CN102418133A - Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film - Google Patents
Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film Download PDFInfo
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- CN102418133A CN102418133A CN2011104103111A CN201110410311A CN102418133A CN 102418133 A CN102418133 A CN 102418133A CN 2011104103111 A CN2011104103111 A CN 2011104103111A CN 201110410311 A CN201110410311 A CN 201110410311A CN 102418133 A CN102418133 A CN 102418133A
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Abstract
The invention discloses a nanohoneycomb titanium dioxide structure thin film with a rough surface and a preparation method of the nanohoneycomb titanium dioxide structure thin film. The thin film is formed on a metal titanium substrate and is integrally in a honeycomb structure; and the rough surface of the inner wall consists of nano titanium dioxide grains. The preparation process of the thin film comprises the following steps of: carrying out anodic oxidization on a pure titanium material to obtain a titanium dioxide nanotube array thin film; soaking the thin film with a strong base solution; and then washing the thin film with acetic acid or acetate and roasting to obtain the anatase type nano honeycomb titanium dioxide structure thin film with the rough surface. The method provided by the invention has the advantages of simple process and convenience for operation. An average diameter of a honeycomb can be controlled by an aperture of a precursor nanotube and the diameter control of the nanotube can be realized by directly changing an anodic oxidation voltage. Compared with the titanium dioxide nanotube array thin film formed by the anodic oxidation, the thin film has a larger specific surface area.
Description
Technical field
The present invention relates to a kind of surface irregularity nano titania honey-combed film and preparation method, belong to the titanium dioxide nano material technology.
Background technology
Nano titanium oxide is a kind of important inorganic functional material, extensively is used as the light anode material of dye sensitization solar battery because it has unique energy band structure and chemicalstability.Traditional light anode is generally the titanium dioxide nanocrystalline particle film, and in recent years, the nano titania array structure obtains people's extensive concern owing to its particular structure characteristic.The nano titania array structure can increase the scattering of photon, has increased the transmission route of photon in electrode materials, helps strengthening the absorption of light; Simultaneously, the array electrode material is owing to have ordered structure, and perpendicular to electrode surface, can reduce the transmission route of electric charge in electrode materials to greatest extent, reduces interface compound chance.But the Nano tube array of titanium dioxide surface of preparation is more smooth at present, has reduced specific surface area, and has been unfavorable for the absorption of dyestuff, influences its application performance.
The method that the titanium dioxide nano-pipe array thin film surface roughening is handled mainly contains two kinds, and a kind of method is through controlling anodised process, change electrolyte ingredient, but this method also can make caliber become big, the tube wall thickening when increasing specific surface area; Another kind method is to adopt titanium tetrachloride solution to handle; The appendix titania nanoparticles on the titania nanotube surface, but this method reaction process is wayward, and the nano particle of formation is inhomogeneous; Appendix makes the tube wall thickening, has reduced specific surface area to a certain extent.The present invention reaches the reaction process of absorption again through the dissolving tube wall, has avoided the increase thickness of pipe, the surface irregularity nano titania honey-combed of preparation, and increasing specific surface area strengthens the scattering of light effect, is beneficial to the absorption of dyestuff.
Summary of the invention
The object of the invention is to provide a kind of surface irregularity nano titania honey-combed film and preparation method.Described film has good photoelectric properties and chemicalstability, and it is simple that this method prepares process, easy handling.
The present invention realizes through following technical proposals, and a kind of surface irregularity nano titania honey-combed film, this film are formed on the matrix of metal titanium; It is characterized in that; This film thickness is 2 ~ 40 μ m, and it is the honey-combed of being piled into by the titania nanoparticles of 3 ~ 5nm, wherein; Nanometer honeycomb mean pore size is 50 ~ 80nm, and the honeycomb wall mean thickness is 20 ~ 30nm.
Above-mentioned surface irregularity nano titania honey-combed method for manufacturing 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; Behind the air drying, in the terepthaloyl moietie electrolytic solution of massfraction 0.25-0.75% Neutral ammonium fluoride, volume(tric)fraction 1% water, with the titanium sheet as anode; Platinum electrode is as negative electrode, and anodic oxidation obtains titanium dioxide nano-pipe array thin film under voltage 40-60V condition;
2) after the titanium dioxide nano-pipe array thin film that step 1) is obtained joins and at room temperature reacts 8 minutes to 168 hours in Pottasium Hydroxide that volumetric molar concentration is 1-8mol/L or the sodium hydroxide solution; The Nano tube array of titanium dioxide reaction forms the nano wire in honeycomb and the honeycomb, and the unordered titanium dioxide layer of top covering one deck constitutes titania coextruded film;
3) with step 2) to add volumetric molar concentration be in the acetic acid or Spirit of Mindererus of 0.3-1mol/L for the laminated film that obtains; After handling 5-60 minute under the room temperature; Remove surperficial unordered titanium dioxide layer in 5 minutes to 15 minutes in deionized water for ultrasonic, obtain the coarse nano titania honey-combed of amorphous surfaces film;
4) the coarse nano titania honey-combed of the amorphous surfaces film that step 3) is obtained places retort furnace, in air atmosphere, with the temperature rise rate of 10 ℃/min, is warming up to 400-500 ℃ of insulation 0.5-5 hour, cools to room temperature with the furnace; Finally obtain Detitanium-ore-type surface irregularity nano titania honey-combed 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 mean diameter of honeycomb can be controlled through the aperture of control forerunner nanotube, and the control of the diameter of nanotube can directly realize through changing anodic oxidation voltage.Compare the Nano tube array of titanium dioxide that anodic oxidation forms, this film has bigger specific surface area.
Description of drawings
Fig. 1 is the SEM figure of embodiment 2 obtained surface irregularity nano titania honey-combed thin film planars.
Fig. 2 is the local SEM figure that amplify of embodiment 2 obtained surface irregularity nano titania honey-combed thin film planars.
Fig. 3 is the TEM figure of embodiment 2 obtained surface irregularity nano titania honey-combed side surface of 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 20x15mm
2, the pure titanium sheet of the polishing attitude of thickness 0.1mm 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 0.324g at 100ml then, with titanium as anode, with platinum electrode as negative electrode; Electrode distance 3cm, voltage 40V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 1h, and in treating processes, continue to stir electrolytic solution; The sample that obtains ultrasonic cleaning in ethanol is immersed into the 1mol/L potassium hydroxide solution of 10ml then, leaves standstill 30min under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into the 0.5mol/L acetum of 10ml, is left standstill 30min under 25 ℃, take out sample with deionized water rinsing to neutral, deionized water for ultrasonic is cleaned 5min; At last the sample of s.t. 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 on the titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 5 μ m, is 52nm by mean pore size, and average wall thickness is that the shaggy nano titania honeycomb of 25nm constitutes.
Embodiment two
With area 20x15mm
2, the pure titanium sheet of the polishing attitude of thickness 0.1mm 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 0.324g 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 2h, and in treating processes, continue to stir electrolytic solution; The sample that obtains ultrasonic cleaning in ethanol is immersed into the 1mol/L potassium hydroxide solution of 10ml then, leaves standstill 30min under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into the 0.5mol/L acetum of 10ml, is left standstill 60min under 25 ℃, take out sample with deionized water rinsing to neutral, ultrasonic cleaning 5min in the aqueous solution; At last the sample of s.t. 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 on the titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 8 μ m, is 65nm by mean pore size, and average wall thickness is that the shaggy nano titania honeycomb of 20nm constitutes.
Embodiment three
With area 20x15mm
2, the pure titanium sheet of the polishing attitude of thickness 0.1mm 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 0.324g 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 the 3mol/L potassium hydroxide solution of 10ml then, leaves standstill 2h under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into the 0.5mol/L Spirit of Mindererus of 10ml, is left standstill 60min under 25 ℃, take out sample with deionized water rinsing to neutral, ultrasonic cleaning 5min in the aqueous solution; At last the sample of s.t. 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 on the titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 17 μ m, is 65nm by mean pore size, and average wall thickness is that the shaggy nano titania honeycomb of 20nm constitutes.
Embodiment four
With area 20x15mm
2, the pure titanium sheet of the polishing attitude of thickness 0.1mm 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 0.324g 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 the 6mol/L sodium hydroxide solution of 10ml then, leaves standstill 7h under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into the 1mol/L acetum of 10ml, is left standstill 1h under 25 ℃, take out sample with deionized water rinsing to neutral, ultrasonic cleaning 5min in the aqueous solution; At last the sample of s.t. is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 500 ℃ are incubated 3h down, cool to room temperature with the furnace.Finally on the titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 32 μ m, is 80nm by mean pore size, and average wall thickness is that the shaggy nano titania honeycomb of 30nm constitutes.
Claims (2)
1. surface irregularity nano titania honey-combed film; This film is formed on the matrix of metal titanium, it is characterized in that this film thickness is 2 ~ 40 μ m; It is the honey-combed of being piled into by the titania nanoparticles of 3 ~ 5nm; Wherein, nanometer honeycomb mean pore size is 50 ~ 80nm, and the honeycomb wall mean thickness is 20 ~ 30nm.
2. one kind prepares the described surface irregularity nano titania of claim 1 honey-combed film process, it 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; Behind the air drying, in the terepthaloyl moietie electrolytic solution of massfraction 0.25-0.75% Neutral ammonium fluoride, volume(tric)fraction 1% water, with the titanium sheet as anode; Platinum electrode is as negative electrode, and anodic oxidation obtains titanium dioxide nano-pipe array thin film under voltage 40-60V condition;
2) after the titanium dioxide nano-pipe array thin film that step 1) is obtained joins and at room temperature reacts 8 minutes to 168 hours in Pottasium Hydroxide that volumetric molar concentration is 1-8mol/L or the sodium hydroxide solution; The Nano tube array of titanium dioxide reaction forms the nano wire in honeycomb and the honeycomb, and the unordered titanium dioxide layer of top covering one deck constitutes titania coextruded film;
3) with step 2) to add volumetric molar concentration be in the acetic acid or acetate solution of 0.3-1mol/L for the laminated film that obtains; After handling 7-60 minute under the room temperature; Remove surperficial unordered titanium dioxide layer at deionized water for ultrasonic 5-15 minute, obtain the coarse nano titania honey-combed of amorphous surfaces film;
4) the coarse nano titania honey-combed of the amorphous surfaces film that step 3) is obtained places retort furnace, in air atmosphere, with the temperature rise rate of 10 ℃/min, is warming up to 400-500 ℃ of insulation 0.5-5 hour, cools to room temperature with the furnace; Finally obtain Detitanium-ore-type surface irregularity nano titania honey-combed film.
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| CN103695984A (en) * | 2013-11-28 | 2014-04-02 | 中国科学院合肥物质科学研究院 | Method for preparing nanoring array SERS (Surface Enhanced Raman Spectroscopy) substrate assembled through Ag nanoparticles |
| CN105590838A (en) * | 2015-12-25 | 2016-05-18 | 台州学院 | Ferromagnetic TiO2 semi semiconductor material, preparation method and spinning electronic device |
| CN106245093A (en) * | 2016-08-31 | 2016-12-21 | 昆明市口腔医院 | Planting material surface is through the preparation method of implantation body's nano-tube array of secondary anode and reaming and surface hydrophilicity |
| CN104309055B (en) * | 2013-10-31 | 2018-03-27 | 比亚迪股份有限公司 | The manufacture method and metal-resin composite of metal-resin composite |
| CN110573660A (en) * | 2017-04-13 | 2019-12-13 | 惠普发展公司，有限责任合伙企业 | Treating alloy substrates having oxide layers |
| CN113699575A (en) * | 2021-08-25 | 2021-11-26 | 江苏城乡建设职业学院 | Preparation method of titanium dioxide nanotube |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674706A (en) * | 2012-06-01 | 2012-09-19 | 天津大学 | Method for preparing titanium dioxide nano multi-level structure thin film on conductive glass |
| CN104309055B (en) * | 2013-10-31 | 2018-03-27 | 比亚迪股份有限公司 | The manufacture method and metal-resin composite of metal-resin composite |
| CN103695984A (en) * | 2013-11-28 | 2014-04-02 | 中国科学院合肥物质科学研究院 | Method for preparing nanoring array SERS (Surface Enhanced Raman Spectroscopy) substrate assembled through Ag nanoparticles |
| CN103695984B (en) * | 2013-11-28 | 2016-05-11 | 中国科学院合肥物质科学研究院 | A kind of preparation method of the nano-rings array SERS substrate of being assembled by Ag nano particle |
| CN105590838A (en) * | 2015-12-25 | 2016-05-18 | 台州学院 | Ferromagnetic TiO2 semi semiconductor material, preparation method and spinning electronic device |
| CN105590838B (en) * | 2015-12-25 | 2018-01-26 | 刘彦平 | Ferromagnetism TiO2Semi-conducting material, preparation method, spin electric device |
| CN106245093A (en) * | 2016-08-31 | 2016-12-21 | 昆明市口腔医院 | Planting material surface is through the preparation method of implantation body's nano-tube array of secondary anode and reaming and surface hydrophilicity |
| CN110573660A (en) * | 2017-04-13 | 2019-12-13 | 惠普发展公司，有限责任合伙企业 | Treating alloy substrates having oxide layers |
| CN113699575A (en) * | 2021-08-25 | 2021-11-26 | 江苏城乡建设职业学院 | Preparation method of titanium dioxide nanotube |
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