CN102418133B - 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
- Publication number
- CN102418133B CN102418133B CN201110410311.1A CN201110410311A CN102418133B CN 102418133 B CN102418133 B CN 102418133B CN 201110410311 A CN201110410311 A CN 201110410311A CN 102418133 B CN102418133 B CN 102418133B
- Authority
- CN
- China
- Prior art keywords
- thin film
- titanium dioxide
- nano
- honeycomb
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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 honeycomb structure film and preparation method, belong to titanium dioxide nano material technology.
Background technology
Nano titanium oxide is a kind of important inorganic functional material, because it has unique energy band structure and chemical stability and is extensively used as the light anode material of dye sensitization solar battery.Traditional light anode is generally titanium dioxide nanocrystalline particle film, and in recent years, nano titania array structure is because its unique constitutional features obtains people's extensive concern.Nano titania array structure can increase the scattering of photon, has increased the transmission route of photon in electrode materials, is conducive to strengthen the absorption of light; Meanwhile, array electrode material is owing to having ordered structure, and perpendicular to electrode surface, can reduce to greatest extent the transmission route of electric charge in electrode materials, reduces the compound chance in interface.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, affects its application performance.
The method that titanium dioxide nano-pipe array thin film surface roughening is processed mainly contains two kinds, and a kind of method is by controlling anodised process, changes electrolyte ingredient, but this method is when increasing specific surface area, also can make caliber become large, tube wall thickening; Another kind method is to adopt titanium tetrachloride solution to process, at titania nanotube surface appendix titania nanoparticles, but this method reaction process is wayward, and the nano particle of formation is inhomogeneous, appendix makes tube wall thickening, has reduced to a certain extent specific surface area.The present invention, by the reaction process of dissolving tube wall and adsorbing, has avoided increase thickness of pipe, the surface irregularity nano titania honeycomb structure of preparation, and increasing specific surface area, strengthens 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 honeycomb structure film and preparation method.Described film has good photoelectric properties and chemical stability, and the method preparation process is simple, easy handling.
The present invention is achieved through the following technical solutions, a kind of surface irregularity nano titania honeycomb structure film, this film-shaped is formed on the matrix of metal titanium, it is characterized in that, this film thickness is 2 ~ 40 μ m, and it is the honeycomb structure that the titania nanoparticles by 3 ~ 5nm is piled into, wherein, nanometer honeycomb mean pore size is 50 ~ 80nm, and honeycomb wall mean thickness is 20 ~ 30nm.
Above-mentioned surface irregularity nano titania honeycomb structure method for manufacturing thin film, is characterized in that comprising the following steps:
1) by industrially pure titanium sheet respectively at deionized water, ultrasonic cleaning in ethanol and acetone, after air drying, in the ethylene glycol electrolytic solution of massfraction 0.25-0.75% Neutral ammonium fluoride, volume fraction 1% water, using titanium sheet as anode, platinum electrode is as negative electrode, and under voltage 40-60V condition, anodic oxidation obtains titanium dioxide nano-pipe array thin film;
2) titanium dioxide nano-pipe array thin film step 1) being obtained joins in potassium hydroxide that volumetric molar concentration is 1-8mol/L or sodium hydroxide solution and at room temperature reacts after 8 minutes to 168 hours, Nano tube array of titanium dioxide reaction forms the nano wire in honeycomb and honeycomb, and covers the unordered titanium dioxide layer formation of one deck titania coextruded film above;
3) by 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, under room temperature, process after 5-60 minute, in deionized water for ultrasonic, within 5 minutes to 15 minutes, remove surperficial unordered titanium dioxide layer, obtain the coarse nano titania honeycomb structure of amorphous surfaces film;
4) the coarse nano titania honeycomb structure of amorphous surfaces film step 3) being obtained is placed in 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 honeycomb structure film.
Compared with prior art, advantage of the present invention is: simple to operate, cost is low.Equipment is common anodic oxidation device, retort furnace, large-scale or complex apparatus without other.The mean diameter of honeycomb can be controlled by controlling the aperture of forerunner's nanotube, and the diameter control of nanotube can directly be realized by changing anodic oxidation voltage.Compare the Nano tube array of titanium dioxide that anodic oxidation forms, this film has larger specific surface area.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the obtained surface irregularity nano titania of embodiment 2 honeycomb structure thin film planar.
Fig. 2 is the local SEM figure amplifying of the obtained surface irregularity nano titania of embodiment 2 honeycomb structure thin film planar.
Fig. 3 is the TEM figure of the obtained surface irregularity nano titania of embodiment 2 honeycomb structure side surface of thin film.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and these embodiment, just for the present invention is described, do not limit the present invention.
Embodiment mono-
By area 20x15mm
2, the pure titanium sheet of polishing state of thickness 0.1mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Then at 100ml, contain in the ethylene glycol solution of the Neutral ammonium fluoride of 0.324g, the deionized water of 1ml and 99ml, using titanium as anode, using 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 obtaining ultrasonic cleaning in ethanol, is then immersed into the 1mol/L potassium hydroxide solution of 10ml, and standing 30min at 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, standing 30min at 25 ℃, take out sample with deionized water rinsing to neutral, deionized water for ultrasonic is cleaned 5min; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 30min at 400 ℃, cools to room temperature with the furnace.Finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 5 μ m, by mean pore size, is 52nm, and the shaggy nano titania honeycomb that average wall thickness is 25nm forms.
Embodiment bis-
By area 20x15mm
2, the pure titanium sheet of polishing state of thickness 0.1mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Then at 100ml, contain in the ethylene glycol solution of the Neutral ammonium fluoride of 0.324g, the deionized water of 1ml and 99ml, using titanium as anode, using 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 obtaining ultrasonic cleaning in ethanol, is then immersed into the 1mol/L potassium hydroxide solution of 10ml, and standing 30min at 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, standing 60min at 25 ℃, take out sample with deionized water rinsing to neutral, ultrasonic cleaning 5min in the aqueous solution; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 30min at 450 ℃, cools to room temperature with the furnace.Finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 8 μ m, by mean pore size, is 65nm, and the shaggy nano titania honeycomb that average wall thickness is 20nm forms.
Embodiment tri-
By area 20x15mm
2, the pure titanium sheet of polishing state of thickness 0.1mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Then at 100ml, contain in the ethylene glycol solution of the Neutral ammonium fluoride of 0.324g, the deionized water of 1ml and 99ml, using titanium as anode, using 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 obtaining ultrasonic cleaning in ethanol, is then immersed into the 3mol/L potassium hydroxide solution of 10ml, and standing 2h at 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, standing 60min at 25 ℃, take out sample with deionized water rinsing to neutral, ultrasonic cleaning 5min in the aqueous solution; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 30min at 450 ℃, cools to room temperature with the furnace.Finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 17 μ m, by mean pore size, is 65nm, and the shaggy nano titania honeycomb that average wall thickness is 20nm forms.
Embodiment tetra-
By area 20x15mm
2, the pure titanium sheet of polishing state of thickness 0.1mm is successively at acetone, and ethanol and deionized water for ultrasonic are cleaned 10min; Then at 100ml, contain in the ethylene glycol solution of the Neutral ammonium fluoride of 0.324g, the deionized water of 1ml and 99ml, using titanium as anode, using 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 obtaining ultrasonic cleaning in ethanol, is then immersed into the 6mol/L sodium hydroxide solution of 10ml, and standing 7h at 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into the 1mol/L acetum of 10ml, standing 1h at 25 ℃, take out sample with deionized water rinsing to neutral, ultrasonic cleaning 5min in the aqueous solution; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 3h at 500 ℃, cools to room temperature with the furnace.Finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 32 μ m, by mean pore size, is 80nm, and the shaggy nano titania honeycomb that average wall thickness is 30nm forms.
Claims (1)
1. the preparation method of a surface irregularity nano titania honeycomb structure film, described surface irregularity nano titania honeycomb structure film-shaped is formed on the matrix of metal titanium, its thickness is 2 ~ 40 μ m, it is the honeycomb structure that the titania nanoparticles by 3 ~ 5nm is piled into, wherein, nanometer honeycomb mean pore size is 50 ~ 80nm, and honeycomb wall mean thickness is 20 ~ 30nm, it is characterized in that comprising the following steps:
1) by industrially pure titanium sheet respectively at deionized water, ultrasonic cleaning in ethanol and acetone, after air drying, in the ethylene glycol electrolytic solution of massfraction 0.25-0.75% Neutral ammonium fluoride, volume fraction 1% water, using titanium sheet as anode, platinum electrode is as negative electrode, and under voltage 40-60V condition, anodic oxidation obtains titanium dioxide nano-pipe array thin film;
2) titanium dioxide nano-pipe array thin film step 1) being obtained joins in potassium hydroxide that volumetric molar concentration is 1-8mol/L or sodium hydroxide solution and at room temperature reacts after 8 minutes to 168 hours, Nano tube array of titanium dioxide reaction forms the nano wire in honeycomb and honeycomb, and covers the unordered titanium dioxide layer formation of one deck titania coextruded film above;
3) by 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, under room temperature, process after 7-60 minute, at deionized water for ultrasonic 5-15 minute, remove surperficial unordered titanium dioxide layer, obtain the coarse nano titania honeycomb structure of amorphous surfaces film;
4) the coarse nano titania honeycomb structure of amorphous surfaces film step 3) being obtained is placed in 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 honeycomb structure film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110410311.1A CN102418133B (en) | 2011-12-12 | 2011-12-12 | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110410311.1A CN102418133B (en) | 2011-12-12 | 2011-12-12 | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102418133A CN102418133A (en) | 2012-04-18 |
| CN102418133B true CN102418133B (en) | 2014-02-12 |
Family
ID=45942771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110410311.1A Expired - Fee Related CN102418133B (en) | 2011-12-12 | 2011-12-12 | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102418133B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674706B (en) * | 2012-06-01 | 2014-07-09 | 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 |
| 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 |
| CN105590838B (en) * | 2015-12-25 | 2018-01-26 | 刘彦平 | Ferromagnetism TiO2Semi-conducting material, preparation method, spin electric device |
| CN106245093B (en) * | 2016-08-31 | 2019-01-22 | 昆明市口腔医院 | The preparation method and surface hydrophilicity of planting body nano-tube array of the planting material surface through secondary anode and reaming |
| WO2018190839A1 (en) * | 2017-04-13 | 2018-10-18 | Hewlett-Packard Development Company, L.P. | Treating alloy substrates having oxidized 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050103639A1 (en) * | 2003-11-18 | 2005-05-19 | Fu-Hsing Lu | Titanium dioxide film synthesizing method and the product thereof |
| CN101537208A (en) * | 2008-03-21 | 2009-09-23 | 中国科学院金属研究所 | Biological active coating on surface of titanium or titanium alloy and preparation method thereof |
| CN101748463A (en) * | 2008-12-02 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for preparing porous titanium dioxide nanotube array |
| CN102191529A (en) * | 2011-04-29 | 2011-09-21 | 中国科学院合肥物质科学研究院 | Honeycomb ordered titanium dioxide nanotube array film and preparation method thereof |
-
2011
- 2011-12-12 CN CN201110410311.1A patent/CN102418133B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050103639A1 (en) * | 2003-11-18 | 2005-05-19 | Fu-Hsing Lu | Titanium dioxide film synthesizing method and the product thereof |
| CN101537208A (en) * | 2008-03-21 | 2009-09-23 | 中国科学院金属研究所 | Biological active coating on surface of titanium or titanium alloy and preparation method thereof |
| CN101748463A (en) * | 2008-12-02 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for preparing porous titanium dioxide nanotube array |
| CN102191529A (en) * | 2011-04-29 | 2011-09-21 | 中国科学院合肥物质科学研究院 | Honeycomb ordered titanium dioxide nanotube array film and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| Fei Chu等.Performance Improvement of Dye-Sensitized Solar Cells Using Room-Temperature-Synthesized Hierarchical TiO2 Honeycomb Nanostructures.《American Chemical Society》.2013,第5卷(第15期),第7170-7175页. |
| Performance Improvement of Dye-Sensitized Solar Cells Using Room-Temperature-Synthesized Hierarchical TiO2 Honeycomb Nanostructures;Fei Chu等;《American Chemical Society》;20130814;第5卷(第15期);第7170-7175页 * |
| Ti02纳米管阵列的制备及其应用研究进展;杨娟等;《化工时刊》;20080909;第22卷(第9期);第56-60页 * |
| TiO2 cellular-protected nanowire array fabricated super-rapidly by the precipitation of colloids in the nanopores;Wei Li等;《J. Mater. Chem.》;20121231;第22卷(第27期);第13820-13825页 * |
| Wei Li等.TiO2 cellular-protected nanowire array fabricated super-rapidly by the precipitation of colloids in the nanopores.《J. Mater. Chem.》.2012,第22卷(第27期),第13820-13825页. |
| 杨娟等.Ti02纳米管阵列的制备及其应用研究进展.《化工时刊》.2008,第22卷(第9期),第56-60页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102418133A (en) | 2012-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102418133B (en) | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film | |
| CN102383164B (en) | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof | |
| CN102674706B (en) | Method for preparing titanium dioxide nano multi-level structure thin film on conductive glass | |
| CN101956223B (en) | Method for preparing cuprous oxide composite titanium dioxide nanotube array | |
| CN101187043A (en) | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance | |
| CN104874384B (en) | Preparation method of titanium dioxide thin film with micro-nano composite structure | |
| CN103285891A (en) | Preparation method of bismuth oxide halide-titanium oxide nanotube array composite photo-catalytic membrane | |
| CN101937946A (en) | Surface texture method of solar battery silicon slice | |
| CN102965710A (en) | Preparation of silver/cadmium sulfide-nanoparticle-comodified titanium dioxide nanotube array | |
| CN105088312A (en) | Method for preparing titania nanotube allay films | |
| CN101254947A (en) | Method for preparing titanium oxide nano-wire array | |
| CN106186205A (en) | A kind of micropore titanio tubular type multidimensional nano-pore embeds stannum antimony membrane electrode and preparation method thereof | |
| CN103395865A (en) | Titanium-base tubular ruthenium dioxide coating membrane electrode and preparation method thereof | |
| CN108560035A (en) | A kind of low cost preparation ZnO＆TiO2The method of hetero-junction thin-film | |
| CN102534727A (en) | Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device | |
| CN105776432B (en) | A kind of compound duct antimony-doped stannic oxide electrode of three-dimensional and its preparation method and application | |
| CN105129847B (en) | Preparation method of nanosheet composed of titanium dioxide nanotubes | |
| Liang et al. | Selective electrodeposition of Ni into the intertubular voids of anodic TiO2 nanotubes for improved photocatalytic properties | |
| CN104801295B (en) | Titanium oxide/tungsten oxide nano-composite film on surface of metallic titanium, preparation and application | |
| CN107326394B (en) | A method of it prepares with core-shell structure carbonitride modified titanic oxide light anode | |
| CN104362301A (en) | Carbon coated titanium-based lead dioxide positive plate for lead-acid storage battery | |
| CN106340404A (en) | Manufacturing method of high-dielectric nano-composite oxide film anode foil used for low voltage aluminum electrolytic capacitor | |
| CN104746129A (en) | Preparation method of immobilized single-crystal anatase TiO2 nanowire membrane layer | |
| CN106757056A (en) | A kind of preparation method of barium titanate/nano titania composite film material | |
| CN104022295A (en) | Direct methanol fuel cell PdAg/TiO2 nanotube electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140212 Termination date: 20171212 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |