CN100391851C - Method for preparing three-dimensional nanometer structure titanium dioxide - Google Patents
Method for preparing three-dimensional nanometer structure titanium dioxide Download PDFInfo
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- CN100391851C CN100391851C CNB2006100494986A CN200610049498A CN100391851C CN 100391851 C CN100391851 C CN 100391851C CN B2006100494986 A CNB2006100494986 A CN B2006100494986A CN 200610049498 A CN200610049498 A CN 200610049498A CN 100391851 C CN100391851 C CN 100391851C
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- titanium dioxide
- titanium
- mass percent
- reaction solution
- deionized water
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 3
- 238000005554 pickling Methods 0.000 claims description 10
- 235000021110 pickles Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002057 nanoflower Substances 0.000 abstract 3
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 14
- 238000007669 thermal treatment Methods 0.000 description 13
- 239000006210 lotion Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- -1 WS 2 Chemical compound 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The present invention discloses a method for preparing titanium dioxide with three-dimensional nano-flower structure. The present invention comprises the following procedures that hydrofluoric acid, nitric acid and deionized water are mixed to prepare acid wash; the nitric acid and hexamethylenetetramine are added to hydrogen peroxide solution to prepare reaction solution; the surface of a metal tianium plate is pickled with the acid wash, dipped into the reaction solution, and reacts for more than 48 hours at a temperature of 60 to 80 DEG C; after reacting, the titanium plate is washed in the deionized water and dried, and the temperature of 300 to 500 DEGC is kept for at least 10 minutes. The titanium dioxide with the nano-flower structure prepared by metal titanium and the hydrogen peroxide solution directly reacting has the advantages of simple and feasible method, low cost, directional and regular shapes of the prepared nano-flower maintained after being processed by heat treatment, excellent crystallization, fine crystal grains, large specific surface area and high purity.
Description
Technical field
The present invention relates to a kind of method for preparing three-dimensional nanometer structure titanium dioxide.
Background technology
Titanium deoxid film or powder with nanostructure, because therefore its tiny grain-size, high specific surface area, unique properties such as nanometer size effect have a wide range of applications in high-tech areas such as photochemical catalysis, gas sensor, solar cell, biomaterial and nano-devices.At present developed the titanium dioxide of preparing multiple zero dimension and one dimension Nano structure, as monodisperse sphere shape nano particle, nano wire, nanofiber, nanotube, nanometer rod etc.3-D nano, structure " nanometer flower " is at C, GaP, ZnO and some sulfide such as WS
2, MoS
2, Bi
2S
3Etc. preparing in the system.These " nanometer flower " structured materials demonstrate some uniquenesses and excellent physical chemistry, as field emission performance etc.But although titanium dioxide has a wide range of applications, the titanium dioxide of " nanometer flower " structure does not also occur.
Summary of the invention
The purpose of this invention is to provide a kind of easy method for preparing three-dimensional nanometer structure titanium dioxide.
The method for preparing three-dimensional nanometer structure titanium dioxide of the present invention may further comprise the steps:
1) be that 50～55% hydrofluoric acid, mass percent concentration are that 65～68% nitric acid mixes with deionized water 1: 2 by volume～4: 5～7 with mass percent concentration, pickle solution;
2) in mass percent concentration is 20～30% hydrogen peroxide solution, add the nitric acid of 0.1～0.8 mol and the Hexamine of 0～0.02 mol, reaction solution;
3) with pickling metal titanium plate with above-mentioned pickle solution pickling after, clean up in ultrasonic wave with deionized water again, be immersed in then in the reaction solution, 60～80 ℃ of down reactions more than 48 hours;
4) reacted titanium sheet washed with de-ionized water is after the drying, 300～500 ℃ of insulations at least 10 minutes.
The present invention's " nanometer flower " structure titanium dioxide before thermal treatment is a non-crystal structure; Acquisition after heat treatment has anatase structured, or the titanium dioxide of anatase octahedrite and rutile mixing crystalline structure " nanometer flower ".The diameter of " nanometer flower " is 300～500 nanometers, and being grown by the titanium dioxide granule orientation " fusion " of diameter approximate number nanometer forms.
Simple, the easy row of method of the titanium dioxide of metal titanium that the present invention adopts and the preparation of aqueous hydrogen peroxide solution direct reaction " nanometer flower " structure, cost is low, and " the nanometer flower " of preparation after heat treatment keeps the rule oriented pattern, the well-crystallized, crystal grain is tiny, and specific surface area is big, the purity height.
Description of drawings
Fig. 1 is the low power field emission scanning electron microscope photo of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 1 preparation;
Fig. 2 is the high power field emission scanning electron microscope photo of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 1 preparation;
Fig. 3 is the high power field emission scanning electron microscope photo of embodiment 1 preparation " nanometer flower " structure titanium dioxide;
Fig. 4 is the x-ray diffraction pattern of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 1 preparation, among the figure, and A: anatase octahedrite, Ti: titanium;
Fig. 5 is the high power field emission scanning electron microscope photo of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 2 preparation;
Fig. 6 is the x-ray diffraction pattern of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 2 preparation, among the figure, and A: anatase octahedrite, R: rutile, Ti: titanium;
Fig. 7 is the high power field emission scanning electron microscope photo of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 3 preparation;
Fig. 8 is the high power field emission scanning electron microscope photo of titanium sheet of surface coverage " nanometer flower " structure titanium dioxide of embodiment 4 preparation.
Embodiment
Further set forth the inventive method below in conjunction with embodiment.But the method that the present invention adopts metal titanium and aqueous hydrogen peroxide solution direct reaction to prepare the titanium dioxide of nanometer flower structure not only is confined to following embodiment.
Embodiment 1
Step 1 preparating acid washing lotion
With mass percent concentration is that 55% hydrofluoric acid, mass percent concentration are 65% nitric acid and 1: 3: 6 by volume mixed of deionized water, pickle solution.
Step 2 pickling metal titanium plate is cleaned
Be of a size of 5 * 5 * 0.01 (cm
3) pickling metal titanium plate is with the pickling under 60 ℃ of temperature of above-mentioned mixing acid, then in ultrasonic wave, clean up with deionized water.
50ml concentration is to add nitric acid and the 100 milligrams of Hexamines (purity＞99.5% mass percent) that 1.0 ml concns are 63% (mass percent) in 30% (mass percent) hydrogen peroxide solution successively, gets reaction solution.
The metallic titanium plate that cleans up is immersed in the 50ml reaction solution, reacted 72 hours down at 80 ℃.
Step 5 thermal treatment
Reacted titanium sheet washes gently with deionized water, and drying is placed in the retort furnace 400 ℃ of insulations 1 hour.
Reaction result
Titanium plate surface evenly generates " nanometer flower " structure titanium dioxide as depicted in figs. 1 and 2, " nanometer flower " about 300 nanometers of diameter.The high power pattern of Fig. 3 shows that " nanometer flower " formed by titanium dioxide granule orientation " fusion " growth of diameter approximate number nanometer." nanometer flower " structure titanium dioxide is a non-crystal structure before the thermal treatment; Fig. 4 shows that the crystalline structure of " nanometer flower " is pure anatase structured after the thermal treatment.
Embodiment 2
Step 1 preparating acid washing lotion
With embodiment 1.
Step 2 pickling metal titanium plate is cleaned
With embodiment 1.
50ml concentration is to add nitric acid and the 100 milligrams of Hexamines (purity＞99.5% mass percent) that 4.0 ml concns are 63% (mass percent) in 30% (mass percent) hydrogen peroxide solution successively, gets reaction solution.
The metallic titanium plate that cleans up is immersed in the 50ml reaction solution, reacted 60 hours down at 60 ℃.
Step 5 thermal treatment
Reacted titanium sheet washes gently with deionized water, and drying is placed in the retort furnace 500 ℃ of insulations 0.5 hour.
Reaction result
Titanium plate surface evenly generates " nanometer flower " structure titanium dioxide as shown in Figure 5, " nanometer flower " about 500 nanometers of diameter." nanometer flower " structure titanium dioxide is a non-crystal structure before the thermal treatment; Fig. 6 shows that the crystalline structure of " nanometer flower " is pure anatase octahedrite and rutile mixing crystalline structure after the thermal treatment, and wherein rutile content is about 62% (mass percent).
Step 1 preparating acid washing lotion
With mass percent concentration is that 50% hydrofluoric acid, mass percent concentration are 68% nitric acid and 1: 4: 7 by volume mixed of deionized water, pickle solution.
Step 2 pickling metal titanium plate is cleaned
With embodiment 1.
50ml concentration is to add nitric acid and the 100 milligrams of Hexamines (purity＞99.5% mass percent) that 2.0 ml concns are 63% (mass percent) in 30% (mass percent) hydrogen peroxide solution successively, gets reaction solution.
With embodiment 1.
Step 5 thermal treatment
With embodiment 1.
Reaction result
Titanium plate surface evenly generates " nanometer flower " structure titanium dioxide as shown in Figure 7, " nanometer flower " about 500 nanometers of diameter." nanometer flower " structure titanium dioxide is a non-crystal structure before the thermal treatment; Crystalline structure is pure anatase structured after the thermal treatment.
Step 1 preparating acid washing lotion
With embodiment 1.
Step 2 pickling metal titanium plate is cleaned
With embodiment 1.
50ml concentration is that interpolation 1.0 ml concns are the nitric acid of 63% (mass percent) in 30% (mass percent) hydrogen peroxide solution, gets reaction solution.
With embodiment 1.
Step 5 thermal treatment
With embodiment 1.
Reaction result
Titanium plate surface generates " nanometer flower " structure titanium dioxide as shown in Figure 8." nanometer flower " structure titanium dioxide is a non-crystal structure before the thermal treatment; Crystalline structure is pure anatase structured after the thermal treatment.
Claims (1)
1. method for preparing three-dimensional nanometer structure titanium dioxide is characterized in that may further comprise the steps:
1) be that 50～55% hydrofluoric acid, mass percent concentration are that 65～68% nitric acid mixes with deionized water 1: 2 by volume～4: 5～7 with mass percent concentration, pickle solution;
2) in mass percent concentration is 20～30% hydrogen peroxide solution, add the nitric acid of 0.1～0.8 mol and the Hexamine of 0～0.02 mol, reaction solution;
3) with pickling metal titanium plate with above-mentioned pickle solution pickling after, clean up in ultrasonic wave with deionized water again, be immersed in then in the reaction solution, 60～80 ℃ of down reactions more than 48 hours;
4) reacted titanium sheet washed with de-ionized water is after the drying, 300～500 ℃ of insulations at least 10 minutes.
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| CN100391851C true CN100391851C (en) | 2008-06-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155086A (en) * | 2020-01-19 | 2020-05-15 | 浙江大学 | Method for growing titanium dioxide nanowire film on surface of stainless steel |
| CN111172535A (en) * | 2020-01-19 | 2020-05-19 | 浙江大学 | Method for growing titanium dioxide nanoflower film on surface of stainless steel in one step |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436644C (en) * | 2006-08-01 | 2008-11-26 | 浙江大学 | Process of preparing single-layer nanometer TiO2 rod film in pure rutile structure |
| CN101508463B (en) * | 2009-03-19 | 2010-11-10 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
| CN101717114B (en) * | 2009-12-02 | 2011-08-24 | 浙江大学 | Titanium dioxide with hollow polyhedral structure and preparation method thereof |
| CN102557130B (en) * | 2012-02-22 | 2013-12-25 | 浙江大学 | Method for preparing titanium dioxide nanoflower array film |
| CN104772149B (en) * | 2015-04-07 | 2017-01-18 | 大连理工大学 | Bi2O3/BiFeO3/TiO2 nano-flower photocatalytic material and preparation method thereof |
| CN105883912B (en) * | 2016-05-15 | 2017-09-29 | 北京工业大学 | A kind of self-supporting titanium dioxide three-dimensional micro-nano structure preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544336A (en) * | 2003-11-27 | 2004-11-10 | 茂名粤桥集团矿业有限公司 | Chemical processing method for promotion of titanium dioxide product quality |
| 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 | |
| JP2005298296A (en) * | 2004-04-14 | 2005-10-27 | Daicel Chem Ind Ltd | Titanium oxide crystal, photocatalyst and oxidation method of organic compound |
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| 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 | |
| CN1544336A (en) * | 2003-11-27 | 2004-11-10 | 茂名粤桥集团矿业有限公司 | Chemical processing method for promotion of titanium dioxide product quality |
| JP2005298296A (en) * | 2004-04-14 | 2005-10-27 | Daicel Chem Ind Ltd | Titanium oxide crystal, photocatalyst and oxidation method of organic compound |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155086A (en) * | 2020-01-19 | 2020-05-15 | 浙江大学 | Method for growing titanium dioxide nanowire film on surface of stainless steel |
| CN111172535A (en) * | 2020-01-19 | 2020-05-19 | 浙江大学 | Method for growing titanium dioxide nanoflower film on surface of stainless steel in one step |
| CN111172535B (en) * | 2020-01-19 | 2021-08-06 | 浙江大学 | Method for growing titanium dioxide nanoflower film on surface of stainless steel in one step |
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