CN102953110A

CN102953110A - Preparation method of titanium dioxide core/shell nanometer cable array

Info

Publication number: CN102953110A
Application number: CN201210392780XA
Authority: CN
Inventors: 胡小晔; 孟国文; 刘毛; 许伟; 韩方明; 王兆明
Original assignee: Hefei Institutes of Physical Science of CAS
Current assignee: Hefei Institutes of Physical Science of CAS
Priority date: 2012-10-16
Filing date: 2012-10-16
Publication date: 2013-03-06
Anticipated expiration: 2032-10-16
Also published as: CN102953110B

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

The preparation method of a kind of titanium dioxide core/shell nano-cable array

Technical field

The present invention relates generally to kind of an a kind of pervasive chemical etching method, relates in particular to the preparation method of a kind of titanium dioxide core/shell nano-cable array

Background technology

Pure titanium sheet (is mainly the organic or inorganic ionogen of fluoride ion) in some ionogen, can obtain the Nano tube array of titanium dioxide of ordered arrangement by anodic oxidation.These are by the Nano tube array of titanium dioxide of anonizing preparation, because of its unique tubular structure, high specific surface area and orderly arrangement mode, it are being had 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 the porous anode alumina formwork), adopt electrochemical deposition technique nano wire such as filler metal, semi-conductor in titania nanotube, obtain the nano-cables such as metal/titanium dioxide, semi-conductor/titanium dioxide, to expand the Application Areas of anodic oxidation titania nanotube.Yet the shortcoming such as anodic oxidation film of Nano tube array of titanium dioxide titanium sheet substrate very crisp, that break easily, support is difficult to remove, titania nanotube low side through hole difficulty is large has restricted the use of titanium dioxide as template.Therefore probe into a kind of simple and effective synthetic method, the controlled titanium dioxide nano thread of preparation complex structure, parameter/nanotube composite structure array is with significant.

Summary of the invention

The object of the invention is exactly in order to remedy the defective of prior art, to provide a kind of cheapness, simple synthetic method, for the preparation of the controlled titanium dioxide nano thread of structural parameter/nanotube composite structure array.

The present invention is achieved by the following technical solutions:

The preparation method of a kind of titanium dioxide core/shell nano-cable array may further comprise the steps:

(1) at first be 94-96% tinsel with the titaniferous amount at concentration ratio is that ultrasonic cleaning 60-70min and then cleans with deionized water repeatedly removing the organism on surface in the mixing solutions of the ethanol of 1-2:1-2 and acetone, and dries;

(2) tinsel after cleaning is dried carries out anodic oxidation in the ethylene glycol solution that contains 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 up and down different Nano tube array of titanium dioxide of two-layer large pipe with small pipe diameter;

(3) take out anodised tinsel, pass through sonic oscillation, the pipe with small pipe diameter titania nanotube of anodic oxidation preparation under small voltage is separated from the Large Diameter Pipeline Nano tube array of titanium dioxide, stay surfacing, fissureless film of Nano tube array of titanium dioxide;

(4) configuration contains the 4mol/L alkaline solution, the film of Nano tube array of titanium dioxide of preparation is soaked wherein 2-4 h after, washed with de-ionized water 1-5 minutes;

(5) configuration contains the acid solution of 0.25-0.5mol/L, and the Nano tube array of titanium dioxide after will soaking in alkaline solution is immersed in 1.5-2 h in the acid solution, and washed with de-ionized water is clean, and oven dry can obtain titanium dioxide core/shell nano-cable array.

Acid solution in the step (4) is KOH or NaOH solution.

Acid solution in the step (5) is H ₂SO ₄, HCL or HNO ₃Etc. the solubility acid solution.

Advantage of the present invention is: present method simple possible, rapidly and efficiently, the product pattern is controlled, has practical value.

Description of drawings

Fig. 1 is that titanium dioxide core/shell nano-cable array prepares each stage synoptic diagram.(a) for prepare under the 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 that forms, Fig. 1 (c) removes the surfacing that obtains behind the pipe with small pipe diameter titania nanotube, crackless Nano tube array of titanium dioxide.The titanium dioxide core of the line that forms after Fig. 1 (d) alkali and the acid etch in pipe/shell nano-cable array;

Fig. 2 (a) is the large size SEM figure with the smooth crackless Nano tube array of titanium dioxide of wide area surface of twice anonizing preparation, and Fig. 2 (b) is the SEM figure that amplify the part with the smooth crackless Nano tube array of titanium dioxide of wide area surface of twice anonizing preparation;

Fig. 3 is that the Nano tube array of titanium dioxide with 4 at room temperature antianode oxidations of mol/L KOH preparations carries out etching 4 h among the present invention, microtexture and the characterization result of the titanium dioxide core that then at room temperature forms behind etching 1.5 h again with 0.5 mol/L HCL/shell nano-cable array.Fig. 3 (a) top is the SEM figure of low power; Fig. 3 (b) high power top SEM figure; Fig. 3 (c) is section S EM figure; Fig. 3 (d) exposes the SEM figure of inner titanium dioxide nano thread for titania nanotube is radially sectioned.Synoptic diagram at the titania nanotube of solid wire in pipe corresponding to the right lateral position of SEM figure.Individual can measuring from figure SEM figure, the gap in the tube chamber between nano wire and the tube wall is approximately 25nm;

Fig. 4 is that the Nano tube array of titanium dioxide of 4 at room temperature antianode oxidations of mol/L KOH preparations carries out etching 4 h, microtexture and the characterization result of the titanium dioxide core that then at room temperature forms behind etching 1.5 h again with 0.3 mol/L HCL/shell nano-cable array.Fig. 4 (a) top is the SEM figure of low power; Fig. 4 (b) high power top SEM figure.From figure SEM figure, can measure, in the tube chamber nano wire and and tube wall between the gap be approximately 35nm;

Fig. 5 is that the Nano tube array of titanium dioxide of 4 at room temperature antianode oxidations of mol/L KOH preparation carries out etching 4 h, then at room temperature uses 0.3 mol/L HNO ₃Microtexture and the characterization result of the titanium dioxide core that forms behind etching 1.5 h again/shell nano-cable array.Fig. 5 (a) top is the SEM figure of low power; Fig. 5 (b) high power top SEM figure.From figure SEM figure, can measure, in the tube chamber nano wire and and tube wall between the gap be approximately 20nm.

Embodiment

Embodiment 1

(1) at first be 96% tinsel with the titaniferous amount at concentration ratio is that ultrasonic cleaning 60min and then cleans with deionized water repeatedly removing the organism on surface in the mixing solutions of the ethanol of 1:1 and acetone, and dries;

(2) tinsel after cleaning is dried carries out anodic oxidation in the ethylene glycol solution that contains 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 up and down different Nano tube array of titanium dioxide of two-layer large pipe with small pipe diameter;

(4) configuration contains 4mol/L KOH solution, the film of Nano tube array of titanium dioxide of preparation is soaked wherein 4 h after, washed with de-ionized water 1 minute;

(5) configuration contains the HCL solution of 0.5mol/L, and the Nano tube array of titanium dioxide after will soaking in KOH solution is immersed in 1.5 h in the solution that contains HCL, and washed with de-ionized water is clean, and oven dry can obtain titanium dioxide core/shell nano-cable array.

Embodiment 2

(5) configuration contains the HNO of 0.3mol/L ₃Solution, the Nano tube array of titanium dioxide after will soaking in KOH solution is immersed in 1.5 h in the solution that contains HCL, and washed with de-ionized water is clean, and oven dry can obtain titanium dioxide core/shell nano-cable array.

Claims

1. the preparation method of titanium dioxide core/shell nano-cable array is characterized in that may further comprise the steps:

(2) tinsel after cleaning is dried carries out anodic oxidation in the ethylene glycol solution that contains 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 up and down different Nano tube array of titanium dioxide of two-layer large pipe with small pipe diameter;

2. the preparation method of titanium dioxide core according to claim 1/shell nano-cable array is characterized in that the acid solution in the described step (4) is KOH or NaOH solution.

3. the preparation method of titanium dioxide core according to claim 1/shell nano-cable array is characterized in that the acid solution in the described step (5) is H ₂SO ₄, HCL or HNO ₃Etc. the solubility acid solution.