CN104790012B - A kind of self-supporting TiO2The preparation method of nano-pipe array thin film - Google Patents
A kind of self-supporting TiO2The preparation method of nano-pipe array thin film Download PDFInfo
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- CN104790012B CN104790012B CN201510121736.9A CN201510121736A CN104790012B CN 104790012 B CN104790012 B CN 104790012B CN 201510121736 A CN201510121736 A CN 201510121736A CN 104790012 B CN104790012 B CN 104790012B
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The present invention relates to a kind of ultra-thin self-supporting TiO2The preparation method of nano-pipe array thin film.Comprise the steps：Process metal titanium sheet；Prepare electrolyte solution；Two-step electrochemical anodizing method prepares self-supporting TiO2Nano-tube film；UF membrane：Nanotube is separated with metal Ti substrates by the smaller organic solvent of selection surface tension and surface tension big hydrone, and realize film transfer.Mould making process of the present invention is simple, simple to operate；Membrane structure queueing discipline, thickness are homogeneous, and skeleton is stable, and aperture is homogeneous, and orderly area is larger.By controlling oxidization time, the TiO of different-thickness can be prepared2Nano-tube film is most thin up to 600nm or so.
Description
Technical field
The present invention relates to technical field of film preparation, more particularly to a kind of TiO of thickness from 600nm to 1460nm2Nanometer
Pipe array self-supported membrane preparation method.
Background technology
Anodic oxidation TiO2Film is using bipolar electrode system, negative electrode graphite or platinum, anode titanium sheet, by electrochemistry
Method prepares nano-pipe array thin film, can be widely applied to ion inserter instrument, photocatalysis, DSSC,
The fields such as perovskite battery, sensor, and show its excellent performance.The shortcoming of the method is the TiO for preparing2Nanotube
Array sticks to metallic titanium surface, and stripping is highly difficult, limits its extensive reference.
Although with regard to self-supporting TiO2Nano-pipe array thin film prepare report have 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 method systems
Standby self-supporting TiO2The method of nano-pipe array thin film can be divided into two classes：1. etching method, is subdivided into etching Titanium and etching TiO2
Two methods, wherein etching TiO2Method can prepare the TiO of through hole respectively by controlling etch period2Film of Nano tube array and one
The TiO that end seal is closed2Film of Nano tube array；2. to prepare orderly nanotube whole for two-step electrochemical anodizing method, i.e. first time anodic oxidation
Row film, after changing experiment parameter, then is taken off the oxidation of film for the second time, is finally prepared TiO2Nano-pipe array thin film.But
It is the method by etching titanium to prepare most thin nano-pipe array thin film method at present, prepares most film about 1 micro-
Rice or so.But, during the first kind prepares the method for film, etching solution used has very big pollution, Equations of The Second Kind method to environment
Prepare film thicker, about two microns are generally used for DSSC or photocatalysis.Develop for this kind of
Self-supporting TiO of process is simple2Nano-pipe array thin film method is particularly significant, and for example, perovskite battery and smart window need thoroughly
The good TiO of photosensitiveness2Film, the thickness that our method can be peeled off, will be further to open up TiO from 600nm to 1460nm2Should
With offer opportunity.
The content of the invention
In view of above-mentioned analysis, the present invention is intended to provide a kind of method for preparing ultra-thin self-supporting nano-tube film, solves
It is existing to peel off ultra-thin TiO2Nano-pipe array thin film technical barrier.
The purpose of the present invention is mainly achieved through the following technical solutions：
A kind of self-supporting TiO2The 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 TiO2Nano-tube film：
(1), under room temperature condition, the metal titanium sheet after step one is processed is put into the electrolysis prepared through step 2
First time anodic oxidation is carried out in matter solution, wherein with graphite or Pt as to electrode, leading to 60V voltages, oxidization time 2-24h it
Afterwards, ethanol purge titanium sheet is used, then ultrasonically treated 15-60min, makes the unformed TiO that oxidation is obtained2Nano-tube film takes off automatically
Fall, so as to obtain the titanium sheet of first time anodic oxidation, bowl-shape oldered array structure occurs in titanium plate surface；
(2) second anodic oxidation is carried out by template of the titanium sheet of first time anodic oxidation：Aoxidize at ambient temperature
Time is 3-10min, and with bowl-shape Titanium as template, gradually the depth of increase bowl, closely forms nanotube-shaped oxidizing process；
(3) UF membrane：After second anodic oxidation terminates, rinsed and fully dried in the air with methyl alcohol, ethanol, acetone or isopropanol
It is dry, 0.5-2h is finally soaked inside water, nano-tube film can be separated with metal titanium sheet automatically, obtain the little self-supporting of adhesion
TiO2The complex of nano-tube film --- metal titanium sheet；
(4) film transfer：By nano-tube film --- metal titanium sheet complex is taken out from water, is put into that surface tension is little to be had
In machine solvent, 10-30min is stood, is reentered in the aqueous solution after original hydrone is spread out completely, nano-tube film
Can separate with metal titanium sheet completely, and be transferred to hard substrate or PET base, obtain intact self-supporting TiO of structure2Nanotube
Film.
Especially, the thickness of the metal titanium sheet is 0.2-0.3mm, and size is 1*1cm, 1*4cm, 2*4cm.
Especially, in the step one process metal titanium sheet method be by metal titanium sheet be respectively put into acetone, methyl alcohol and
Each ultrasonic more than 15min in water, each ultrasound are dried up with nitrogen after finishing.
Especially, in the step 2 electrolyte solution be in ethylene glycol solution add volume ratio for 1%-5% go from
Sub- water and the NH that mass fraction is 0.2-1%4F。
Especially, in the step 2 electrolyte solution be in ethylene glycol solution add volume ratio for 1%-5% go from
The NH of sub- water, mass fraction for 0.2-1%4F and volume ratio 0.1-0.5%H3PO4。
Especially, in the step 3, the little organic solvent of surface tension is methyl alcohol, ethanol, acetone or isopropanol.
Invention has the beneficial effect that：
1st, mould making process of the present invention is simple, simple to operate；
2nd, membrane structure queueing discipline of the invention, thickness are homogeneous, and skeleton is stable, and aperture is homogeneous, and orderly area is larger.
3rd, by controlling oxidization time, the TiO of different-thickness can be prepared2Nano-tube film, it is most thin left up to 600nm
It is right.
4th, by the hydrone that selects the smaller organic solvent of surface tension and surface tension big by nanotube and metal
Ti substrates are separated, and realize film transfer.
Other features and advantages of the present invention will be illustrated in the following description, also, the partial change from specification
Obtain it is clear that or being understood by implementing the present invention.The purpose of the present invention and other advantages can be by the explanations write
In book, claims and accompanying drawing, specifically noted structure is realizing and obtain.
Description of the drawings
Accompanying drawing is only used for the purpose for illustrating specific embodiment, and is not considered as limitation of the present invention, in whole accompanying drawing
In, identical reference symbol represents identical part.
Fig. 1 is self-supporting TiO2Nano-pipe array thin film front SEM schemes
Fig. 2 is self-supporting TiO2Ti metals SEM figures after nano-pipe array thin film glass-film
Fig. 3 is 605nm self-supportings TiO2Nano-pipe array thin film SEM schemes
Fig. 4 is 1290nm self-supportings TiO2Nano-pipe array thin film SEM schemes
Fig. 5 is 1460nm self-supportings TiO2Nano-pipe array thin film SEM schemes
Fig. 6 is self-supporting TiO2Nano-pipe array thin film preparation flow figure
Specific embodiment
Below in conjunction with the accompanying drawings specifically describing the preferred embodiments of the present invention, wherein, accompanying drawing constitutes the application part, and
It is used for explaining the principle of the present invention together with the enforcement example of the present invention.
Specific embodiment one：
The process of step one, Industrial Metal titanium sheet：Industrial titanium sheet better crystallinity degree, the quality for preparing nanotube films are high, will
Thickness is 0.2mm, area for 1*1cm sizes Industrial Metal titanium sheet respectively in acetone, first alcohol and water each ultrasonic 15min with
On, each ultrasound is dried up with gas after finishing；
The preparation of step 2, electrolyte：In ethylene glycol solution, add volume ratio to be 1%-5% deionized waters and quality point
NH of the number for 0.2-1%4F。
Step 3, two-step electrochemical anodizing method prepare self-supporting nano-tube film：
(1) anodic oxidation is carried out with the voltage of 60V under room temperature condition, wherein leading to 60V electric as to electrode with graphite or Pt
Pressure, after oxidization time 2h, uses ethanol purge titanium sheet, then ultrasonically treated 15min, makes the unformed TiO that oxidation is obtained2Nanometer
Pipe film Automatic-falling.Now, the structure of metallic titanium surface is bowl-shape oldered array structure, and brilliant white is presented；
(2) second oxidation is with the titanium sheet for aoxidizing for the first time as template, because the brilliant white obtained after the first oxidation
The spherical cavity array structure that titanium sheet microstructure is ordered into, second oxidizing process can with orderly micro-structural as template based on after
Continuous oxidation, under room temperature condition, oxidization time is 3min, if oxidization time is less than 3min, UF membrane can be more difficult；If when
Between exceed 10min, the nanotube on film surface is easily corroded, and nanotube ordered structure can be destroyed.TiO2Nanotube can with per point
The growth rate of clock about 200nm；
(3) UF membrane：After anodic oxidation terminates, rinsed and dried with methyl alcohol, ethanol, acetone or isopropanol, finally in water
The inside immersion 0.5h, nano-tube film can be separated with metal Ti pieces automatically, obtain little self-supporting TiO of adhesion2Nanotube is thin
Film --- the complex of metal Ti.
(4) film transfer：It is careful the nano-tube film separated --- metal Ti piece complexs are taken out from water,
It is put in the smaller organic solvent of surface tension, such as, in methyl alcohol, ethanol, acetone or isopropanol, stands 10min, treat original
Hydrone is reentered into after spreading out completely in the aqueous solution, and nano-tube film is kept completely separate with Titanium, and is transferred to hard
Substrate or PET base, obtain the intact self-supporting nano-tube film of structure.
So as to obtain 605nm self-supportings TiO2Nano-pipe array thin film.As shown in Figure 3.
Specific embodiment two：
The process of step one, Industrial Metal titanium sheet：Industrial titanium sheet better crystallinity degree, the quality for preparing nanotube films are high, will
Thickness is 0.3mm, area for 2*4cm sizes Industrial Metal titanium sheet respectively in acetone, first alcohol and water each ultrasonic 15min with
On, each ultrasound is dried up with gas after finishing；
The preparation of step 2, electrolyte：In ethylene glycol solution, add volume ratio to be 1%-5% deionized waters, quality point
NH of the number for 0.2-1%4F and volume ratio 0.1-0.5%H3PO4, add H3PO4The netted TiO of nanotube surface can be removed2,
Make nanotube permutation more regular in order.
Step 3, two-step electrochemical anodizing method prepare self-supporting nano-tube film：
(1) anodic oxidation is carried out with the voltage of 60V under room temperature condition, wherein leading to 60V electric as to electrode with graphite or Pt
Pressure, after oxidization time 24h, uses ethanol purge titanium sheet, then ultrasonically treated 60min, makes the unformed TiO that oxidation is obtained2Receive
Mitron film Automatic-falling.Now, the structure of metallic titanium surface is bowl-shape oldered array structure, and brilliant white is presented；
(2) second oxidation is with the titanium sheet for aoxidizing for the first time as template, because the brilliant white obtained after the first oxidation
The spherical cavity array structure that titanium sheet microstructure is ordered into, second oxidizing process can with orderly micro-structural as template based on after
Continuous oxidation, under room temperature condition, oxidization time is 6min, if oxidization time is less than 3min, UF membrane can be more difficult；If when
Between exceed 10min, the nanotube on film surface is easily corroded, and nanotube ordered structure can be destroyed.TiO2Nanotube can with per point
The growth rate of clock about 200nm；
(3) UF membrane：After anodic oxidation terminates, rinsed and dried with ethanol, acetone or isopropanol, finally soaked inside water
Bubble 2h, nano-tube film can be separated with metal Ti pieces automatically, obtain little self-supporting TiO of adhesion2Nano-tube film and metal
The complex of Ti.
(4) film transfer：It is careful the nano-tube film separated --- metal Ti piece complexs are taken out from water,
It is put in the smaller organic solvent of surface tension, such as, in methyl alcohol, ethanol, acetone or isopropanol, stands 30min, treat original
Hydrone is reentered into after spreading out completely in the aqueous solution, and nano-tube film can be kept completely separate with Titanium, and is transferred to hard
Matter substrate or PET base, obtain the intact self-supporting nano-tube film of structure.
So as to obtain 1290nm self-supportings TiO2Nano-pipe array thin film.As shown in Figure 4.
Specific embodiment three：
Present embodiment and specific embodiment one are not both in step 2 using oxidization time 7min, other and concrete reality
Applying method one is identical.So as to obtain 1460nm self-supportings TiO2Nano-pipe array thin film.As shown in Figure 5.
Specific embodiment four：
Present embodiment and specific embodiment one are not both in step 2 using oxidization time 10min, other with it is concrete
Implementation one is identical.
In sum, a kind of preparation method of ultra-thin titanium dioxide nano-pipe array thin film is embodiments provided,
The method preparation process is simple, it is easy to operate, cost is low.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
Should all be included within the scope of the present invention.
Claims (6)
1. a kind of self-supporting TiO2The preparation method of nano-pipe array thin film, it is characterised in that comprise the steps：
Step one, process metal titanium sheet；
Step 2, preparation electrolyte solution；
Step 3, two-step electrochemical anodizing method prepare self-supporting TiO2Nano-tube film：
(1), under room temperature condition, the metal titanium sheet after step one is processed is put into the electrolyte prepared through step 2 molten
First time anodic oxidation is carried out in liquid, wherein lead to 60V voltage as to electrode with graphite or Pt, after oxidization time 2-24h,
Ethanol purge titanium sheet is used, then ultrasonically treated 15-60min, make the unformed TiO that oxidation is obtained2Nano-tube film Automatic-falling,
So as to obtain the titanium sheet of first time anodic oxidation；
(2) second anodic oxidation is carried out by template of the titanium sheet of first time anodic oxidation：Oxidization time at ambient temperature
For 3-10min；
(3) UF membrane：After second anodic oxidation terminates, rinsed and dried with ethanol, acetone or isopropanol, finally inside water
Immersion 0.5-2h, nano-tube film can be separated with metal titanium sheet automatically, obtain little self-supporting TiO of adhesion2Nano-tube film
With the complex of metal titanium sheet；
(4) film transfer：Nano-tube film and metal titanium sheet complex are taken out from water, the little organic solvent of surface tension is put into
In, 10-30min being stood, is reentered in the aqueous solution after original hydrone is spread out completely, nano-tube film can be with gold
Category titanium sheet is kept completely separate, and is transferred to hard substrate or PET base, obtains intact self-supporting TiO of structure2Nano-tube film.
2. a kind of self-supporting TiO according to claim 12The preparation method of nano-pipe array thin film, it is characterised in that：Institute
The thickness for stating metal titanium sheet is 0.2-0.3mm, and size is 1*1cm, 1*4cm, 2*4cm.
3. a kind of self-supporting TiO according to claim 12The preparation method of nano-pipe array thin film, it is characterised in that：Institute
State process in step one metal titanium sheet method be metal titanium sheet is respectively put into into acetone, first alcohol and water in each ultrasonic 15min with
On, each ultrasound is dried up with nitrogen after finishing.
4. a kind of self-supporting TiO according to claim 12The preparation method of nano-pipe array thin film, it is characterised in that：Institute
It is in ethylene glycol solution, to add volume ratio to be 1%-5% deionized waters and mass fraction is to state electrolyte solution in step 2
The NH of 0.2-1%4F。
5. a kind of self-supporting TiO according to claim 12The preparation method of nano-pipe array thin film, it is characterised in that：Institute
It is in ethylene glycol solution, add volume ratio to be that 1%-5% deionized waters, mass fraction are to state electrolyte solution in step 2
The NH of 0.2-1%4F and volume ratio are 0.1-0.5%H3PO4。
6. a kind of self-supporting TiO according to claim 12The preparation method of nano-pipe array thin film, it is characterised in that：Institute
In stating step 3, the little organic solvent of surface tension is methyl alcohol, ethanol, acetone or isopropanol.
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| 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 |
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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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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 |
|---|
| A Simple Method for Preparation of Through-Hole Porous Anodic Alumina Membrane;J. H. Yuan et al;《Chemistry of Materials》;20040422;第16卷(第10期);第1841-1844页 * |
| Freestanding TiO2 Nanotube Arrays with Ultrahigh Aspect Ratio via Electrochemical Anodization;Jun Wang et al;《Chemisty of Materials》;20080115;第20卷(第4期);第1257-1261页 * |
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