CN101717984A - Method for preparing titanium dioxide nanotube membrane - Google Patents
Method for preparing titanium dioxide nanotube membrane Download PDFInfo
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- CN101717984A CN101717984A CN200910222408A CN200910222408A CN101717984A CN 101717984 A CN101717984 A CN 101717984A CN 200910222408 A CN200910222408 A CN 200910222408A CN 200910222408 A CN200910222408 A CN 200910222408A CN 101717984 A CN101717984 A CN 101717984A
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Abstract
The invention discloses a method for preparing a titanium dioxide (TiO2) nanotube membrane with two permeable ends of a nanotube thereof. The method for preparing the titanium dioxide nanotube membrane comprises the following steps of: firstly, generating a titanium dioxide membrane with a required thickness on the surface of a titanium substrate material in a mode of electrolytic oxidation; secondly, thinning a barrier layer at the bottom of the titanium dioxide nanotube membrane by adopting gradual voltage-lowering oxidation; and finally, applying a high-voltage pulse higher than an anode oxidation voltage to continue oxidizing after finishing the last process until the titanium dioxide nanotube membrane with two permeable ends is shed from the substrate.
Description
Technical field
The two ends that the present invention relates to a kind of its nanotube are penetrating titanium dioxide (TiO
2) preparation method of nano-tube film.Titanic oxide nano tube thin-film of the present invention is at first that the surface cleaning of titanium base material is clean and carry out chemical rightenning and handle, again base material is put into electrolytic solution, with metal sheet is that counter electrode carries out electrochemical anodic oxidation, generates the titanium deoxid film of desired thickness to substrate material surface.
Background technology
Since Japanese Fujishima in 1972 finds titanium dioxide single crystalline electrode photochemical catalyzing [Nature, 1972,238 (5358): 37-38.], photocatalysis technology has obtained paying close attention to widely.Photocatalysis technology might solve human following energy dilemma and problem of environmental pollution.Photocatalysis technology just can carry out under normal temperature, normal pressure, can thoroughly destroy the organic or inorganic pollutent, and makes it to be oxidized to fully, fast CO
2, H
2Innoxious substances such as O have been avoided secondary pollution, thereby reach the purpose of environment purification.Early stage titanium dioxide mainly is the nano particle for preparing by gas phase synthesis method and liquid phase synthesizing method, is mainly used in photocatalysis technology and inorganic paint.In recent years since titania nanotube at dye sensitization solar battery, photocatalyst, hydrogen gas sensor, bone embedded material, template electric-sedimentation prepares aspects such as metal or semiconductor nanowires and has broad application prospects, and has become both at home and abroad the competitively focus of research.At present the preparation method of titania nanotube mainly contains 3 kinds of methods: utilize porous alumina, the organic polymer template preparation method as template, utilize the hydrothermal method that titanium dioxide powder reacts and utilize electrochemistry anodic oxidation under alkaline condition.What hydrothermal method made is the multi-layer nano structure titanium dioxide, and what template and electrochemistry anodic oxidation obtained is the Nano tube array of titanium dioxide of high-sequential.Wherein, electrochemistry anodic oxidation is the effective means of preparation titania nanotube, and this method can form the titanium dioxide nano-pipe array thin film of high-sequential in substrate, and experiment condition is controlled, working method is simple, thereby more and more is subject to people's attention.
Calendar year 2001 U.S. scientist Varghese utilizes the method for electrochemical anodic oxidation, prepares Nano tube array of titanium dioxide material (Dawei G., et al in the aqueous solution of HF first, J.Mater.Res., 2001,16:3331), caused people's very big concern.But under acidic conditions, titanium dioxide and F ionic reaction generate soluble complexes [TiF
6]
2-Speed very fast, suppressed the increase of nano-tube film layer thickness, generally can only reach the hundreds of nanometer.Germany scientist Schmuki adopts NaF or NH by changing the composition of electrolytic solution
4The salt of fluoride ions such as F replaces HF, under neutrallty condition, prepare thicknesses of layers greater than the Nano tube array of titanium dioxide of 2 μ m (Patrik Schmuki, et, al, Angew.Chem.Int.Ed., 2005,44:2100).Nearest Grimes, people such as Schmuki attempt to increase to the understanding of titania nanotube growth mechanism with to the control of titania nanotube pattern by a large amount of experimental studies, by the process of growth that experimental results demonstrate titania nanotube is the equilibrium process of an electrochemical oxidation growth and chemical dissolution, and the caliber of titania nanotube and pipe range can be controlled respectively by anodic oxidation voltage and time.Yet, face two main problems when preparing titanic oxide nano tube thin-film with anonizing: the one,, resulting titanic oxide nano tube thin-film always had the not penetrable titanium dioxide barrier layer of one deck after anodic oxidation was finished between nanotube bottom and titanium substrate, and its thickness has 10-100nm usually.The obstruction that this layer barrier layer is serious titanic oxide nano tube thin-film use widely, such as it can hinder directly electrically contacting with chemistry of nano-tube film and conductive substrates and contacts in the application for preparing metal or semiconductor nanowires at dc electrodeposition.The 2nd,, resulting titanic oxide nano tube thin-film is always being tied up in the titanium substrate firmly, is difficult to obtain independently titanic oxide nano tube thin-film, has also influenced its some special applications.
In order to obtain independence and titanium substrate and the penetrating TiO in two ends
2Nano-tube film, people such as Schmuki utilize a kind of corrosive brominated methanol solution to come optionally chemical etching to remove the titanium substrate, remove the TiO of film bottom then with the HF solution chemistry etching of dilution
2Barrier layer is referring to " Self-Organized, Free-StandingTiO
2Nanotube Membrane for Flow-through Photocatalytic Applications " Nano Lett., Vol.7, No.5,2007,1286-1289.People such as Grimes utilize in solution ultransonic method with TiO
2Nano-tube film comes off from the titanium substrate, removes the TiO of film bottom then with HF steam chemical etching
2Barrier layer.Above method is prepared is independent of substrate and the penetrating TiO in its two ends
2The chemical etchant that nano-tube film all needs to introduce out-phase is come chemical dissolution titanium or aluminium substrate, so also just inevitably to whole TiO
2Nano-tube film; Another deficiency of these methods is to have introduced extra pollution in its preparation process, as: Hg
2+, Br
-Deng.Humans such as nearest Dusan Losic progressively reduce the thickness that voltage method reduces titania nanotube bottom barrier layer after oxidising process is finished, and then titanic oxide nano tube thin-film is peeled off from the titanium substrate surface by supersound process, obtain the penetrating titanic oxide nano tube thin-film in two ends at last, referring to " A simple approach for synthesis of TiO
2Nanotubes with through-holemorphology ", P hys.Status Solidi RRL 3, No.5,139-141 (2009)/DOI10.1002/pssr.200903087.Because the committed step of this method is still to adopt the ultrasonic wave means with TiO
2Nano-tube film strips down to mechanism from the base, the same similar shortcoming of method that exists with other mechanically peels.For example, because TiO
2Nano-tube film itself is comparatively fragile, and is very difficult to hyperacoustic power and the control of the time of application when using the ultrasonic wave overburden operation, and is difficult to avoid because of the ultrasonic film partial fracture that excessively causes; In addition, if the ultrasonic power improper use can't guarantee that also nanotube two ends all in the resulting film are penetrating.
Summary of the invention
The invention provides a kind of prior art deficiency that overcomes, can prepare the penetrating titanic oxide nano tube thin-film in two ends, and in preparation process, do not introduce foreign peoples's contaminated ion, do not use the preparation method of the mechanically peel means of supersound process simultaneously.
Preparation method of the present invention is earlier that the surface cleaning of titanium base material is clean and carry out chemical rightenning and handle, again base material is put into electrolytic solution, with metal sheet is that counter electrode carries out electrochemical anodic oxidation, generate the titanium deoxid film of desired thickness to substrate material surface, adopt then and progressively fall the barrier layer attenuation that the voltage oxidation makes the titanic oxide nano tube thin-film bottom, finish applying a high voltage pulse that is higher than anodic oxidation voltage again after this process and proceed oxidation, the titanic oxide nano tube thin-film penetrating until two ends comes off from substrate.
Among the preparation method of the present invention, the minimum voltage value of employed high voltage pulse is 1.15 times of anodic oxidation voltage.Relevant test shows when the oxidation voltage that applies again is 1.3-1.5 times of original oxidation voltage best effect, like this can be at relatively shorter high-voltage oxidation rear demoulding.
By aforementioned content as can be known, all processes all are to finish in same electrolytic solution among the preparation method of the present invention, can obtain complete, its nanotube two ends is penetrating titanic oxide nano tube thin-film, can not introduce other ions in whole preparation, also can not be subjected to the corrosion of highly corrosive agents.Another advantage of the present invention is can be by anodised voltage of control and time, and the magnitude of voltage of high voltage pulse and burst length control film bottom opening degree and size are to form the different titanic oxide nano tube thin-films that require.Because the penetrating titania nanotube in two ends with the present invention's preparation can make the solution exchange rapider, can improve its photocatalysis performance greatly, and application more widely may be arranged in other field.
Description of drawings
Fig. 1 prepares the photo of the penetrating titanic oxide nano tube thin-film in two ends for the embodiment of the invention.
Fig. 2 is the stereoscan photograph of the titanic oxide nano tube thin-film of embodiment of the invention preparation, and wherein: being positive (a), (b) being the bottom surface, (c) is the side.
Fig. 3 is respectively the penetrating titanium dioxide (TiO in two ends of the embodiment of the invention 2～4 preparations
2) stereoscan photograph of nano-tube film bottom.
Fig. 4 is respectively the penetrating titanium dioxide (TiO in two ends of the embodiment of the invention 5～7 preparations
2) stereoscan photograph of nano-tube film bottom.
Embodiment
Some embodiments of the present invention below are provided.
Embodiment 1:
Pure titanium plate is cut into the substrate of 3.0cm * 1.0cm size and 250 μ m thickness, uses acetone successively, Virahol, methyl alcohol and deionized water ultrasonic cleaning are then at HF and HNO
3Volume ratio is to carry out chemical rightenning, N in 1: 8 the mixing solutions
2It is standby to dry up the back.At room temperature, make anode with the titanium sheet, aluminium sheet is made counter electrode, gets 85ml (NH
4F (0.25wt%)+H
2O (0.3vol%)+HOCH
2CH
2OH) electrolytic solution, after the constant voltage that applies 60V carries out anodic oxidation 2h, make the surface of titanium substrate produce the titanium dioxide layer of required thickness in advance, to reduce oxidation voltage with the speed of 1V/15s again, proceed oxidation, after voltage reduced to 0, the pulse high-voltage that applies a 80V again continued oxidation 6min, and titanium deoxid film can come off on substrate voluntarily.Take out the print washed with de-ionized water, dry in the air, its resulting sample is seen Fig. 1, can obtain undamaged TiO from scheming to go up visible method according to this electrochemical stripping
2Nano-tube film.The TiO of Fig. 2 for obtaining according to embodiment 1
2The scanning electron microscope of nano-tube film (SEM) photo.Be high-sequential, high length-diameter ratio and the equal opening in two ends porous tubular structured up and down from scheming to go up visible nano-tube array.
Similar with embodiment 1, its difference is pure titanium plate is cut into the substrate of 3.0cm * 1.0cm size and 250 μ m thickness, uses acetone successively, Virahol, and methyl alcohol and deionized water ultrasonic cleaning are then at HF and HNO
3Volume ratio is to carry out chemical rightenning, N in 1: 8 the mixing solutions
2It is standby to dry up the back.At room temperature, make anode with the titanium sheet, aluminium sheet is made counter electrode, gets 85ml (NH
4F (0.25wt%)+H
2O (0.3vol%)+HOCH
2CH
2OH) electrolytic solution applies the voltage anodic oxidation 2h of 60V.Thereafter, oxidation voltage begins interval with 1V/15s from 60V and progressively reduces up to voltage to be 1V, to apply a 65V (example 2) at last again, 70V (example 3), and 75V (example 4) takes out the print washed with de-ionized water, dries in the air.The TiO of Fig. 3 for obtaining according to embodiment 2
2The scanning electron microscope of nano-tube film (SEM) photo.From scheming to go up the difference of visible nano-pipe array thin film bottom along with the pulsed voltage size that applies at last, the degree of its opening is also inequality, the nano-tube film bottom that obtains when pulsed voltage is higher than oxidation voltage 8% to 15% can not be opened completely, but the magnitude of voltage with high voltage pulse is big more, the tube bank that its bottom is opened is many more, and its extent of opening is big more; When pulsed voltage is higher than oxidation voltage 25%, can be opened completely bottom the resulting nano-tube film when promptly pulsed voltage is 75V.
Claims (2)
1. the preparation method of a titanic oxide nano tube thin-film, the surface cleaning of titanium base material is clean and carry out chemical rightenning and handle, again base material is put into electrolytic solution, with metal sheet is that counter electrode carries out electrochemical anodic oxidation, generate the titanium deoxid film of desired thickness to substrate material surface, adopt then and progressively fall the barrier layer attenuation that the voltage oxidation makes the titanic oxide nano tube thin-film bottom, it is characterized in that applying a high voltage pulse that is higher than anodic oxidation voltage again and carry out oxidation, the titanic oxide nano tube thin-film penetrating until two ends comes off from substrate.
2. the preparation method of titanic oxide nano tube thin-film according to claim 1, the minimum voltage that it is characterized in that high voltage pulse is 1.15 times of anodic oxidation voltage.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280258A (en) * | 2010-07-22 | 2011-12-14 | 香港理工大学 | Method for stripping titanium dioxide nanotube film and method for manufacturing dye-sensitized solar cell |
| CN103590087A (en) * | 2013-10-16 | 2014-02-19 | 中国科学院合肥物质科学研究院 | TiO2 nanotube array film with periodically-changing inner aperture and adjustable period and preparation method thereof |
| CN103668389A (en) * | 2013-11-21 | 2014-03-26 | 中国科学院合肥物质科学研究院 | Preparation method of ultra-thin two-way titanium-dioxide nanopore-array film with adjustable aperture and thickness |
| CN103998536A (en) * | 2011-12-05 | 2014-08-20 | 纳诺精密医疗有限公司 | Device having titania nanotube membrane for drug delivery |
| CN104882288A (en) * | 2015-05-06 | 2015-09-02 | 同济大学 | Method for preparing Ti-Fe alloy oxide photonic crystal electrode with high periodicity |
| CN111634941A (en) * | 2020-07-27 | 2020-09-08 | 南开大学 | Self-peeling titanium dioxide nanotube |
-
2009
- 2009-11-05 CN CN200910222408A patent/CN101717984A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280258A (en) * | 2010-07-22 | 2011-12-14 | 香港理工大学 | Method for stripping titanium dioxide nanotube film and method for manufacturing dye-sensitized solar cell |
| CN102280258B (en) * | 2010-07-22 | 2013-06-05 | 香港理工大学 | Method for stripping titanium dioxide nanotube film and method for manufacturing dye-sensitized solar cell |
| CN103998536A (en) * | 2011-12-05 | 2014-08-20 | 纳诺精密医疗有限公司 | Device having titania nanotube membrane for drug delivery |
| CN103998536B (en) * | 2011-12-05 | 2017-09-15 | 纳诺精密医疗有限公司 | The device with titania nanotube film for medicine delivery |
| CN103590087A (en) * | 2013-10-16 | 2014-02-19 | 中国科学院合肥物质科学研究院 | TiO2 nanotube array film with periodically-changing inner aperture and adjustable period and preparation method thereof |
| CN103590087B (en) * | 2013-10-16 | 2016-03-16 | 中国科学院合肥物质科学研究院 | Internal orifice dimension mechanical periodicity and cycle adjustable TiO 2nano-pipe array thin film and preparation method thereof |
| CN103668389A (en) * | 2013-11-21 | 2014-03-26 | 中国科学院合肥物质科学研究院 | Preparation method of ultra-thin two-way titanium-dioxide nanopore-array film with adjustable aperture and thickness |
| CN103668389B (en) * | 2013-11-21 | 2016-05-11 | 中国科学院合肥物质科学研究院 | The preparation method of the ultra-thin bilateral titanium dioxide nano-pore array thin film that aperture and thickness are adjustable |
| CN104882288A (en) * | 2015-05-06 | 2015-09-02 | 同济大学 | Method for preparing Ti-Fe alloy oxide photonic crystal electrode with high periodicity |
| CN104882288B (en) * | 2015-05-06 | 2018-02-09 | 同济大学 | A kind of preparation method with high degree of periodicity Ti Fe alloyed oxide photonic crystal electrodes |
| CN111634941A (en) * | 2020-07-27 | 2020-09-08 | 南开大学 | Self-peeling titanium dioxide nanotube |
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Application publication date: 20100602 |