CN103936066A - Method for preparing rutile titanium dioxide nanometer flower array thin film - Google Patents
Method for preparing rutile titanium dioxide nanometer flower array thin film Download PDFInfo
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- CN103936066A CN103936066A CN201410185650.8A CN201410185650A CN103936066A CN 103936066 A CN103936066 A CN 103936066A CN 201410185650 A CN201410185650 A CN 201410185650A CN 103936066 A CN103936066 A CN 103936066A
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Abstract
The invention discloses a method for preparing a rutile titanium dioxide nanometer flower array thin film. The method comprises the following steps: mixing hydrofluoric acid, nitric acid and deionized water so as to prepare a pickling solution; immersing a metallic titanium plate cleaned with the pickling solution in a hydrogen peroxide solution with the mass concentration of 10-12%, and reacting so as to form a titanium dioxide porous thin film with an amorphous structure on the surface of the metallic titanium plate; and then immersing the metallic titanium plate in hot water, adjusting the pH value to 1.0-2.0 by using sulfuric acid, reacting for 36-55 hours, washing by using deionized water, and drying. According to the method, the titanium plate is directly put in the hydrogen peroxide and reacts. The method is simple, easy to carry out, good in repeatability, short in production cycle, low in cost and suitable for large-scale industrial production. The prepared thin film is firmly bonded with a substrate. The method can be widely applied to many fields such as photocatalysis, photoelectrocatalysis, thin-film solar cells, gas sensors and biological materials.
Description
Technical field
The present invention relates to a kind of method of titanium dioxide nanoflower array film.
Background technology
Relate in the application of surface reaction and carrier mobility some such as photochemical catalysis, photoelectrocatalysis, thin-film solar cells, gas sensor etc., three-dimensional flower-shaped nanostructure has unique performance advantage.With regard to three-dimensional nanometer structure titanium dioxide, existing preparation method or relate to TiCl
4, the facile hydrolysis reagent such as tetrabutyl titanate, or need the high temperature and high pressure environments such as hydro-thermal, industrialization cost is higher.The disclosed method of preparing titanium dioxide nanoflower array film of CN102557130A, still needs to add the reagent such as trimeric cyanamide and nitric acid, and relative cost is also higher.
Summary of the invention
The object of this invention is to provide a kind of low cost, can big area prepare the method for well-crystallized's rutile titanium dioxide nano flower array film.
The method of preparing rutile titanium dioxide nano flower array film of the present invention, comprises the steps:
1) nitric acid that the hydrofluoric acid that is 50～55% by mass percent concentration, mass percent concentration are 65～68% and deionized water by volume 1:3:6 mix, and obtain pickle solution;
2) metallic titanium plate cleaning up is immersed in the hydrogen peroxide solution that mass concentration is 10～20%, at 80 DEG C, react 1～48 hour, form the titanium dioxide porous film of non-crystal structure in pickling metal titanium plate;
3) by step 2) titanium dioxide porous film that makes is immersed in 60～80 DEG C of hot water, with sulphur acid for adjusting pH value to 1.0 ~ 2.0, react after 36～55 hours and takes out, with deionized water rinsing, dry, obtains rutile titanium dioxide nano flower array film.
Preparation method of the present invention directly puts into hydrogen peroxide by titanium sheet and reacts, and without adding the reagent such as trimeric cyanamide, nitric acid, simple, reproducible, with short production cycle, cost is low, and institute's made membrane is combined firmly with substrate.Can be widely used in the various fields such as photochemical catalysis, photoelectrocatalysis, thin-film solar cells, gas sensor, biomaterial.
Brief description of the drawings
Fig. 1 is the electron microscope picture of the rutile titanium dioxide nano flower array film of preparation;
Fig. 2 is the X-ray diffractogram of rutile titanium dioxide nano flower array film, in X-ray diffractogram, and A: anatase octahedrite, R: rutile, Ti: titanium.
Embodiment
Further set forth below in conjunction with embodiment the method that the present invention prepares rutile titanium dioxide nano flower array film.But the present invention is not only confined to following embodiment.
embodiment 1
1) nitric acid that the hydrofluoric acid that is 50～55% by mass percent concentration, mass percent concentration are 65～68% and deionized water by volume 1:3:6 mix, and obtain pickle solution;
2) metallic titanium plate cleaning up is immersed in the hydrogen peroxide solution that 50 milliliters of mass concentrations are 20%, at 80 DEG C, react 1 hour, form the titanium dioxide porous film of non-crystal structure in pickling metal titanium plate;
3) by step 2) titanium dioxide porous film that makes is immersed in 80 DEG C of hot water, with sulphur acid for adjusting pH value to 2.0, react after 45 hours and takes out, with deionized water rinsing, dry, obtains rutile titanium dioxide nano flower array film.
The electron microscope picture of the rutile titanium dioxide nano flower array film that this example makes as shown in Figure 1, has generated uniform titanium dioxide nanoflower array film at titanium plate surface as seen.Nano flower diameter is about 400nm, and width of blade is about 60nm, and end is sharp-pointed, the nano flower arrangement that is interweaved.Its X-ray diffractogram is shown in Fig. 2, shows that nano flower array film crystalline phase consists of rutile and Anatase, and further analytical results shows, top layer nano flower is rutile structure.
embodiment 2
1) nitric acid that the hydrofluoric acid that is 50～55% by mass percent concentration, mass percent concentration are 65～68% and deionized water by volume 1:3:6 mix, and obtain pickle solution;
2) metallic titanium plate cleaning up is immersed in the hydrogen peroxide solution that 50 milliliters of mass concentrations are 10%, at 80 DEG C, react 3 hours, form the titanium dioxide porous film of non-crystal structure in pickling metal titanium plate;
3) by step 2) titanium dioxide porous film that makes is immersed in 60 DEG C of hot water, with sulphur acid for adjusting pH value to 1.2, react after 36 hours and takes out, with deionized water rinsing, dry, obtains rutile titanium dioxide nano flower array film.Nano titania flower array pattern approaches embodiment 1.
embodiment 3
1) nitric acid that the hydrofluoric acid that is 50～55% by mass percent concentration, mass percent concentration are 65～68% and deionized water by volume 1:3:6 mix, and obtain pickle solution;
2) metallic titanium plate cleaning up is immersed in the hydrogen peroxide solution that 50 milliliters of mass concentrations are 10%, at 80 DEG C, react 48 hours, form the titanium dioxide porous film of non-crystal structure in pickling metal titanium plate;
3) by step 2) titanium dioxide porous film that makes is immersed in 60 DEG C of hot water, with sulphur acid for adjusting pH value to 1.0, react after 55 hours and takes out, with deionized water rinsing, dry, obtains the even titanium dioxide nanoflower array film in titanium plate surface generation.
embodiment 4
1) nitric acid that the hydrofluoric acid that is 50～55% by mass percent concentration, mass percent concentration are 65～68% and deionized water by volume 1:3:6 mix, and obtain pickle solution;
2) metallic titanium plate cleaning up is immersed in the hydrogen peroxide solution that 50 milliliters of mass concentrations are 15%, at 80 DEG C, react 20 hours, form the titanium dioxide porous film of non-crystal structure in pickling metal titanium plate;
3) by step 2) titanium dioxide porous film that makes is immersed in 60 DEG C of hot water, with sulphur acid for adjusting pH value to 1.5, react after 50 hours and takes out, with deionized water rinsing, dry, obtains the even titanium dioxide nanoflower array film in titanium plate surface generation.
Claims (1)
1. prepare a method for rutile titanium dioxide nano flower array film, it is characterized in that comprising the steps:
1) nitric acid that the hydrofluoric acid that is 50～55% by mass percent concentration, mass percent concentration are 65～68% and deionized water by volume 1:3:6 mix, and obtain pickle solution;
2) metallic titanium plate cleaning up is immersed in the hydrogen peroxide solution that mass concentration is 10～20%, at 80 DEG C, react 1～48 hour, form the titanium dioxide porous film of non-crystal structure in pickling metal titanium plate;
3) by step 2) titanium dioxide porous film that makes is immersed in 60～80 DEG C of hot water, with sulphur acid for adjusting pH value to 1.0 ~ 2.0, react after 36～55 hours and takes out, with deionized water rinsing, dry, obtains rutile titanium dioxide nano flower array film.
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| CN201410185650.8A CN103936066A (en) | 2014-05-05 | 2014-05-05 | Method for preparing rutile titanium dioxide nanometer flower array thin film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597719A (en) * | 2015-11-17 | 2016-05-25 | 山东大学 | Foamed titanium-titanium oxide composite photoelectrocatalytic material and application thereof |
| JP6963853B1 (en) * | 2021-01-15 | 2021-11-10 | 株式会社シケン | Manufacturing method of semiconductor titanium oxide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544684A (en) * | 2003-11-24 | 2004-11-10 | Process for preparing titanium dioxide film on metal Ti surface and Ti plate with titanium dioxide film coated surface prepared thereby | |
| CN1740392A (en) * | 2005-09-13 | 2006-03-01 | 浙江大学 | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium |
| CN1888135A (en) * | 2006-08-01 | 2007-01-03 | 浙江大学 | Process of preparing single-layer nanometer TiO2 rod film in pure rutile structure |
| CN101844077A (en) * | 2010-06-18 | 2010-09-29 | 上海交通大学 | Preparation method of carbon and nitrogen modified nano-titanium dioxide thin film with visible light activity |
| CN101916670A (en) * | 2010-08-25 | 2010-12-15 | 广东工业大学 | Titanium dioxide nanoflower film photoanode and preparation method thereof |
| CN101949054A (en) * | 2010-08-17 | 2011-01-19 | 浙江大学 | Method for preparing single-crystal anatase titanium dioxide film |
| CN102534590A (en) * | 2012-02-22 | 2012-07-04 | 浙江大学 | Method for preparing crystal titanium dioxide nanorod array film |
| CN102557130A (en) * | 2012-02-22 | 2012-07-11 | 浙江大学 | Method for preparing titanium dioxide nanoflower array film |
-
2014
- 2014-05-05 CN CN201410185650.8A patent/CN103936066A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544684A (en) * | 2003-11-24 | 2004-11-10 | Process for preparing titanium dioxide film on metal Ti surface and Ti plate with titanium dioxide film coated surface prepared thereby | |
| CN1740392A (en) * | 2005-09-13 | 2006-03-01 | 浙江大学 | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium |
| CN1888135A (en) * | 2006-08-01 | 2007-01-03 | 浙江大学 | Process of preparing single-layer nanometer TiO2 rod film in pure rutile structure |
| CN101844077A (en) * | 2010-06-18 | 2010-09-29 | 上海交通大学 | Preparation method of carbon and nitrogen modified nano-titanium dioxide thin film with visible light activity |
| CN101949054A (en) * | 2010-08-17 | 2011-01-19 | 浙江大学 | Method for preparing single-crystal anatase titanium dioxide film |
| CN101916670A (en) * | 2010-08-25 | 2010-12-15 | 广东工业大学 | Titanium dioxide nanoflower film photoanode and preparation method thereof |
| CN102534590A (en) * | 2012-02-22 | 2012-07-04 | 浙江大学 | Method for preparing crystal titanium dioxide nanorod array film |
| CN102557130A (en) * | 2012-02-22 | 2012-07-11 | 浙江大学 | Method for preparing titanium dioxide nanoflower array film |
Non-Patent Citations (1)
| Title |
|---|
| 祁彬: """纳米花"结构二氧化钛光催化薄膜"", 《中国优秀硕士论文数据库 工程Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597719A (en) * | 2015-11-17 | 2016-05-25 | 山东大学 | Foamed titanium-titanium oxide composite photoelectrocatalytic material and application thereof |
| JP6963853B1 (en) * | 2021-01-15 | 2021-11-10 | 株式会社シケン | Manufacturing method of semiconductor titanium oxide |
| WO2022153650A1 (en) * | 2021-01-15 | 2022-07-21 | 株式会社シケン | Method for manufacturing titanium oxide semiconductor |
| EP4279178A4 (en) * | 2021-01-15 | 2024-08-07 | Shiken Co Ltd | Method for manufacturing titanium oxide semiconductor |
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Application publication date: 20140723 |