CN102953110B - Preparation method of titanium dioxide core/shell nanometer cable array - Google Patents
Preparation method of titanium dioxide core/shell nanometer cable array Download PDFInfo
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- CN102953110B CN102953110B CN201210392780.XA CN201210392780A CN102953110B CN 102953110 B CN102953110 B CN 102953110B CN 201210392780 A CN201210392780 A CN 201210392780A CN 102953110 B CN102953110 B CN 102953110B
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Abstract
The invention discloses a preparation method of a titanium dioxide core/shell nanometer cable array. The method comprises: firstly, preparing a layer of TiO2 nanotube array film with small tube diameter on a titanium chip under a low oxidation voltage; and then, increasing the anode oxidation voltage, and obtaining a titanium dioxide nanotube array with large tube diameter below the titanium dioxide nanotube array with small tube diameter; performing ultrasonic oscillating; soaking the titanium dioxide nanotube array with a titanium chip substrate in a high-concentration alkaline solution, and cleaning the titanium dioxide nanotube array through deionized water; and soaking the titanium dioxide array in an acid solution for a period, taking out the titanium dioxide array, cleaning the titanium dioxide array with deionized water, and drying the titanium dioxide array to obtain the titanium dioxide core/shell nanometer cable array. The method is simple, feasible, quick and effective, the shape and outline of the product are controllable, and the method has practical value.
Description
Technical field
The present invention relates generally to kind of an a kind of pervasive chemical etching method, particularly relates to a kind of preparation method of titanium dioxide core/shell nanometer cable array
Background technology
Pure titanium sheet (is mainly the organic or inorganic ionogen of fluoride ion) in some ionogen, can be obtained the Nano tube array of titanium dioxide of ordered arrangement by anodic oxidation.These Nano tube array of titanium dioxide prepared by anonizing, because of the tubular structure of its uniqueness, high specific surface area and orderly arrangement mode, make it have broad application prospects at environment, the energy, biology and optical field.In recent years, people utilize anodised Nano tube array of titanium dioxide as template (being similar to porous anode alumina formwork), adopt electrochemical deposition technique nano wire such as filler metal, semi-conductor in titania nanotube, obtain the nano-cable such as metal/titanium dioxide, semi-conductor/titanium dioxide, to expand the Application Areas of anodic oxidation titania nanotube.But anodic oxidation film of Nano tube array of titanium dioxide is very crisp, easily break, the titanium sheet substrate that supports is difficult to shortcomings such as removing, titania nanotube low side through hole difficulty is large, constrains the use of titanium dioxide as template.Therefore probe into a kind of simple and effective synthetic method, prepare the controlled titanium dioxide nano thread/nanotube composite structure array of complex structure, parameter by significant.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of cheap, simple synthetic method, for the preparation of titanium dioxide nano thread/nanotube composite structure array that structural parameter are controlled.
The present invention is achieved by the following technical solutions:
A preparation method for titanium dioxide core/shell nanometer cable array, comprises the following steps:
(1) first by titaniferous amount be 94-96% tinsel be that in the ethanol of 1-2:1-2 and the mixing solutions of acetone, ultrasonic cleaning 60-70min, to remove the organism on surface, and then to clean with deionized water repeatedly at concentration ratio, and to dry;
(2) tinsel after cleaning being dried carries out anodic oxidation in containing the ethylene glycol solution of 0.20-0.30mol/L hydrofluoric acid, and wherein oxidation voltage is 10-20v, and oxidization time is 10-15min; Then increase anodic oxidation voltage to 40-60v, oxidation 1.5-2h, forms the Nano tube array of titanium dioxide that upper and lower two-layer large pipe with small pipe diameter is different;
(3) anodised tinsel is taken out, pass through sonic oscillation, the pipe with small pipe diameter titania nanotube prepared in small voltage anodic oxygen is separated from Large Diameter Pipeline Nano tube array of titanium dioxide, leaves surfacing, fissureless film of Nano tube array of titanium dioxide;
(4) configuration is containing 4mol/L alkaline solution, is soaked by the film of Nano tube array of titanium dioxide of preparation wherein after 2-4 h, washed with de-ionized water 1-5 minutes;
(5) acid solution of configuration containing 0.25-0.5mol/L, by the Nano tube array of titanium dioxide after immersion in alkaline solution, is immersed in 1.5-2 h in acid solution, and washed with de-ionized water is clean, dries, can obtain titanium dioxide core/shell nanometer cable array.
Acid solution in step (4) is KOH or NaOH solution.
Acid solution in step (5) is H
2sO
4, HCL or HNO
3etc. solubility acid solution.
Advantage of the present invention is: present method simple possible, and rapidly and efficiently, product morphology is controlled, has practical value.
Accompanying drawing explanation
Fig. 1 is that titanium dioxide core/shell nanometer cable array prepares each stage schematic diagram.(a) for prepare under small voltage Nano tube array of titanium dioxide, after Fig. 1 (b) increases anodic oxidation voltage, the two-layer Nano tube array of titanium dioxide formed, the surfacing that Fig. 1 (c) obtains after removing pipe with small pipe diameter titania nanotube, crackless Nano tube array of titanium dioxide.The titanium dioxide core/shell nanometer cable array of line in pipe formed after Fig. 1 (d) alkali and acid etch;
Fig. 2 (a) to be the large size SEM figure with the smooth crackless Nano tube array of titanium dioxide of wide area surface prepared by twice anonizing, Fig. 2 (b) be SEM figure with the partial enlargement of the smooth crackless Nano tube array of titanium dioxide of wide area surface prepared by twice anonizing;
Fig. 3 carries out etching 4 h, the microtexture of the titanium dioxide core/shell nanometer cable array formed after then at room temperature etching 1.5 h again with 0.5 mol/L HCL and characterization result with the Nano tube array of titanium dioxide of 4 mol/L KOH at room temperature antianode oxidation preparation in the present invention.Fig. 3 (a) top is the SEM figure of low power; Fig. 3 (b) high power top SEM schemes; Fig. 3 (c) is section S EM figure; Fig. 3 (d), for titania nanotube radial direction to be sectioned, exposes the SEM figure of inner silica titanium nano wire.At the schematic diagram of the titania nanotube of solid wire in pipe corresponding to the right lateral position of SEM figure.From scheming individual SEM figure can measuring, the gap in tube chamber between nano wire and tube wall is approximately 25nm;
Fig. 4 is that the Nano tube array of titanium dioxide of 4 mol/L KOH at room temperature antianode oxidation preparation carries out etching 4 h, the microtexture of the titanium dioxide core/shell nanometer cable array formed after then at room temperature etching 1.5 h again with 0.3 mol/L HCL and characterization result.Fig. 4 (a) top is the SEM figure of low power; Fig. 4 (b) high power top SEM schemes.Can to measure from figure SEM figure, in tube chamber nano wire and and tube wall between gap be approximately 35nm;
Fig. 5 is that the Nano tube array of titanium dioxide of 4 mol/L KOH at room temperature antianode oxidation preparation carries out etching 4 h, then at room temperature uses 0.3 mol/L HNO
3the microtexture of the titanium dioxide core/shell nanometer cable array formed after etching 1.5 h again and characterization result.Fig. 5 (a) top is the SEM figure of low power; Fig. 5 (b) high power top SEM schemes.Can to measure from figure SEM figure, in tube chamber nano wire and and tube wall between gap be approximately 20nm.
Embodiment
Embodiment 1
(1) first by titaniferous amount be 96% tinsel be that in the ethanol of 1:1 and the mixing solutions of acetone, ultrasonic cleaning 60min, to remove the organism on surface, and then to clean with deionized water repeatedly at concentration ratio, and to dry;
(2) tinsel after cleaning being dried carries out anodic oxidation in the ethylene glycol solution containing 0.30mol/L hydrofluoric acid, and wherein oxidation voltage is 15v, and oxidization time is 15min; Then increase anodic oxidation voltage to 50v, oxidation 2h, forms the Nano tube array of titanium dioxide that upper and lower two-layer large pipe with small pipe diameter is different;
(3) anodised tinsel is taken out, pass through sonic oscillation, the pipe with small pipe diameter titania nanotube prepared in small voltage anodic oxygen is separated from Large Diameter Pipeline Nano tube array of titanium dioxide, leaves surfacing, fissureless film of Nano tube array of titanium dioxide;
(4) configuration is containing 4mol/L KOH solution, after the immersion of the film of Nano tube array of titanium dioxide of preparation wherein 4 h, and washed with de-ionized water 1 minute;
(5) the HCL solution of configuration containing 0.5mol/L, by the Nano tube array of titanium dioxide after immersion in KOH solution, is immersed in 1.5 h in the solution containing HCL, and washed with de-ionized water is clean, dries, can obtain titanium dioxide core/shell nanometer cable array.
Embodiment 2
(1) first by titaniferous amount be 96% tinsel be that in the ethanol of 1:1 and the mixing solutions of acetone, ultrasonic cleaning 60min, to remove the organism on surface, and then to clean with deionized water repeatedly at concentration ratio, and to dry;
(2) tinsel after cleaning being dried carries out anodic oxidation in the ethylene glycol solution containing 0.30mol/L hydrofluoric acid, and wherein oxidation voltage is 15v, and oxidization time is 15min; Then increase anodic oxidation voltage to 50v, oxidation 2h, forms the Nano tube array of titanium dioxide that upper and lower two-layer large pipe with small pipe diameter is different;
(3) anodised tinsel is taken out, pass through sonic oscillation, the pipe with small pipe diameter titania nanotube prepared in small voltage anodic oxygen is separated from Large Diameter Pipeline Nano tube array of titanium dioxide, leaves surfacing, fissureless film of Nano tube array of titanium dioxide;
(4) configuration is containing 4mol/L KOH solution, after the immersion of the film of Nano tube array of titanium dioxide of preparation wherein 4 h, and washed with de-ionized water 1 minute;
(5) HNO of configuration containing 0.3mol/L
3solution, by the Nano tube array of titanium dioxide after immersion in KOH solution, is immersed in 1.5 h in the solution containing HCL, and washed with de-ionized water is clean, dries, can obtain titanium dioxide core/shell nanometer cable array.
Claims (1)
1. a preparation method for titanium dioxide core/shell nanometer cable array, is characterized in that comprising the following steps:
(1) first by titaniferous amount be 94-96% tinsel be that in the ethanol of 1-2:1-2 and the mixing solutions of acetone, ultrasonic cleaning 60-70min, to remove the organism on surface, and then to clean with deionized water repeatedly at concentration ratio, and to dry;
(2) tinsel after cleaning being dried carries out anodic oxidation in containing the ethylene glycol solution of 0.20-0.30mol/L hydrofluoric acid, and wherein oxidation voltage is 10-20v, and oxidization time is 10-15min; Then increase anodic oxidation voltage to 45-55v, oxidation 1.5-2h, forms the Nano tube array of titanium dioxide that upper and lower two-layer large pipe with small pipe diameter is different;
(3) anodised tinsel is taken out, pass through sonic oscillation, the pipe with small pipe diameter titania nanotube prepared in small voltage anodic oxygen is separated from Large Diameter Pipeline Nano tube array of titanium dioxide, leaves surfacing, fissureless film of Nano tube array of titanium dioxide;
(4) configuration is containing 4mol/L alkaline solution, and this alkaline solution is KOH or NaOH solution, is soaked by the film of Nano tube array of titanium dioxide of preparation wherein after 2-4 h, washed with de-ionized water 1-5 minutes;
(5) acid solution of configuration containing 0.25-0.5mol/L, this acid solution is H
2sO
4, HCl or HNO
3solution, by the Nano tube array of titanium dioxide after immersion in alkaline solution, is immersed in 1.5-2 h in acid solution, and washed with de-ionized water is clean, dries, can obtain titanium dioxide core/shell nanometer cable array.
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| 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 |
| CN113445102B (en) * | 2021-06-01 | 2022-09-02 | 西安理工大学 | Preparation method of biological piezoelectric coating on surface of titanium-based material |
| CN114159617B (en) * | 2021-10-11 | 2022-08-12 | 安徽医科大学第二附属医院 | Titanium implant with nano bionic three-dimensional porous titanium trabecular structure and preparation method and application thereof |
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| US6267861B1 (en) * | 2000-10-02 | 2001-07-31 | Kemet Electronics Corporation | Method of anodizing valve metals |
| CN101230479A (en) * | 2007-11-09 | 2008-07-30 | 清华大学 | Method for preparing gradient TiO2 nano-tube arrry thin film by using multistep anodic oxidation process |
| CN101660189A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Branch controllable titanium dioxide nanotube array film and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267861B1 (en) * | 2000-10-02 | 2001-07-31 | Kemet Electronics Corporation | Method of anodizing valve metals |
| CN101230479A (en) * | 2007-11-09 | 2008-07-30 | 清华大学 | Method for preparing gradient TiO2 nano-tube arrry thin film by using multistep anodic oxidation process |
| CN101660189A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Branch controllable titanium dioxide nanotube array film and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Controllable fabrication of multibranched TiO2 nanotubes via a two-step anodization method;Zhen Jin et al.;《Chemistry Letters》;20090331;第38卷(第3期);第288-289页 * |
| High Efficiency Dye-Sensitized Solar Cells Based on Hierarchically Structured Nanotubes;Meidan Ye et al.;《ADVANCED MATERIALS》;20110705(第11期);第1964-1967页 * |
| High Efficiency Dye-Sensitized Solar Cells Based on Hierarchically Structured Nanotubes;Meidan Ye et al.;《NaNo Letters》;20110705(第11期);第3214-3220页 * |
| Large-Scale, Noncurling, and Free-Standing Crystallized TiO2 Nanotube Arrays for Dye-Sensitized Solar Cells;Qingwei Chen，Dongsheng Xu;《J.Phys.Chem.C》;20090210;第113卷(第15期);第6310-6314页 * |
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