CN102383164A - Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof - Google Patents
Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof Download PDFInfo
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- CN102383164A CN102383164A CN2011103488653A CN201110348865A CN102383164A CN 102383164 A CN102383164 A CN 102383164A CN 2011103488653 A CN2011103488653 A CN 2011103488653A CN 201110348865 A CN201110348865 A CN 201110348865A CN 102383164 A CN102383164 A CN 102383164A
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Abstract
The invention discloses a titanium dioxide nano-honeycomb nested nanowire array film and a preparation method thereof. The film is formed on a substrate of metallic titanium and consists of a titanium dioxide nano-honeycomb and a nanowire array nested in the center of the nano-honeycomb. The preparation method comprises the following steps of: oxidizing an anode made of a pure titanium material to obtain a titanium dioxide nanotube array film; soaking the film in a strong alkaline solution; and pickling and calcining to obtain the anatase type titanium dioxide nano-honeycomb nesting nanowire array film. The method is simple and convenient to implement. The diameter of the nanowire in the prepared film can be controlled by controlling voltage at the early stage of anode oxidization. The nanowire is positioned in the center of a honeycomb hole and cannot bend laterally to contact the hole wall due to a symmetrical capillary force field, so that the nanowire is separated highly. Compared with a single nanowire or nanotube array, the film has larger specific surface area.
Description
Technical field
The present invention relates to nested nano wire film of a kind of nano titania honeycomb and preparation method, belong to the titanium dioxide nano material technology.
Background technology
Nano titanium oxide is because its unique energy band structure, good conduction property and chemicalstability and be widely used in preparing the anode of dye sensitization solar battery.Traditional anode adopts the titania nanoparticles slurry to apply and prepares.In order to obtain the high performance electronic transmittability, two-dimentional dispersive nano-array film begins to be used and replaces particle packing film preparation anode.These nano-arrays comprise nano wire, nanometer rod, nano-tube array.The method of these nano-arrays of preparation comprises hydrothermal treatment consists, anodic oxidation and template at present.The nano titania array of these method preparations is inner to be tended to lateral bending and reunites because monomer nano wire (pipe, rod) is in the uneven capillary field of force, loses the characteristic of monodimension nanometer material, and then has influenced its application performance.
In recent years, coaxial many walls Nano tube array of titanium dioxide is studied confirmation and has better properties than single wall titania nanotube.Many walls nanotube is compared single-walled nanotube has bigger specific surface area, and inner simultaneously nanotube does not receive the capillary force effect because of being in the symmetric outer lumen, therefore lateral bending can not take place reunite, and then have better electronic transmission performance.These advantages make multi-walled pipes have comprehensive performance than single-walled pipe.The method for preparing at present multi-walled pipes has template, anonizing.Template requires repeatedly molding, and anonizing also requires initial titanium material alloying, and the multi-walled pipes of preparing is not pure titanium oxide.About film of the embedded nano-wire array of nano titania honeycomb and preparation method thereof, do not see relevant report at present as yet, this structure has the advantage similar with the multi-walled pipes array.
Summary of the invention
The object of the invention aims to provide the film and the preparation method of the nested nano-wire array of a kind of nano titania honeycomb.Described film has good conduction property and chemicalstability, and its preparation method process is simple.
The present invention realizes through following technical proposals, and the film of the nested nano-wire array of a kind of nano titania honeycomb, this film are formed on the matrix of metal titanium; It is characterized in that this film thickness is 2～40 μ m, it is made up of nano titania honeycomb and the single nano-wire array that is nested in nanometer honeycomb center; Wherein, Nanometer honeycomb mean pore size is 80～95nm, and the hole wall mean thickness is 10nm, and the diameter of nano wire is 40～55nm.
The method for manufacturing thin film of the nested nano-wire array of above-mentioned nano titania honeycomb is characterized in that may further comprise the steps:
1) with block industrially pure titanium material at acetone; Deionized water for ultrasonic is cleaned; Dry back adds in the terepthaloyl moietie electrolytic solution; Wherein this electrolytic solution contains massfraction 0.25-0.75% Neutral ammonium fluoride and contains volume(tric)fraction 1% water, is anode with the titanium then, is that negative electrode anodic oxidation under voltage 40-60V condition obtains titanium dioxide nano-pipe array thin film with platinum;
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; In Nano tube array of titanium dioxide, form 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 hydrochloric acid of 0.3-1mol/L for the laminated film that obtains, under room temperature, handles obtaining the nested nano-wire array film of amorphous titania nanometer honeycomb in 10-60 minute;
4) the nested nano-wire array film of amorphous titania nanometer honeycomb that step 3) is obtained with 10 ℃/min of temperature rise rate, is warming up to 400-500 ℃ of insulation 1-5 hour under air atmosphere, cool to room temperature then with the furnace; Obtain the embedded nano-wire array film of anatase titanium dioxide nanometer honeycomb at last.
Compared with prior art, the invention has the beneficial effects as follows: simple to operate, cost is low.Equipment is common anodic oxidation device, and incinerator need not other large-scale or complex apparatus.The mean diameter of nano wire can be controlled through the aperture of control forerunner nanotube, and the control of the diameter of nanotube possibly realize through changing anodic oxidation voltage easily.Compare independent nano wire or nano-tube array, this film has bigger specific surface area.The nano wire of preparation is in central position in the corresponding nanoporous, because the symmetric capillary field of force and can lateral bending not take place and contact with hole wall, thereby has kept the separating size of nanowire height.
Description of drawings
Fig. 1 is the nested nano-wire array film planar of embodiment 2 obtained nano titania honeycombs SEM figure
Fig. 2 is the lateral SEM figure of the nested nano-wire array film of embodiment 2 obtained nano titania honeycombs
Fig. 3 is the TEM figure of the nested nano-wire array film of embodiment 2 obtained nano titania honeycombs
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 polishing attitude pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; The Neutral ammonium fluoride that comprises 0.25% massfraction then in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, with titanium as anode; With platinum electrode as negative electrode; Electrode distance 2.5cm, voltage 40V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 1h, and in treating processes, keep stirring electrolytic solution; The goods that obtain ultrasonic cleaning in alcohol is immersed into the 3mol/L potassium hydroxide solution then, leaves standstill 30min under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, leave standstill 1h under 25 ℃, take out with deionized water rinsing to neutral; At last the sample of s.t. is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 400 ℃ are incubated 3h down, cool to room temperature with the furnace.The most finally obtain one deck anatase titania film on the titanium sheet matrix, this film thickness is 2 μ m, is 84nm by mean pore size, and the hole wall mean thickness is that the mean diameter of inlaying in honeycomb and the honeycomb of 10nm is that the titanium dioxide nanowire array of 43nm constitutes.
Embodiment two
With area 20x15mm
2, the polishing attitude pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; The Neutral ammonium fluoride that comprises 0.25% massfraction then in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, with titanium as anode; With platinum electrode as negative electrode; Electrode distance 2.5cm, voltage 50V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 2h, and in treating processes, keep stirring electrolytic solution; The goods that obtain ultrasonic cleaning in alcohol is immersed into the 2mol/L potassium hydroxide solution then, leaves standstill 12h under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, leave standstill 1h under 25 ℃, take out with deionized water rinsing to neutral; At last the sample of s.t. is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 450 ℃ are incubated 1h down, cool to room temperature with the furnace.The most finally obtain one deck anatase titania film on the titanium sheet matrix, this film thickness is 3.6 μ m, is 90nm by mean pore size, and the hole wall mean thickness is that the mean diameter of inlaying in honeycomb and the honeycomb of 10nm is that the titanium dioxide nanowire array of 47nm constitutes.
Embodiment three
With area 20x15mm
2, the polishing attitude pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; The Neutral ammonium fluoride that comprises 0.25% massfraction then in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, with titanium as anode; With platinum electrode as negative electrode; Electrode distance 2.5cm, voltage 60V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 2h, and in treating processes, keep stirring electrolytic solution; The goods that obtain ultrasonic cleaning in alcohol is immersed into the 1mol/L sodium hydroxide solution then, leaves standstill 48h under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, leave standstill 1h under 25 ℃, take out with deionized water rinsing to neutral; At last the sample of s.t. is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 500 ℃ are incubated 1h down, cool to room temperature with the furnace.The most finally obtain one deck anatase titania film on the titanium sheet matrix, this film thickness is 3.3 μ m, is 95nm by mean pore size, and the hole wall mean thickness is that the mean diameter of inlaying in honeycomb and the honeycomb of 10nm is that the titanium dioxide nanowire array of 50nm constitutes.
Embodiment four
With area 20x15mm
2, the polishing attitude pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; The Neutral ammonium fluoride that comprises 0.25% massfraction then in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, with titanium as anode; With platinum electrode as negative electrode; Electrode distance 2.5cm, voltage 60V, electrolyzer keeps 25 ℃ of constant temperature; Anodic oxidation 6h, and in treating processes, keep stirring electrolytic solution; The goods that obtain ultrasonic cleaning in alcohol is immersed into the 2mol/L potassium hydroxide solution then, leaves standstill 72h under 25 ℃, takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, leave standstill 1h under 25 ℃, take out with deionized water rinsing to neutral; At last the sample of s.t. is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, 450 ℃ are incubated 1h down, cool to room temperature with the furnace.The most finally obtain one deck anatase titania film on the titanium sheet matrix, this film thickness is 7 μ m, is 95nm by mean pore size, and the hole wall mean thickness is that the mean diameter of inlaying in honeycomb and the honeycomb of 10nm is that the titanium dioxide nanowire array of 50nm constitutes.
Claims (2)
1. the film of the nested nano-wire array of nano titania honeycomb, this film are formed on the matrix of metal titanium, it is characterized in that; This film thickness is 2～40 μ m; It is made up of nano titania honeycomb and the single nano-wire array that is nested in nanometer honeycomb center, and wherein, nanometer honeycomb mean pore size is 80～95nm; The hole wall mean thickness is 10hm, and the diameter of nano wire is 40～55nm.
2. film process for preparing the nested nano-wire array of the described nano titania honeycomb of claim 1 is characterized in that may further comprise the steps:
1) with block industrially pure titanium material at acetone; Deionized water for ultrasonic is cleaned; Dry back adds in the terepthaloyl moietie electrolytic solution; Wherein this electrolytic solution contains massfraction 0.25-0.75% Neutral ammonium fluoride and contains volume(tric)fraction 1% water, is anode with the titanium then, is that negative electrode anodic oxidation under voltage 40-60V condition obtains titanium dioxide nano-pipe array thin film with platinum;
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; In Nano tube array of titanium dioxide, form 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 hydrochloric acid of 0.3-1mol/L for the laminated film that obtains, under room temperature, handles obtaining the nested nano-wire array film of amorphous titania nanometer honeycomb in 10-60 minute;
4) the nested nano-wire array film of amorphous titania nanometer honeycomb that step 3) is obtained with 10 ℃/min of temperature rise rate, is warming up to 400-500 ℃ of insulation 1-5 hour under air atmosphere, cool to room temperature then with the furnace; Obtain the embedded nano-wire array film of anatase titanium dioxide nanometer honeycomb at last.
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Cited By (9)
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| CN102677123A (en) * | 2012-06-01 | 2012-09-19 | 天津大学 | Preparation method of independent titanium dioxide nanotube array film |
| 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 |
| CN103243336A (en) * | 2013-05-15 | 2013-08-14 | 中南大学 | Preparation method of nano platinum/titanium dioxide nanotube array composite material |
| 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 |
| 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 |
| CN104269274A (en) * | 2014-10-15 | 2015-01-07 | 北京纳米能源与系统研究所 | Titanium/titanium dioxide micrometer cone-nanowire electrode and preparation method and application thereof |
| CN113699575A (en) * | 2021-08-25 | 2021-11-26 | 江苏城乡建设职业学院 | Preparation method of titanium dioxide nanotube |
| CN115090279A (en) * | 2022-07-08 | 2022-09-23 | 中国计量大学 | Titanium dioxide supported catalyst for purifying malodorous VOCs in grain and oil processing industry and preparation method thereof |
| CN116393123A (en) * | 2023-06-08 | 2023-07-07 | 成都达奇科技股份有限公司 | Preparation method of non-carbon-based denitration catalyst |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102677123A (en) * | 2012-06-01 | 2012-09-19 | 天津大学 | Preparation method of independent titanium dioxide nanotube array film |
| CN103243336B (en) * | 2013-05-15 | 2015-08-12 | 中南大学 | A kind of preparation method of nano platinum/titanium dioxide nanotube array composite material |
| CN103243336A (en) * | 2013-05-15 | 2013-08-14 | 中南大学 | Preparation method of nano platinum/titanium dioxide nanotube array composite material |
| 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 |
| 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 |
| CN104269274A (en) * | 2014-10-15 | 2015-01-07 | 北京纳米能源与系统研究所 | Titanium/titanium dioxide micrometer cone-nanowire electrode and preparation method and application thereof |
| CN104269274B (en) * | 2014-10-15 | 2017-03-08 | 北京纳米能源与系统研究所 | Titanium/titanium dioxide micrometer cone nano line electrode and its preparation method and application |
| CN113699575A (en) * | 2021-08-25 | 2021-11-26 | 江苏城乡建设职业学院 | Preparation method of titanium dioxide nanotube |
| CN115090279A (en) * | 2022-07-08 | 2022-09-23 | 中国计量大学 | Titanium dioxide supported catalyst for purifying malodorous VOCs in grain and oil processing industry and preparation method thereof |
| CN115090279B (en) * | 2022-07-08 | 2023-10-10 | 中国计量大学 | Titanium dioxide supported catalyst for purifying malodorous VOCs in grain and oil processing industry and preparation method thereof |
| CN116393123A (en) * | 2023-06-08 | 2023-07-07 | 成都达奇科技股份有限公司 | Preparation method of non-carbon-based denitration catalyst |
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