CN102677123A - Preparation method of independent titanium dioxide nanotube array film - Google Patents
Preparation method of independent titanium dioxide nanotube array film Download PDFInfo
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- CN102677123A CN102677123A CN2012101772448A CN201210177244A CN102677123A CN 102677123 A CN102677123 A CN 102677123A CN 2012101772448 A CN2012101772448 A CN 2012101772448A CN 201210177244 A CN201210177244 A CN 201210177244A CN 102677123 A CN102677123 A CN 102677123A
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Abstract
The invention discloses a preparation method of an independent titanium dioxide nanotube array film. The film preparation process comprises oxidizing a pure titanium anode to obtain a titanium dioxide nanotube array film, utilizing hydrofluoric acid solution to immerse the film to enable the film to be separated from a titanium matrix to obtain an independent amorphous titanium dioxide nanotube array film, then washing the independent amorphous titanium dioxide nanotube array film through deionized water, and performing calcination to obtain the independent anatase type titanium dioxide nanotube array film. The preparation method is simple in process and convenient to operate. The thickness of the titanium dioxide film can be controlled by controlling oxidizing time of the anode, and the diameter of the titanium dioxide film can be controlled by changing oxidizing voltage of the anode. Compared with a titanium dioxide nanotube array film with a titanium sheet serving as a substrate, the independent titanium dioxide nanotube array film has large area, can be transferred to a transparent flexible substrate, and has wide application range.
Description
Technical field
The present invention relates to a kind of preparation method of independently titanium dioxide nano-pipe array thin film, belong to the titanium dioxide nano material technology of preparing.
Background technology
The orderly Nano tube array of titanium dioxide structure of one dimension is widely used in fields such as solar cell, hydrogen manufacturing, photochemical catalysis, transmitter and biological chemistry because of its unique appearance structure and energy band structure characteristic; But because the titania nanotube for preparing through anonizing is substrate with the titanium sheet; Make it on using, receive certain restriction; Therefore, need to adopt simple effective method to obtain independently titanium dioxide nano-pipe array thin film.
At present; The preparation of titanium dioxide nano-pipe array thin film mainly is to adopt anonizing; Anonizing can obtain certain thickness titanium dioxide nano-pipe array thin film on the titanium sheet; Through physics or chemical process divided thin film is left again, obtain independently titanium dioxide nano-pipe array thin film.Physical method mainly contains that solvent evaporation makes that divided thin film leaves, sonic oscillation leaves divided thin film or is directly down sticking with adhesive tape, and physical method is difficult to obtain the complete independent titanium deoxid film of big area, and often appearance can't isolating situation; Chemical process has two-step anodization and chemical solution dissolved method; The two-step anodization method leaves divided thin film through changing voltage or temperature; But technology is relatively complicated, and the solution that the solution dissolving is adopted mainly contains ydrogen peroxide 50, hydrochloric acid etc., and speed of response is relatively slow.The present invention prepares the titanium dioxide nano-pipe array thin film of different thickness through anonizing, handles with the hydrofluoric acid of different concns, obtains large-area independent titanium dioxide nano-pipe array thin film.
Summary of the invention
The object of the invention is to provide a kind of preparation method of independently large-area titanium dioxide nano-pipe array thin film, and it is simple that this method prepares process, advantages such as easy handling.
The present invention realizes that through following technical proposals a kind of independently titanium dioxide nano-pipe array thin film is characterized in that may further comprise the steps:
1) with the industrially pure titanium sheet respectively at deionized water, ultrasonic cleaning in ethanol and the acetone is behind the air drying; In the terepthaloyl moietie electrolytic solution that contains massfraction 0.25-0.75% Neutral ammonium fluoride, volume(tric)fraction 1-2% water; As anode, platinum electrode is as negative electrode with the titanium sheet, and anodic oxidation 1-24h obtains titanium dioxide nano-pipe array thin film under voltage 40-120V condition; The ethanol ultrasonic cleaning, air drying;
What 2) step 1) is obtained is that the titanium dioxide nano-pipe array thin film of substrate joins in the hydrofluoric acid solution that massfraction is 0.1-5% with the titanium sheet; After at room temperature reacting 30 seconds to 5 minutes; Titanium dioxide nano-pipe array thin film separates with substrate titanium sheet, obtains unbodied independently titanium dioxide nano-pipe array thin film;
3) with step 2) the independently titanium dioxide nano-pipe array thin film that obtains with deionized water wash to neutral; Drying is placed in the retort furnace, in air atmosphere, with the temperature rise rate of 10 ℃/min; Be warming up to 400-500 ℃ of insulation 0.5-5 hour, cool to room temperature with the furnace; Finally obtain independently anatase titanium dioxide nano-pipe array thin film.
Compared with prior art, advantage of the present invention is: simple to operate, cost is low.Equipment is common anodic oxidation device and retort furnace, need not other large-scale or complex apparatus.The thickness of titanium deoxid film can be controlled through controlling the anodised time, and the diameter of titania nanotube can be controlled through changing anodic oxidation voltage.Than being the titanium dioxide nano-pipe array thin film of substrate with the titanium sheet, this film size is bigger, can be transferred in the transparent flexible substrate, and range of application is more extensive.
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Description of drawings
Fig. 1 is embodiment 1 an obtained independently titanium dioxide nano-pipe array thin film photomacrograph.
Fig. 2 is the embodiment 1 obtained independently SEM above titanium dioxide nano-pipe array thin film figure.
Fig. 3 is the SEM figure below the embodiment 1 obtained independently titanium dioxide nano-pipe array thin film.
Embodiment
Below in conjunction with embodiment the present invention is further described, these embodiment just are used to explain the present invention, do not limit the present invention.
Embodiment one
With area 60x55mm
2, the pure titanium sheet of the polishing attitude of thickness 0.5mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Contain in the ethylene glycol solution of deionized water and 98ml of Neutral ammonium fluoride, 2ml of 0.445g at 100ml then, with titanium as anode, with platinum electrode as negative electrode; Electrode distance 3cm, voltage 60V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 10h, and in treating processes, continue to stir electrolytic solution; The sample that obtains ultrasonic cleaning in ethanol is immersed into massfraction 1% hydrofluoric acid solution of 100ml then, leaves standstill 2min under 25 ℃, and film separates with the titanium sheet, take out titanium deoxid film with deionized water rinsing to neutral; At last dried film is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 450 ℃ are incubated 30min down, cool to room temperature with the furnace.Finally obtain independently anatase titanium dioxide nano-pipe array thin film, this film size 30.25cm
2, thickness is 25 μ m, and the titania nanotube mean pore size on it is 110nm, and average wall thickness is 10nm.
Embodiment two
With area 60x55mm
2, the pure titanium sheet of the polishing attitude of thickness 0.5mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Contain in the ethylene glycol solution of deionized water and 98ml of Neutral ammonium fluoride, 2ml of 0.445g at 100ml then, with titanium as anode, with platinum electrode as negative electrode; Electrode distance 3cm, voltage 60V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 24h, and in treating processes, continue to stir electrolytic solution; The sample that obtains ultrasonic cleaning in ethanol is immersed into massfraction 4% hydrofluoric acid solution of 100ml then, leaves standstill 1min under 25 ℃, and film separates with the titanium sheet, take out titanium deoxid film with deionized water rinsing to neutral; At last dried film is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 400 ℃ are incubated 30min down, cool to room temperature with the furnace.Finally obtain independently anatase titanium dioxide nano-pipe array thin film, this film thickness is 40 μ m, and mean pore size is 115nm, and average wall thickness is 10nm.
Embodiment three
With area 60x55mm
2, the pure titanium sheet of the polishing attitude of thickness 0.5mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Contain in the ethylene glycol solution of deionized water and 99ml of Neutral ammonium fluoride, 1ml of 0.278g at 100ml then, with titanium as anode, with platinum electrode as negative electrode; Electrode distance 3cm, voltage 50V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 8h, and in treating processes, continue to stir electrolytic solution; The sample that obtains ultrasonic cleaning in ethanol is immersed into massfraction 1% hydrofluoric acid solution of 100ml then, leaves standstill 1min under 25 ℃, and film separates with the titanium sheet, take out titanium deoxid film with deionized water rinsing to neutral; At last dried film is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 400 ℃ are incubated 30min down, cool to room temperature with the furnace.Finally obtain independently anatase titanium dioxide nano-pipe array thin film, this film thickness is 20 μ m, and mean pore size is 85nm, and average wall thickness is 8nm.
Embodiment four
With area 60x55mm
2, the pure titanium sheet of the polishing attitude of thickness 0.5mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Contain in the ethylene glycol solution of deionized water and 99ml of Neutral ammonium fluoride, 1ml of 0.278g at 100ml then, with titanium as anode, with platinum electrode as negative electrode; Electrode distance 3cm, voltage 50V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 5h, and in treating processes, continue to stir electrolytic solution; The sample that obtains ultrasonic cleaning in ethanol is immersed into massfraction 1% hydrofluoric acid solution of 100ml then, leaves standstill 30s under 25 ℃, and film separates with the titanium sheet, take out titanium deoxid film with deionized water rinsing to neutral; At last dried film is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 400 ℃ are incubated 30min down, cool to room temperature with the furnace.Finally obtain independently anatase titanium dioxide nano-pipe array thin film, this film thickness is 15 μ m, and mean pore size is 85nm, and average wall thickness is 8nm.
Claims (1)
1. preparation method of titanium dioxide nano-pipe array thin film independently is characterized in that may further comprise the steps:
1) with the industrially pure titanium sheet respectively at deionized water, ultrasonic cleaning in ethanol and the acetone is behind the air drying; In the terepthaloyl moietie electrolytic solution that contains massfraction 0.25-0.75% Neutral ammonium fluoride, volume(tric)fraction 1-2% water; As anode, platinum electrode is as negative electrode with the titanium sheet, and anodic oxidation 1-24h obtains titanium dioxide nano-pipe array thin film under voltage 40-120V condition; The ethanol ultrasonic cleaning, air drying;
What 2) step 1) is obtained is that the titanium dioxide nano-pipe array thin film of substrate joins in the hydrofluoric acid solution that massfraction is 0.1-5% with the titanium sheet; After at room temperature reacting 30 seconds to 5 minutes; Titanium dioxide nano-pipe array thin film separates with substrate titanium sheet, obtains unbodied independently titanium dioxide nano-pipe array thin film;
3) with step 2) the independently titanium dioxide nano-pipe array thin film that obtains with deionized water wash to neutral; Drying is placed in the retort furnace, in air atmosphere, with the temperature rise rate of 10 ℃/min; Be warming up to 400-500 ℃ of insulation 0.5-5 hour, cool to room temperature with the furnace; Finally obtain independently anatase titanium dioxide nano-pipe array thin film.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225104A (en) * | 2013-04-10 | 2013-07-31 | 华南理工大学 | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof |
| CN103614761A (en) * | 2013-12-02 | 2014-03-05 | 天津大学 | Method for preparing highly-ordered titanium dioxide nanotube and application in dye-sensitized solar cell |
| CN103774169A (en) * | 2014-01-20 | 2014-05-07 | 西安理工大学 | Preparation method of TiO2 nanotube with scattered through holes |
| CN105132989A (en) * | 2015-09-14 | 2015-12-09 | 电子科技大学 | Preparation method of transparent titanium dioxide nanotube film |
| CN105951154A (en) * | 2016-04-27 | 2016-09-21 | 中国计量大学 | Anodic oxidation preparation method for titanium dioxide nanotube array photocatalyst for degrading rhodamine B |
| CN106498478A (en) * | 2016-11-22 | 2017-03-15 | 华南理工大学 | A kind of preparation method of transparent independent titanium dioxide nano-pipe array thin film |
| CN108251881A (en) * | 2018-01-22 | 2018-07-06 | 天津工业大学 | A kind of POROUS TITANIUM/titania nanotube composite flat membrane and preparation method thereof |
| KR20190084671A (en) * | 2018-01-09 | 2019-07-17 | 삼성전자주식회사 | Method of manufacturing photocatalytic filter for air cleaning |
| CN114411222A (en) * | 2021-12-22 | 2022-04-29 | 深圳华越再生医学生物科技有限公司 | Titanium dioxide film and preparation method and application thereof |
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| CN102383164A (en) * | 2011-11-08 | 2012-03-21 | 天津大学 | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof |
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| CN102383164A (en) * | 2011-11-08 | 2012-03-21 | 天津大学 | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof |
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| STEFANI SUSILO: "ANODIZATION GROWTH AND INTEGRATION OF TITANIUM DIOXIDE NANOTUBES IN DYE SENSITIZED SOLAR CELLS", 《DREXEL UNIVERSITY硕士论文》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225104A (en) * | 2013-04-10 | 2013-07-31 | 华南理工大学 | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof |
| CN103614761A (en) * | 2013-12-02 | 2014-03-05 | 天津大学 | Method for preparing highly-ordered titanium dioxide nanotube and application in dye-sensitized solar cell |
| CN103774169A (en) * | 2014-01-20 | 2014-05-07 | 西安理工大学 | Preparation method of TiO2 nanotube with scattered through holes |
| CN103774169B (en) * | 2014-01-20 | 2016-08-17 | 西安理工大学 | A kind of TiO disperseing through hole2the preparation method of nanotube |
| CN105132989A (en) * | 2015-09-14 | 2015-12-09 | 电子科技大学 | Preparation method of transparent titanium dioxide nanotube film |
| CN105951154A (en) * | 2016-04-27 | 2016-09-21 | 中国计量大学 | Anodic oxidation preparation method for titanium dioxide nanotube array photocatalyst for degrading rhodamine B |
| CN106498478A (en) * | 2016-11-22 | 2017-03-15 | 华南理工大学 | A kind of preparation method of transparent independent titanium dioxide nano-pipe array thin film |
| WO2018095290A1 (en) * | 2016-11-22 | 2018-05-31 | 华南理工大学 | Method for preparing transparent independent titania nanotube array films |
| US10882754B2 (en) | 2016-11-22 | 2021-01-05 | South China University Of Technology | Method for preparing transparent free-standing titanium dioxide nanotube array film |
| KR20190084671A (en) * | 2018-01-09 | 2019-07-17 | 삼성전자주식회사 | Method of manufacturing photocatalytic filter for air cleaning |
| US11576995B2 (en) | 2018-01-09 | 2023-02-14 | Samsung Electronics Co., Ltd | Method for manufacturing photocatalytic filter for air purification |
| KR102535580B1 (en) * | 2018-01-09 | 2023-05-23 | 삼성전자주식회사 | Method of manufacturing photocatalytic filter for air cleaning |
| CN108251881A (en) * | 2018-01-22 | 2018-07-06 | 天津工业大学 | A kind of POROUS TITANIUM/titania nanotube composite flat membrane and preparation method thereof |
| CN114411222A (en) * | 2021-12-22 | 2022-04-29 | 深圳华越再生医学生物科技有限公司 | Titanium dioxide film and preparation method and application thereof |
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Application publication date: 20120919 |