preparation, for example, Zhang etc. are with TiCl
4Be the Ti source, utilize no template hydro-thermal reaction technology to obtain the graduation hollow TiO that assembles by rutile nano-stick
2Microballoon (Zhang Y F, Feng X H, Liu H, Wang C C, Liu J Z, Wei Y.Self-Assembly TiO
2Hierarchical Hollow Microsphereswith Rutile Nanorods by Template-Free Hydrothermal Method.Chem.Lett., 2008,37 (12): 1264～1265).Yang etc. are with TiF
4For the titanium source has obtained hollow TiO by hydro-thermal reaction
2Nanometer ball (Yang H G, Zeng H C.Preparation of Hollow Anatase TiO
2Nanospheres viaOstwald Ripening.J.Phys.Chem.B, 2004,108 (11): 3492～3495).Zhou etc. are with TiF
4For the titanium source has prepared micron-scale hollow TiO by hydro-thermal reaction
2(Zhou J K, Lv L, Yu J Q, Li H L, Guo P Z, Sun H, Zhao X S.Synthesis of Self-Organized Polycrystalline F-dopedTiO
2Hollow Microspheres and Their Photocatalytic Activity under Visible Light.J.Phys.Chem.C, 2008,112 (14): 5316～5321).But these preparation hollow TiO
2The titanium source of adopting in the method for nano material is TiCl
4Or TiF
4Very unstable in air, run into damp atmosphere violent hydrolysis reaction can take place, and have strong impulse, these have brought inconvenience to experimental implementation, and there is detrimentally affect in environment, are unfavorable for scale operation.Therefore, adopt stable and cheap titanium-containing compound to prepare hollow TiO as the titanium source
2Nano material still exists great challenge.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of technology simple, with low cost, eco-friendly hollow TiO
2The preparation method of nanometer ball.
Hollow TiO
2The preparation method of nanometer ball is: fluoroborate is dissolved in the deionized water, continue to stir and add titanous chloride and hydrogen peroxide down, the ratio of the amount of substance of titanous chloride and fluoroborate is 1.5～2, the ratio of the amount of substance of hydrogen peroxide and titanous chloride is 2～3, obtain settled solution, pack into and have in the teflon-lined stainless steel cauldron, sealing, put into 160～200 ℃ of baking ovens, be incubated 10～16 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 12～24 hours under 80～100 ℃, obtains the hollow titanium dioxide nano-sphere.
Described fluoroborate can be potassium fluoborate or Sodium tetrafluoroborate.
All reagent of the present invention are commercially available reagent, and are cheap and easy to get, need not further purification process.Have characteristics such as equipment is simple, easy and simple to handle, with low cost, environmental friendliness.The hollow TiO for preparing
2Nanometer ball is expected to scale operation and is applied to numerous areas such as catalyzer, dye sensitization solar battery material, li-ion electrode materials.
Description of drawings
Fig. 1 is the hollow TiO that adopts the inventive method preparation
2The X-ray diffractogram of nanometer ball;
Fig. 2 (a) is the hollow TiO that adopts the inventive method preparation
2The low magnification field emission scanning electron microscope figure of nanometer ball;
Fig. 2 (b) is the hollow TiO that adopts the inventive method preparation
2The high-amplification-factor field emission scanning electron microscope figure of nanometer ball;
Fig. 3 is the hollow TiO that adopts the inventive method preparation
2The ultraviolet-visible of the nanometer ball spectrogram that diffuses;
Fig. 4 is the hollow TiO that adopts the inventive method preparation
2(Ahv) of nanometer ball
1/2Graph of a relation with (hv).
Embodiment
Below in conjunction with example the present invention is further specified.
The 4mmol potassium fluoborate is dissolved in the 80mL deionized water, continue to stir down and add 8mmol titanous chloride (16～18% solution) and 20mmol hydrogen peroxide (30% solution), obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, sealing, put into 180 ℃ of baking ovens, be incubated 12 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 24 hours under 80 ℃, obtains the hollow titanium dioxide nano-sphere.Fig. 1 is the X-ray diffractogram of the hollow titanium dioxide nano-sphere of preparation, and is consistent with standard card JCPDS No.21-1272, is pure anatase octahedrite phase, and product has high crystallinity and purity.Fig. 2 (a) is the low magnification field emission scanning electron microscope figure of hollow titanium dioxide nano-sphere of preparation, can see that product is made up of a large amount of ball-like structures, and and there is the ball-like structure of partly splitting in mean diameter about 500nm.Fig. 2 (b) is the high-amplification-factor field emission scanning electron microscope figure of the hollow titanium dioxide nano-sphere of preparation, can see the pattern of an independent nanometer ball that splits, and its outer wall is about 200nm, and the center cavity diameter is about 100nm.Fig. 3 is the ultraviolet-visible of hollow titanium dioxide nano-sphere of the preparation spectrogram that diffuses, and can find that product exists intensive to absorb at UV-light zone (less than 400nm).Fig. 4 is (Ahv) of the hollow titanium dioxide nano-sphere of preparation
1/2Graph of a relation with (hv), this graph of a relation is by the data conversion among Fig. 3, utilize this graph of a relation to do tangent line, the non-direct band gap of semi-conductor that can determine product can be 3.06eV, this value is bigger than the value of the titanium dioxide nanocrystalline of reporting usually, and this characteristic is significant for the photoelectric efficiency that improves titanium dioxide.
The 4mmol Sodium tetrafluoroborate is dissolved in the 80mL deionized water, continue to stir down and add 8mmol titanous chloride (16～18% solution) and 20mmol hydrogen peroxide (30% solution), obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, sealing, put into 180 ℃ of baking ovens, be incubated 12 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 24 hours under 80 ℃, obtains the hollow titanium dioxide nano-sphere.The structure of product is all identical with embodiment 1 with pattern.
The 5.3mmol potassium fluoborate is dissolved in the 80mL deionized water, continue to stir down and add 8mmol titanous chloride (16～18% solution) and 16mmol hydrogen peroxide (30% solution), obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, sealing, put into 160 ℃ of baking ovens, be incubated 16 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 24 hours under 80 ℃, obtains the hollow titanium dioxide nano-sphere.The structure of product is all identical with embodiment 1 with pattern.
The 4mmol Sodium tetrafluoroborate is dissolved in the 80mL deionized water, continue to stir down and add 8mmol titanous chloride (16～18% solution) and 24mmol hydrogen peroxide (30% solution), obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, sealing, put into 180 ℃ of baking ovens, be incubated 12 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 24 hours under 80 ℃, obtains the hollow titanium dioxide nano-sphere.The structure of product is all identical with embodiment 1 with pattern.
The 4mmol potassium fluoborate is dissolved in the 80mL deionized water, continue to stir down and add 8mmol titanous chloride (16～18% solution) and 20mmol hydrogen peroxide (30% solution), obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, sealing, put into 200 ℃ of baking ovens, be incubated 10 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 24 hours under 80 ℃, obtains the hollow titanium dioxide nano-sphere.The structure of product is all identical with embodiment 1 with pattern.
The 4mmol Sodium tetrafluoroborate is dissolved in the 80mL deionized water, continue to stir down and add 8mmol titanous chloride (16～18% solution) and 20mmol hydrogen peroxide (30% solution), obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, sealing, put into 180 ℃ of baking ovens, be incubated 12 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 12 hours under 100 ℃, obtains the hollow titanium dioxide nano-sphere.The structure of product is all identical with embodiment 1 with pattern.
Claims (2)
1. the preparation method of a hollow titanium dioxide nano-sphere, it is characterized in that: fluoroborate is dissolved in the deionized water, continue to stir and add titanous chloride and hydrogen peroxide down, the ratio of the amount of substance of titanous chloride and fluoroborate is 1.5～2, the ratio of the amount of substance of hydrogen peroxide and titanous chloride is 2～3, obtain settled solution, packing into has in the teflon-lined stainless steel cauldron, and 160～200 ℃ of baking ovens are put in sealing, be incubated 10～16 hours, cool to room temperature, the precipitation that obtains is cleaned repeatedly through deionized water and dehydrated alcohol, centrifugation, drying is 12～24 hours under 80～100 ℃, obtains the hollow titanium dioxide nano-sphere.
2. the preparation method of a kind of hollow titanium dioxide nano-sphere according to claim 1 is characterized in that described fluoroborate is potassium fluoborate or Sodium tetrafluoroborate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717114B (en) * | 2009-12-02 | 2011-08-24 | 浙江大学 | Titanium dioxide with hollow polyhedral structure and preparation method thereof |
| CN102234133A (en) * | 2010-04-21 | 2011-11-09 | 中国科学院上海硅酸盐研究所 | Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof |
| CN102718257A (en) * | 2012-06-28 | 2012-10-10 | 中南民族大学 | Method for preparing titanium dioxide hollow microsphere by utilizing hollow nanoparticles |
| CN103894163A (en) * | 2012-12-24 | 2014-07-02 | 北京有色金属研究总院 | High-performance nanometer TiO2 photocatalyst material and preparation method thereof |
| CN107867717A (en) * | 2017-09-30 | 2018-04-03 | 常熟理工学院 | Based on hollow-core construction purple TiO2Michaelis resonance anti-fake product and its method for anti-counterfeit |
| CN108264087A (en) * | 2018-03-16 | 2018-07-10 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction, which prepares to have, aligns Nb2O5The method of nanometer rods |
| CN114789048A (en) * | 2022-04-28 | 2022-07-26 | 安徽工程大学 | Two-dimensional carbon/boron-titanium dioxide composite oxide, preparation method thereof and application thereof in photocatalytic hydrogen production |
-
2009
- 2009-05-18 CN CN200910098714XA patent/CN101555037B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717114B (en) * | 2009-12-02 | 2011-08-24 | 浙江大学 | Titanium dioxide with hollow polyhedral structure and preparation method thereof |
| CN102234133A (en) * | 2010-04-21 | 2011-11-09 | 中国科学院上海硅酸盐研究所 | Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof |
| CN102234133B (en) * | 2010-04-21 | 2013-08-14 | 中国科学院上海硅酸盐研究所 | Semiconductor compound porous wall titanium dioxide hollow sphere material and preparation method thereof |
| CN102718257A (en) * | 2012-06-28 | 2012-10-10 | 中南民族大学 | Method for preparing titanium dioxide hollow microsphere by utilizing hollow nanoparticles |
| CN103894163A (en) * | 2012-12-24 | 2014-07-02 | 北京有色金属研究总院 | High-performance nanometer TiO2 photocatalyst material and preparation method thereof |
| CN103894163B (en) * | 2012-12-24 | 2016-02-24 | 北京有色金属研究总院 | A kind of high-performance nano TiO 2photocatalyst material and preparation method thereof |
| CN107867717A (en) * | 2017-09-30 | 2018-04-03 | 常熟理工学院 | Based on hollow-core construction purple TiO2Michaelis resonance anti-fake product and its method for anti-counterfeit |
| CN107867717B (en) * | 2017-09-30 | 2019-10-18 | 常熟理工学院 | Based on hollow structure purple TiO2Michaelis resonance anti-fake product and its method for anti-counterfeit |
| CN108264087A (en) * | 2018-03-16 | 2018-07-10 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction, which prepares to have, aligns Nb2O5The method of nanometer rods |
| CN108264087B (en) * | 2018-03-16 | 2020-05-05 | 中国科学院广州地球化学研究所 | Single reagent self-reaction preparation of Nb with directional arrangement2O5Method for producing nano-rod |
| CN114789048A (en) * | 2022-04-28 | 2022-07-26 | 安徽工程大学 | Two-dimensional carbon/boron-titanium dioxide composite oxide, preparation method thereof and application thereof in photocatalytic hydrogen production |
| CN114789048B (en) * | 2022-04-28 | 2023-08-15 | 安徽工程大学 | Two-dimensional carbon/boron-titanium dioxide composite oxide, preparation method thereof and application thereof in photocatalytic hydrogen production |
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| CN101555037B (en) | 2010-12-01 |
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