CN100352970C - Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium - Google Patents
Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium Download PDFInfo
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- CN100352970C CN100352970C CNB2005100607513A CN200510060751A CN100352970C CN 100352970 C CN100352970 C CN 100352970C CN B2005100607513 A CNB2005100607513 A CN B2005100607513A CN 200510060751 A CN200510060751 A CN 200510060751A CN 100352970 C CN100352970 C CN 100352970C
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- acid
- metal titanium
- deionized water
- titanium
- titanium plate
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010936 titanium Substances 0.000 title claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002073 nanorod Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000005554 pickling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- BFSPAPKTIGPYOV-BQYQJAHWSA-N (e)-1-[4-(4-hydroxyphenyl)piperazin-1-yl]-3-thiophen-2-ylprop-2-en-1-one Chemical compound C1=CC(O)=CC=C1N1CCN(C(=O)\C=C\C=2SC=CC=2)CC1 BFSPAPKTIGPYOV-BQYQJAHWSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle 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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Abstract
The present invention relates to a method for preparing an array of titania nanometer sticks in directional arrangement on the surface of metal titanium. The present invention comprises the following steps that step 1, HF acid with the concentration of 50 to 60 wt% and HNO3 acid with the concentration of 60 to 68 wt% are mixed with deionized water according to a volume ratio of 1: 3: 6 to form mixed acid solution; step 2, the surface of a metal titanium plate is cleaned with the mixed acid at the temperature of 50 to 70 DEG C, and then cleaned with the deionized water in ultrasonic waves; step 3, the cleaned metal titanium plate is dipped into hydrogen peroxide solution with the concentration of 30 wt% to react for 24 to 72 hours at the temperature of 60 to 85 DEG C. The present invention has the advantages of simple and feasible method and low cost; the prepared nanometer stick array has directional and regular growth, excellent crystallization, fine crystal grains, great specific surface area, high purity and excellent combination of films and substrates.
Description
Technical field
The present invention relates to align the method for titanic oxide nanorod array at metal titanium surface preparation crystalline structure.
Background technology
Titanium deoxid film has a wide range of applications in high-tech areas such as photochemical catalysis, gas sensor, solar cell and biomaterials.By the nanostructure that rule oriented is arranged, as nano wire, nanotube, nanometer rod etc., the film of composition has particular performances: the nanometer size effect of tiny grain-size, high specific surface area and uniqueness etc.
At present, adopted various physics, chemistry and electrochemical techniques to prepare powders such as titanium dioxide nano thread, nanotube, nanometer rod.The film that aligns the titania nanotube composition also obtains by electrochemistry and high-temperature heat treatment crystallization process subsequently, and shows excellent air-sensitive performance.But aforesaid method mostly relates to complex apparatus or complicated process, introduces various organic and inorganic impurity easily.In addition, for the titanium dioxide that obtains crystalline structure, remove the grain growth that high-temperature heat treatment that organic impurities introduces can cause titanium dioxide inevitably, specific surface area reduces.
Summary of the invention
The purpose of this invention is to provide the short-cut method of arranging titanic oxide nanorod array under a kind of cold condition in metal titanium surface preparation crystalline structure rule oriented, and need not the common subsequent heat treatment crystallization process that is adopted.
Metal titanium surface preparation of the present invention aligns the method for titanic oxide nanorod array, and its step is as follows:
1) with mass percent concentration is 50～60% HF acid, 60～68% HNO
3Acid and deionized water get mixed acid solution with 1: 3: 6 mixed of volume ratio;
2) pickling metal titanium plate is cleaned under 50～70 ℃ of temperature with above-mentioned mixing acid, then clean up in ultrasonic wave with deionized water again;
3) metallic titanium plate that cleans up being immersed in mass percent concentration is in 30% the hydrogen peroxide solution, 60～85 ℃ of reactions 24～72 hours down.
Simple, the easy row of the inventive method, cost is low, the nanometer stick array rule oriented growth of preparation, the well-crystallized, crystal grain is tiny, and specific surface area is big, and the purity height is combined between film and the matrix.
Description of drawings
Fig. 1 aligns the low power field emission scanning electron microscope photo of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 1 preparation;
Fig. 2 aligns the high power field emission scanning electron microscope photo (top view) of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 1 preparation;
Fig. 3 aligns the field emission scanning electron microscope photo (sectional view) of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 1 preparation;
Fig. 4 aligns the middle layer high power field emission scanning electron microscope photo (sectional view) of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 1 preparation;
Fig. 5 is the transmission electron microscope photo of the titanium dioxide nano-rod of embodiment 1 preparation;
Fig. 6 aligns the x-ray diffraction pattern of film top layer of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 1 preparation;
Fig. 7 aligns the x-ray diffraction pattern of membrane middle layer of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 1 preparation;
Fig. 8 aligns the high power field emission scanning electron microscope photo (top view) of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 2 preparations;
Fig. 9 aligns the high power field emission scanning electron microscope photo (top view) of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 3 preparations;
Figure 10 aligns the high power field emission scanning electron microscope photo (top view) of the titanium sheet of titanium dioxide nano-rod for the surface coverage of embodiment 4 preparations.
Embodiment
Further set forth the present invention below in conjunction with embodiment.But the method that the present invention arranges titanic oxide nanorod array in metal titanium surface preparation crystalline structure rule oriented not only is confined to following embodiment.
Embodiment 1
1) be 55%HF acid, 65%HNO with mass percent concentration
3Acid and deionized water get mixed acid solution with 1: 3: 6 mixed of volume ratio;
2) will be of a size of 5 * 5 * 0.01 (cm
3) pickling metal titanium plate cleans under 60 ℃ of temperature with above-mentioned mixing acid, then clean up in ultrasonic wave with deionized water again;
3) metallic titanium plate that cleans up being immersed in the 50ml mass percent concentration is in 30% the hydrogen peroxide solution, 80 ℃ of reactions 72 hours down.
Fig. 1～Fig. 6 has shown that the metal titanium surface evenly generates the result who aligns titanic oxide nanorod array:
By Fig. 1 and Fig. 2 as seen, pickling metal titanium plate evenly generates and aligns titanic oxide nanorod array.
By Fig. 3 and Fig. 4 as seen, pickling metal titanium plate is for aligning titanium dioxide nano-rod, about 1 micron of thickness; Be the compact titanium dioxide nano-particle layer between nanometer rod layer and the titanium plate, about 2 microns of thickness.Fig. 5 shows about 20～30 nanometers of the diameter of nanometer rod monomer size, about 150 nanometers of length.
As seen from Figure 6, A among the figure: anatase octahedrite; R: rutile phase; Ti: titanium, aligning titanic oxide nanorod array is that crystalline structure is the titanium dioxide of anatase octahedrite and rutile mixing crystal formation, and wherein rutile is selected outstanding growth mutually, and mass percentage content is about 30%.Fig. 7 shows that the middle layer crystalline structure is the titanium dioxide of anatase octahedrite, A among the figure: anatase octahedrite; Ti: titanium.
Embodiment 2
1) be 50%HF acid, 60%HNO with mass percent concentration
3Acid and deionized water get mixed acid solution with 1: 3: 6 mixed of volume ratio;
2) will be of a size of 2.5 * 2.5 * 0.01 (cm
3) pickling metal titanium plate cleans under 50 ℃ of temperature with above-mentioned mixing acid, then clean up in ultrasonic wave with deionized water again;
3) metallic titanium plate that cleans up being immersed in the 50ml mass percent concentration is in 30% the hydrogen peroxide solution, 60 ℃ of reactions 48 hours down.
The result as shown in Figure 8, pickling metal titanium plate evenly generates and aligns titanium dioxide nano-rod.
Embodiment 3
1) be 60%HF acid, 68%HNO with mass percent concentration
3Acid and deionized water get mixed acid solution with 1: 3: 6 mixed of volume ratio;
2) will be of a size of 2.5 * 2.5 * 0.01 (cm
3) pickling metal titanium plate cleans under 70 ℃ of temperature with above-mentioned mixing acid, then clean up in ultrasonic wave with deionized water again;
3) metallic titanium plate that cleans up being immersed in the 20ml mass percent concentration is in 30% the hydrogen peroxide solution, 85 ℃ of reactions 24 hours down.
The result as shown in Figure 9, pickling metal titanium plate evenly generates and aligns titanium dioxide nano-rod.
Embodiment 4
Step 1) is with embodiment 1.
Step 2) with embodiment 2.
It is in 30% (mass percent) hydrogen peroxide solution that step 3) is immersed in 10ml concentration with the metallic titanium plate that cleans up, and reacts 72 hours down at 80 ℃.
The result as shown in figure 10, pickling metal titanium plate evenly generates and aligns titanium dioxide nano-rod.
Claims (1)
1. the metal titanium surface preparation aligns the method for titanic oxide nanorod array, it is characterized in that may further comprise the steps:
1) with mass percent concentration is 50～60% HF acid, 60～68% HNO
3Acid and deionized water get mixed acid solution with 1: 3: 6 mixed of volume ratio;
2) pickling metal titanium plate is cleaned under 50～70 ℃ of temperature with above-mentioned mixing acid, then clean up in ultrasonic wave with deionized water again;
3) metallic titanium plate that cleans up being immersed in mass percent concentration is in 30% the hydrogen peroxide solution, 60～85 ℃ of reactions 24～72 hours down.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100607513A CN100352970C (en) | 2005-09-13 | 2005-09-13 | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium |
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| CNB2005100607513A CN100352970C (en) | 2005-09-13 | 2005-09-13 | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium |
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| CN100352970C true CN100352970C (en) | 2007-12-05 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396651B (en) * | 2008-10-17 | 2010-04-21 | 浙江大学 | Nano phototranslating composite film in order structure and preparation method thereof |
| CN101508463B (en) * | 2009-03-19 | 2010-11-10 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
| CN101618891B (en) * | 2009-07-02 | 2011-01-05 | 浙江大学 | Preparation method of self-assembled superlattice materials of titanium dioxide nano rod |
| CN101935015A (en) * | 2010-06-29 | 2011-01-05 | 东华大学 | Method for preparing titanium dioxide nanorod array electrode with mixed crystal structure |
| CN101949054B (en) * | 2010-08-17 | 2012-12-12 | 浙江大学 | Method for preparing single-crystal anatase titanium dioxide film |
| CN102153140A (en) * | 2011-04-15 | 2011-08-17 | 河南大学 | Hydrothermal synthesis method of TiO2 nanorod array |
| CN102249299A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing TiO2 overlong micro rod in NaCl molten salt system |
| CN102895963A (en) * | 2012-09-14 | 2013-01-30 | 浙江大学 | Method of loading titanium dioxide nanorod arrays on surface of titanium wire mesh |
| CN103936066A (en) * | 2014-05-05 | 2014-07-23 | 浙江大学 | Method for preparing rutile titanium dioxide nanometer flower array thin film |
| CN105186007B (en) * | 2015-06-26 | 2018-06-01 | 浙江大学 | The Ti/TiO of nanostructured2Combination electrode and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1544684A (en) * | 2003-11-24 | 2004-11-10 | 甘 宪 | Process for preparing titanium dioxide film on metal Ti surface and Ti plate with titanium dioxide film coated surface prepared thereby |
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| CN1544684A (en) * | 2003-11-24 | 2004-11-10 | 甘 宪 | Process for preparing titanium dioxide film on metal Ti surface and Ti plate with titanium dioxide film coated surface prepared thereby |
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Granted publication date: 20071205 Termination date: 20120913 |