CN102383164B - 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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- CN102383164B CN102383164B CN201110348865.3A CN201110348865A CN102383164B CN 102383164 B CN102383164 B CN 102383164B CN 201110348865 A CN201110348865 A CN 201110348865A CN 102383164 B CN102383164 B CN 102383164B
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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 a kind of titanium dioxide nano-honeycomb nested nano wire film and preparation method, belong to titanium dioxide nano material technology.
Background technology
Nano titanium oxide is because its unique energy band structure, good conduction property and chemical stability and be widely used in preparing the anode of dye sensitization solar battery.Traditional anode adopts titania nanoparticles slurry to apply and prepares.In order to obtain high performance electron transport ability, the nano-array film that two dimension is disperseed starts to be used to replace 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.Nano titania array prepared by these methods is inner because monomer nano wire (pipe, rod), in the inhomogeneous capillary field of force, tends to lateral bending and reunites, and loses the characteristic of monodimension nanometer material, and then has affected its application performance.
In recent years, the studied confirmation of coaxial many walls Nano tube array of titanium dioxide has better properties than single wall titania nanotube.Many walls nanotube is compared single-walled nanotube larger specific surface area, and simultaneously inner nanotube, because in symmetrical outer lumen and be not subject to capillary force effect, therefore lateral bending can not occur reunite, and then have better electronic transmission performance.These advantages make multi-walled pipes have better over-all properties than single-walled pipe.The method of 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 dioxide.About film of the embedded nano-wire array of nano titania honeycomb and preparation method thereof, have not yet to see relevant report, this structure has the advantage similar to multi-walled pipes array.
Summary of the invention
The object of the invention aims to provide a kind of film and preparation method of titanium dioxide nano-honeycomb nested nano-wire array.Described film has good conduction property and chemical stability, and its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of film of titanium dioxide nano-honeycomb nested nano-wire array, 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 consists 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 hole wall mean thickness is 10nm, and the diameter of nano wire is 40～55nm.
The method for manufacturing thin film of above-mentioned titanium dioxide nano-honeycomb nested nano-wire array, is characterized in that comprising the following steps:
1) by block industrially pure titanium material at acetone, deionized water for ultrasonic is cleaned, after dry, add in ethylene glycol electrolytic solution, wherein this electrolytic solution is containing massfraction 0.25-0.75% Neutral ammonium fluoride and containing volume fraction 1% water, then take titanium as anode, the platinum of take obtains titanium dioxide nano-pipe array thin film as negative electrode anodic oxidation under voltage 40-60V condition;
2) by step 1) titanium dioxide nano-pipe array thin film that obtains 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, in Nano tube array of titanium dioxide, form the nano wire in honeycomb and honeycomb, and cover 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 hydrochloric acid of 0.3-1mol/L for the laminated film that obtains, under room temperature, process and within 10-60 minute, obtain the nested nano-wire array film of amorphous titania nanometer honeycomb;
4) by step 3) the nested nano-wire array film of amorphous titania nanometer honeycomb that obtains under air atmosphere, with 10 ℃/min of temperature rise rate, be warming up to 400-500 ℃ of insulation 1-5 hour, then cool to room temperature with the furnace; Finally obtain the embedded nano-wire array film of anatase titanium dioxide nanometer honeycomb.
Compared with prior art, the invention has the beneficial effects as follows: simple to operate, cost is low.Equipment is common anodic oxidation device, incinerator, large-scale or complex apparatus without other.The mean diameter of nano wire can be controlled by controlling the aperture of forerunner's nanotube, and the diameter control of nanotube may be realized by changing anodic oxidation voltage easily.Compare independent nano wire or nano-tube array, this film has larger specific surface area., can not there is lateral bending due to the symmetrical capillary field of force and contact with hole wall in nano wire central position in corresponding nanoporous of preparation, thereby kept the resolution of nanowire height.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the obtained titanium dioxide nano-honeycomb nested nano-wire array film of embodiment 2 plane
Fig. 2 is the SEM figure of the obtained titanium dioxide nano-honeycomb nested nano-wire array film of embodiment 2 side
Fig. 3 is the TEM figure of the obtained titanium dioxide nano-honeycomb nested nano-wire array film of embodiment 2
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 polishing state pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; Then the Neutral ammonium fluoride that comprises 0.25% massfraction in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, using titanium as anode, using 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 then immersed into 3mol/L potassium hydroxide solution, and standing 30min at 25 ℃ takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, standing 1h at 25 ℃, takes out with deionized water rinsing to neutral; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 3h at 400 ℃, cools to room temperature with the furnace.The most finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 2 μ m, by mean pore size, is 84nm, and the titanium dioxide nanowire array that the mean diameter of inlaying in the honeycomb that hole wall mean thickness is 10nm and honeycomb is 43nm forms.
Embodiment bis-
By area 20x15mm
2, the polishing state pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; Then the Neutral ammonium fluoride that comprises 0.25% massfraction in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, using titanium as anode, using 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 then immersed into 2mol/L potassium hydroxide solution, and standing 12h at 25 ℃ takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, standing 1h at 25 ℃, takes out with deionized water rinsing to neutral; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 1h at 450 ℃, cools to room temperature with the furnace.The most finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 3.6 μ m, by mean pore size, is 90nm, and the titanium dioxide nanowire array that the mean diameter of inlaying in the honeycomb that hole wall mean thickness is 10nm and honeycomb is 47nm forms.
Embodiment tri-
By area 20x15mm
2, the polishing state pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; Then the Neutral ammonium fluoride that comprises 0.25% massfraction in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, using titanium as anode, using 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 then immersed into 1mol/L sodium hydroxide solution, and standing 48h at 25 ℃ takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, standing 1h at 25 ℃, takes out with deionized water rinsing to neutral; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 1h at 500 ℃, cools to room temperature with the furnace.The most finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 3.3 μ m, by mean pore size, is 95nm, and the titanium dioxide nanowire array that the mean diameter of inlaying in the honeycomb that hole wall mean thickness is 10nm and honeycomb is 50nm forms.
Embodiment tetra-
By area 20x15mm
2, the polishing state pure titanium foil of thickness 0.1mm is successively at acetone, and deionized water for ultrasonic is cleaned 10min; Then the Neutral ammonium fluoride that comprises 0.25% massfraction in 100ml, in the ethylene glycol solution of the deionized water of 1% volume ratio, using titanium as anode, using 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 then immersed into 2mol/L potassium hydroxide solution, and standing 72h at 25 ℃ takes out with deionized water rinsing to neutral; Then the film of alkaline purification is put into 0.57mol/L hydrochloric acid, standing 1h at 25 ℃, takes out with deionized water rinsing to neutral; Finally the sample of acid treatment is heat-treated under air atmosphere, 10 ℃/min of temperature rise rate, is incubated 1h at 450 ℃, cools to room temperature with the furnace.The most finally on titanium sheet matrix, obtain one deck anatase titania film, this film thickness is 7 μ m, by mean pore size, is 95nm, and the titanium dioxide nanowire array that the mean diameter of inlaying in the honeycomb that hole wall mean thickness is 10nm and honeycomb is 50nm forms.
Claims (2)
1. the film of a titanium dioxide nano-honeycomb nested nano-wire array, this film-shaped is formed on the matrix of metal titanium, it is characterized in that, this film thickness is 2～40 μ m, it consists 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, hole wall mean thickness is 10nm, and the diameter of nano wire is 40～55nm.
2. a film process of preparing titanium dioxide nano-honeycomb nested nano-wire array claimed in claim 1, is characterized in that comprising the following steps:
1) by block industrially pure titanium material at acetone, deionized water for ultrasonic is cleaned, after dry, add in ethylene glycol electrolytic solution, wherein this electrolytic solution is containing massfraction 0.25-0.75% Neutral ammonium fluoride and containing volume fraction 1% water, then take titanium as anode, the platinum of take obtains titanium dioxide nano-pipe array thin film as negative electrode anodic oxidation under voltage 40-60V condition;
2) by step 1) titanium dioxide nano-pipe array thin film that obtains 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, in Nano tube array of titanium dioxide, form the nano wire in honeycomb and honeycomb, and cover 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 hydrochloric acid of 0.3-1mol/L for the laminated film that obtains, under room temperature, process and within 10-60 minute, obtain the nested nano-wire array film of amorphous titania nanometer honeycomb;
4) by step 3) the nested nano-wire array film of amorphous titania nanometer honeycomb that obtains under air atmosphere, with 10 ℃/min of temperature rise rate, be warming up to 400-500 ℃ of insulation 1-5 hour, then cool to room temperature with the furnace; Finally obtain the embedded nano-wire array film of anatase titanium dioxide nanometer honeycomb.
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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 |
| 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 |
| 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 |
| 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 |
| CN104269274B (en) * | 2014-10-15 | 2017-03-08 | 北京纳米能源与***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 |
| 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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