CN104790012A - Preparation method for self-supported TiO2 nanotube array thin films - Google Patents
Preparation method for self-supported TiO2 nanotube array thin films Download PDFInfo
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- CN104790012A CN104790012A CN201510121736.9A CN201510121736A CN104790012A CN 104790012 A CN104790012 A CN 104790012A CN 201510121736 A CN201510121736 A CN 201510121736A CN 104790012 A CN104790012 A CN 104790012A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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Abstract
The invention relates to a preparation method for ultrathin self-supported TiO2 nanotube array thin films. The preparation method includes the following steps: treatment of a metal titanium sheet; preparation of an electrolyte solution; preparation of the self-supported TiO2 nanotube thin films through a secondary anodic oxidation method; and membrane separation comprising the steps of selecting an organic solvent having relatively small surface tension and water molecules having relatively large surface tension to separate nanatubes with a metal Ti substrate, so as to realize film transfer. The mold preparation process is simple, and operations are simple; the thin film structure is arranged regularly, the thickness is uniform, the framework is stable, the pore size is uniform, and the ordered area is relatively large. By controlling the oxidation time, the TiO2 nanotube thin films with different thicknesses can be prepared, and the thinnest thickness can be up to about 600 nm.
Description
Technical field
The present invention relates to technical field of film preparation, particularly relate to the TiO of a kind of thickness from 600nm to 1460nm
2nano-tube array self-supported membrane preparation method.
Background technology
Anodic oxidation TiO
2film adopts two electrodes system, anode graphite or platinum, and negative electrode titanium sheet, prepares nano-pipe array thin film by electrochemical method, ion inserter instrument can be widely used in, photochemical catalysis, dye sensitization solar battery, uhligite battery, sensor field, and the performance demonstrating its excellence.The shortcoming of the method is the TiO prepared
2nano-tube array sticks to metallic titanium surface, peels off very difficult, limits extensively quoting of it.
Although about self-supporting TiO
2report prepared by nano-pipe array thin film has a lot (Small, 2008,4,1063; Chemistry of Materials, 2010,22,66556; Chemical Communications, 2012,48,8748:; Electrochemistry Communications, 2010,12,1062. patent No.s: CN 101857966A), these methods prepare self-supporting TiO
2the method of nano-pipe array thin film can be divided into two classes: 1. etching method, is subdivided into etching metal titanium and etching TiO
2two kinds of methods, wherein etch TiO
2method can prepare the TiO of through hole respectively by controlling etching time
2the TiO that film of Nano tube array and one end are closed
2film of Nano tube array; 2. two-step electrochemical anodizing method, namely orderly nanotube permutation film is prepared in first time anodic oxidation, after changing experiment parameter, then carries out the oxidation that second time takes off film, finally prepares TiO
2nano-pipe array thin film.But preparing the thinnest nano-pipe array thin film method is at present by etching the method for titanium metal, prepare most about 1 microns of film.But the first kind prepares etching solution used in the method for film has very large pollution to environment, it is thicker that Equations of The Second Kind method prepares film, and about two microns, are generally used for dye sensitization solar battery or photochemical catalysis.Develop the simple self-supporting TiO of a kind of technique for this reason
2nano-pipe array thin film method is very important, and such as, uhligite battery and smart window need the TiO that light transmission is good
2film, the thickness that our method can be peeled off, will for opening up TiO further from 600nm to 1460nm
2application provides opportunity.
Summary of the invention
In view of above-mentioned analysis, the present invention aims to provide a kind of method preparing ultra-thin self-supporting nano-tube film, solves the ultra-thin TiO of existing stripping
2nano-pipe array thin film technical barrier.
Object of the present invention is mainly achieved through the following technical solutions:
A kind of self-supporting TiO
2the preparation method of nano-pipe array thin film, comprises the steps:
Step one, process metal titanium sheet;
Step 2, preparation electrolyte solution;
Step 3, two-step electrochemical anodizing method prepare self-supporting TiO
2nano-tube film:
(1) under room temperature condition, metal titanium sheet after step one processes is put into the electrolyte solution prepared through step 2 and carry out first time anodic oxidation, wherein with graphite or Pt as to electrode, logical 60V voltage, after oxidization time 2-24h, use ethanol purge titanium sheet, then supersound process 15-60min, the unformed TiO that oxidation is obtained
2nano-tube film Automatic-falling, thus the titanium sheet obtaining first time anodic oxidation, there is bowl-shape oldered array structure in titanium plate surface;
(2) with the titanium sheet of first time anodic oxidation for template carries out second time anodic oxidation: oxidization time is for 3-10min at ambient temperature, and oxidising process for template, increases the degree of depth of bowl with bowl-shape metal titanium gradually, near and formed nanotube-shaped;
(3) membrane sepn: after second time anodic oxidation terminates, rinse and fully dry, finally soak 0.5-2h inside water with methyl alcohol, ethanol, acetone or Virahol, nano-tube film can be separated with metal titanium sheet automatically, obtains the self-supporting TiO that bonding force is little
2the complex body of nano-tube film---metal titanium sheet;
(4) film transfer: by nano-tube film---metal titanium sheet complex body takes out from water, put into the organic solvent that surface tension is little, leave standstill 10-30min, be reentered into after original water molecules spreads out completely in the aqueous solution, nano-tube film can be separated with metal titanium sheet completely, and transfer to hard substrate or PET base, obtain the self-supporting TiO that structure is intact
2nano-tube film.
Especially, the thickness of described metal titanium sheet is 0.2-0.3mm, is of a size of 1*1cm, 1*4cm, 2*4cm.
Especially, process the method for metal titanium sheet in described step one for metal titanium sheet is put into acetone, each ultrasonic more than the 15min of first alcohol and water respectively, dry up with nitrogen after at every turn ultrasonic.
Especially, in described step 2, electrolyte solution is that in ethylene glycol solution, add volume ratio be 1%-5% deionized water and massfraction is the NH of 0.2-1%
4f.
Especially, in described step 2, electrolyte solution is in ethylene glycol solution, add that volume ratio is 1%-5% deionized water, massfraction is the NH of 0.2-1%
4f and volume ratio 0.1-0.5%H
3pO
4.
Especially, the organic solvent that in described step 3, surface tension is little is methyl alcohol, ethanol, acetone or Virahol.
Invention beneficial effect is as follows:
1, mould making process of the present invention is simple, simple to operate;
2, membrane structure queueing discipline of the present invention, thickness is homogeneous, and skeleton is stablized, and aperture is homogeneous, and orderly area is larger.
3, by the controlled oxidization time, the TiO of different thickness can be prepared
2nano-tube film, the thinlyyest reaches about 600nm.
4, by the water molecules that the organic solvent that option table surface tension is smaller is large with surface tension, nanotube is separated with metal Ti substrate, and realizes film transfer.
Other features and advantages of the present invention will be set forth in the following description, and, becoming apparent from specification sheets of part, or understand by implementing the present invention.Object of the present invention and other advantages realize by structure specifically noted in write specification sheets, claims and accompanying drawing and obtain.
Accompanying drawing explanation
Accompanying drawing only for illustrating the object of specific embodiment, and does not think limitation of the present invention, and in whole accompanying drawing, identical reference symbol represents identical parts.
Fig. 1 is self-supporting TiO
2nano-pipe array thin film front SEM schemes
Fig. 2 is self-supporting TiO
2ti metal SEM after nano-pipe array thin film glassy membrane schemes
Fig. 3 is 605nm self-supporting TiO
2nano-pipe array thin film SEM schemes
Fig. 4 is 1290nm self-supporting TiO
2nano-pipe array thin film SEM schemes
Fig. 5 is 1460nm self-supporting TiO
2nano-pipe array thin film SEM schemes
Fig. 6 is self-supporting TiO
2nano-pipe array thin film preparation flow figure
Embodiment
Specifically describe the preferred embodiments of the present invention below in conjunction with accompanying drawing, wherein, accompanying drawing forms the application's part, and is used from enforcement example one of the present invention and explains principle of the present invention.
Embodiment one:
The process of step one, Industrial Metal titanium sheet: industrial titanium sheet better crystallinity degree, the quality preparing nanotube films is high, be 0.2mm by thickness, area is Industrial Metal titanium sheet each ultrasonic more than 15min in acetone, first alcohol and water respectively of 1*1cm size, dries up after at every turn ultrasonic with gas;
Step 2, electrolytical preparation: in ethylene glycol solution, add volume ratio be 1%-5% deionized water and massfraction is the NH of 0.2-1%
4f.
Step 3, two-step electrochemical anodizing method prepare self-supporting nano-tube film:
(1) carry out anodic oxidation with the voltage of 60V under room temperature condition, wherein with graphite or Pt as to electrode, logical 60V voltage, after oxidization time 2h, uses ethanol purge titanium sheet, then supersound process 15min, the unformed TiO that oxidation is obtained
2nano-tube film Automatic-falling.Now, the structure of metallic titanium surface is bowl-shape oldered array structure, presents brilliant white;
(2) second time oxidation is for template with the titanium sheet be oxidized for the first time, because the brilliant white titanium sheet microtexture obtained after the first oxidation is orderly ball chamber array structure, second time oxidising process can by orderly microstructure for continuing oxidation based on template, under room temperature condition, oxidization time is 3min, if oxidization time is lower than 3min, membrane sepn can be more difficult; If the time exceeds 10min, the nanotube on film surface is easily corroded, and nanotube ordered structure can be destroyed.TiO
2nanotube can with the growth rate of the about 200nm of per minute;
(3) membrane sepn: after anodic oxidation terminates, rinses with methyl alcohol, ethanol, acetone or Virahol and dries, finally inside water, soaking 0.5h, and nano-tube film can be separated with metal Ti sheet automatically, obtains the self-supporting TiO that bonding force is little
2the complex body of nano-tube film-metal Ti.
(4) film transfer: careful takes out the nano-tube film separated-metal Ti sheet complex body from water, put into the smaller organic solvent of surface tension, such as, in methyl alcohol, ethanol, acetone or Virahol, leave standstill 10min, be reentered into after original water molecules spreads out completely in the aqueous solution, nano-tube film is separated completely with metal titanium, and transfers to hard substrate or PET base, obtains the self-supporting nano-tube film that structure is intact.
Thus obtain 605nm self-supporting TiO
2nano-pipe array thin film.As shown in Figure 3.
Embodiment two:
The process of step one, Industrial Metal titanium sheet: industrial titanium sheet better crystallinity degree, the quality preparing nanotube films is high, be 0.3mm by thickness, area is Industrial Metal titanium sheet each ultrasonic more than 15min in acetone, first alcohol and water respectively of 2*4cm size, dries up after at every turn ultrasonic with gas;
Step 2, electrolytical preparation: in ethylene glycol solution, add that volume ratio is 1%-5% deionized water, massfraction is the NH of 0.2-1%
4f and volume ratio 0.1-0.5%H
3pO
4, add H
3pO
4the netted TiO of nanotube surface can be removed
2, make nanotube permutation more in order regular.
Step 3, two-step electrochemical anodizing method prepare self-supporting nano-tube film:
(1) carry out anodic oxidation with the voltage of 60V under room temperature condition, wherein with graphite or Pt as to electrode, logical 60V voltage, after oxidization time 24h, uses ethanol purge titanium sheet, then supersound process 60min, the unformed TiO that oxidation is obtained
2nano-tube film Automatic-falling.Now, the structure of metallic titanium surface is bowl-shape oldered array structure, presents brilliant white;
(2) second time oxidation is for template with the titanium sheet be oxidized for the first time, because the brilliant white titanium sheet microtexture obtained after the first oxidation is orderly ball chamber array structure, second time oxidising process can by orderly microstructure for continuing oxidation based on template, under room temperature condition, oxidization time is 6min, if oxidization time is lower than 3min, membrane sepn can be more difficult; If the time exceeds 10min, the nanotube on film surface is easily corroded, and nanotube ordered structure can be destroyed.TiO
2nanotube can with the growth rate of the about 200nm of per minute;
(3) membrane sepn: after anodic oxidation terminates, rinses with ethanol, acetone or Virahol and dries, finally inside water, soaking 2h, and nano-tube film can be separated with metal Ti sheet automatically, obtains the self-supporting TiO that bonding force is little
2the complex body of nano-tube film and metal Ti.
(4) film transfer: careful takes out the nano-tube film separated-metal Ti sheet complex body from water, put into the smaller organic solvent of surface tension, such as, in methyl alcohol, ethanol, acetone or Virahol, leave standstill 30min, be reentered into after original water molecules spreads out completely in the aqueous solution, nano-tube film can be separated completely with metal titanium, and transfers to hard substrate or PET base, obtains the self-supporting nano-tube film that structure is intact.
Thus obtain 1290nm self-supporting TiO
2nano-pipe array thin film.As shown in Figure 4.
Embodiment three:
Present embodiment and embodiment one are not both in step 2 and adopt oxidization time 7min, and other are identical with specific implementation method one.Thus obtain 1460nm self-supporting TiO
2nano-pipe array thin film.As shown in Figure 5.
Embodiment four:
Present embodiment and embodiment one are not both in step 2 and adopt oxidization time 10min, and other are identical with specific implementation method one.
In sum, embodiments provide a kind of preparation method of ultra-thin titanium dioxide nano-pipe array thin film, the method preparation technology is simple, and easy handling, cost is low.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (6)
1. a self-supporting TiO
2the preparation method of nano-pipe array thin film, is characterized in that comprising the steps:
Step one, process metal titanium sheet;
Step 2, preparation electrolyte solution;
Step 3, two-step electrochemical anodizing method prepare self-supporting TiO
2nano-tube film:
(1) under room temperature condition, metal titanium sheet after step one processes is put into the electrolyte solution prepared through step 2 and carry out first time anodic oxidation, wherein with graphite or Pt as to electrode, logical 60V voltage, after oxidization time 2-24h, use ethanol purge titanium sheet, then supersound process 15-60min, the unformed TiO that oxidation is obtained
2nano-tube film Automatic-falling, thus the titanium sheet obtaining first time anodic oxidation;
(2) with the titanium sheet of first time anodic oxidation for template carries out second time anodic oxidation: oxidization time is for 3-10min at ambient temperature;
(3) membrane sepn: after second time anodic oxidation terminates, rinse and dry, finally soak 0.5-2h inside water with ethanol, acetone or Virahol, nano-tube film can be separated with metal titanium sheet automatically, obtains the self-supporting TiO that bonding force is little
2the complex body of nano-tube film and metal titanium sheet;
(4) film transfer: nano-tube film and metal titanium sheet complex body are taken out from water, put into the organic solvent that surface tension is little, leave standstill 10-30min, be reentered into after original water molecules spreads out completely in the aqueous solution, nano-tube film can be separated completely with metal titanium sheet, and transfer to hard substrate or PET base, obtain the self-supporting TiO that structure is intact
2nano-tube film.
2. a kind of self-supporting TiO according to claim 1
2the preparation method of nano-pipe array thin film, is characterized in that: the thickness of described metal titanium sheet is 0.2-0.3mm, is of a size of 1*1cm, 1*4cm, 2*4cm.
3. a kind of self-supporting TiO according to claim 1
2the preparation method of nano-pipe array thin film, is characterized in that: process the method for metal titanium sheet in described step one for metal titanium sheet is put into acetone, each ultrasonic more than the 15min of first alcohol and water respectively, dries up after at every turn ultrasonic with nitrogen.
4. a kind of self-supporting TiO according to claim 1
2the preparation method of nano-pipe array thin film, is characterized in that: in described step 2, electrolyte solution is that in ethylene glycol solution, add volume ratio be 1%-5% deionized water and massfraction is the NH of 0.2-1%
4f.
5. a kind of self-supporting TiO according to claim 1
2the preparation method of nano-pipe array thin film, is characterized in that: in described step 2, electrolyte solution is in ethylene glycol solution, add that volume ratio is 1%-5% deionized water, massfraction is the NH of 0.2-1%
4f and volume ratio are 0.1-0.5%H
3pO
4.
6. a kind of self-supporting TiO according to claim 1
2the preparation method of nano-pipe array thin film, is characterized in that: the organic solvent that in described step 3, surface tension is little is methyl alcohol, ethanol, acetone or Virahol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036566A (en) * | 2015-07-30 | 2015-11-11 | 哈尔滨工业大学 | Preparation method of electrochromic film of anodic oxidation TiO2 nanotube array |
| CN105957965A (en) * | 2016-05-12 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Efficient and stable perovskite solar cell without hole transporting layer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857966A (en) * | 2009-03-19 | 2010-10-13 | 北京大学 | Self-standing TiO2 nanotube array membrane and preparation method thereof |
| CN102433579A (en) * | 2011-11-30 | 2012-05-02 | 中国科学院上海硅酸盐研究所 | Method for preparing independent and ordered titanium oxide nano tube array film |
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2015
- 2015-03-19 CN CN201510121736.9A patent/CN104790012B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857966A (en) * | 2009-03-19 | 2010-10-13 | 北京大学 | Self-standing TiO2 nanotube array membrane and preparation method thereof |
| CN102433579A (en) * | 2011-11-30 | 2012-05-02 | 中国科学院上海硅酸盐研究所 | Method for preparing independent and ordered titanium oxide nano tube array film |
Non-Patent Citations (2)
| Title |
|---|
| J. H. YUAN ET AL: "A Simple Method for Preparation of Through-Hole Porous Anodic Alumina Membrane", 《CHEMISTRY OF MATERIALS》 * |
| JUN WANG ET AL: "Freestanding TiO2 Nanotube Arrays with Ultrahigh Aspect Ratio via Electrochemical Anodization", 《CHEMISTY OF MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036566A (en) * | 2015-07-30 | 2015-11-11 | 哈尔滨工业大学 | Preparation method of electrochromic film of anodic oxidation TiO2 nanotube array |
| CN105957965A (en) * | 2016-05-12 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Efficient and stable perovskite solar cell without hole transporting layer and preparation method thereof |
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