CN102776543B - Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays - Google Patents
Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays Download PDFInfo
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- CN102776543B CN102776543B CN201210138713.5A CN201210138713A CN102776543B CN 102776543 B CN102776543 B CN 102776543B CN 201210138713 A CN201210138713 A CN 201210138713A CN 102776543 B CN102776543 B CN 102776543B
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Abstract
The invention discloses a preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays. According to the preparation method, different-voltage two-step anodic oxidation methods are successively used or electrolyte is changed for carrying out secondary anodic oxidation on titanium sheets, two layers of anodic oxidation titanium dioxide nanometer tube array films with great pipe diameter differences are formed, and then, products are obtained by an improved ultrasonic treatment method. The method has the advantages that simplicity is realized, the implementation is easy, economy and reliability are realized, the products are controllable, practical values are realized, and the titanium dioxide nanometer tube arrays with the perfect surface appearance can be prepared only through carrying out simple step-by-step oxidation on the titanium sheets.
Description
Technical field
The invention belongs to pervasive anonizing and post-treating method field thereof, particularly relate to the preparation method of the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of a kind of wide area surface.
Background technology
Titanium dioxide is a kind of well-known semiconductor material with wide forbidden band, is widely used in many-sided fields such as environment, catalysis, the energy, biology and sensing.Wherein titanium dioxide nanostructure and nano material are owing to having high specific surface area, have shown good performance in many-sided practical application.Nano tube array of titanium dioxide particularly by carrying out anodic oxidation acquisition to pure titanium sheet has also possessed the structure of cycle ordered arrangement and the titanium substrate of conduction while having high-specific surface area, obtains great concern especially in multiaspects such as solar cell, photolysis water hydrogen, photocatalysts capable of circulation.Usual anodic oxidation nano-tube array adopts an anonizing, can form the nanotube of the unordered impurity of one deck and lodging, blocked the opening of array, usually had larger impact to practical application at the open top end of nanotube.In order to remove unordered impurity layer, the method usually adopted is ultrasonic vibration in water, utilizes hyperacoustic energy to destroy nano-tube array to reach the object removing impurity layer.Doing the side effect that usually can bring like this is then the Nano tube array of titanium dioxide surface irregularity injustice formed, and the crack of the countless nanoscale be full of or micro-meter scale.These cracks usually can cause the short circuit of electrode in the practical application such as solar cell, photolysis water hydrogen.The consequence that nano-tube array departs from from conduction titanium substrate also can be caused when hyperacoustic energy is enough strong time.Utilize supercritical co in addition or use the hydrofluoric acid of high density to carry out the method such as corroding, these methods are not easy to operation usually, have certain danger, and are difficult to the pattern and the sample quality that control final product accurately.Therefore, probe into a kind of simple, reliable, economy, effective means are significant to synthesize the large face fissureless Nano tube array of titanium dioxide of smooth surface.
Summary of the invention
The object of the invention is the preparation method proposing a kind of equipment economy, the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of the simple and effective wide area surface of working method.
The present invention adopts following technical scheme to achieve these goals:
A preparation method for the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of wide area surface, is characterized in that:
Comprise the following steps:
(1), first pure titanium sheet ultrasonic cleaning 30 about min in volume ratio is the ethanol of 1:0.8-1.2 and acetone mixing solutions, to remove the organism on surface, is then used deionized water repeatedly to clean, dries up, obtain the titanium sheet after cleaning-drying under nitrogen gas stream;
(2), by the titanium sheet after step (1) gained cleaning-drying containing about 0.2 M hydrofluoric acid ethylene glycol solution in carry out first time anodic oxidation, wherein oxidation voltage is about 30 V, and oxidization time is about 3 h, after carry out second time anodic oxidation again;
(3), the anodic oxidation titania nanotube sample after two-step anodization is inserted in the ultrasonic container of the sonification medium filling with thickness vibrate, the anodic titanium dioxide nanotube array layer that the caliber that first time anodic oxidation is formed is less and the anodic oxidation titanium dioxide nanotube array layer that two-step anodization is formed depart from, and obtain the fissureless anodic oxidation titanium dioxide nano-pipe array thin film of overlarge area smooth surface;
(4), by fissureless for the overlarge area smooth surface of step 4 gained anodic oxidation titanium dioxide nano-pipe array thin film use deionized water rinsing clean, nitrogen atmosphere is dried, and obtains product.
The preparation method of the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of described a kind of wide area surface, it is characterized in that: described pure titanium sheet is the titanium sheet of purity >96%, the sonification medium of described thickness refers to ethylene glycol or glycerol.
The preparation method of the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of described a kind of wide area surface, is characterized in that, described second time anodic oxidation has two kinds of methods to realize:
First method is: voltage is raised to 100 V, directly continues to carry out second time anodic oxidation in the ethylene glycol solution of the hydrofluoric acid containing about 0.2 M, and oxidization time is about 1 h;
Second method is: put into the titanium sheet after first time oxidation containing NH
4in the ethylene glycol solution of F, then voltage is adjusted to 60 V, is oxidized about 1 h.
The preparation method of the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of described a kind of wide area surface, is characterized in that: described contains NH
4the collocation method of the ethylene glycol solution of F is by the NH of about 1 g
4f is dissolved in the deionized water of about 6 mL, then adds the ethylene glycol of about 300 mL, is mixed by solution.
Principle of the present invention is: the present invention relates to a kind of pervasive anonizing and post-treating method thereof, the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of overlarge area surface cleaning for the preparation of a kind of morphology controllable, the i.e. parallel orderly titanium dioxide open porous tube array of amorphous, the nano-tube array caliber formed is controlled, close to leakless in the scope of centimeter scale.Core concept of the present invention successively uses two step anonizings of different voltage or change electrolytic solution to carry out two-step anodization to titanium sheet, form the two-layer anodic oxidation titanium dioxide nano-pipe array thin film of pipe diameter size great disparity, then the ultrasonic processing method by improving, due to the sharply change of pipe diameter size, the interface cohesion place intensity of two-layer anodic oxidation Nano tube array of titanium dioxide is very fragile, again by sonic oscillation in the ultrasonic vibration medium of thickness, two-layer anodic oxidation Nano tube array of titanium dioxide is separated, leave smooth surface fissureless bottom anodic oxidation Nano tube array of titanium dioxide and titanium substrate combines simultaneously.
Beneficial effect of the present invention:
1, present method is simple, economic and reliable, and product is controlled, has practical value, just can prepare the perfect Nano tube array of titanium dioxide of surface topography by means of only carrying out simple step-by-step oxidation to titanium sheet.The anodic oxidation Nano tube array of titanium dioxide preparing gained by the method is expected to the widespread use for multiaspects such as photochemical catalysis, water pollutions process, dye sensitization solar battery, chemical sensor and photolysis water hydrogens;
2, because the energy of this method sonic oscillation in ultrasonication mainly concentrates the interface cohesion place with two-layer Nano tube array of titanium dioxide, use the sonification medium of thickness simultaneously, make ultrasonic energy very small portion act on titania nanotube array entirety, ensure that the complete of anodic titanium dioxide nanotube array entirety and there will not be crack.Because the arrangement of the anodic titanium dioxide nanotube array layer on upper strata is separated, the anodic oxidation Nano tube array of titanium dioxide obtained is made to have smooth surface.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram that anonizing prepares super-large dimension area smooth surface leakless anodic titanium dioxide nanotube array;
Fig. 2 is the process schematic that the present invention prepares overlarge area smooth surface leakless anodic titanium dioxide nanotube array; Figure (a) is cleaned titanium sheet; Figure (b) is the anodic oxidation Nano tube array of titanium dioxide formed after an anodic oxidation; The bilayer anode ferric oxide/titanium dioxide nano pipe array that figure (c) is the pipe diameter size great disparity after two-step anodization; Figure (d) is for after sonic oscillation process, and the bilayer anode ferric oxide/titanium dioxide nano pipe array of pipe diameter size great disparity is separated in interface, forms the process of the fissureless anodic oxidation Nano tube array of titanium dioxide of overlarge area smooth surface;
Fig. 3 is the scanning electron microscopic picture that a common anonizing prepares the anodic oxidation Nano tube array of titanium dioxide of gained, and figure (a) is the top view of the anodic oxidation Nano tube array of titanium dioxide prepared through an anonizing of sonic oscillation process; The top view of the anodic oxidation Nano tube array of titanium dioxide that figure (b) is prepared for time anonizing of after sonic oscillation process; The electron microscopic picture of the titanium substrate separation of the anodic oxidation Nano tube array of titanium dioxide that figure (c) is prepared for a common anonizing that sonic oscillation causes and conduction;
Fig. 4 is the side-view of the scanning electron microscopic picture of the bilayer anode ferric oxide/titanium dioxide nano pipe array by pipe diameter size great disparity prepared in step of the present invention (2) and (3), the bilayer anode ferric oxide/titanium dioxide nano pipe array that figure (a) is pipe diameter size great disparity; Figure (b) is the side-view of the bilayer anode ferric oxide/titanium dioxide nano pipe array of the pipe diameter size great disparity be separated; Insert the interface cohesion place scanning electron microscope side view picture that figure is the bilayer anode ferric oxide/titanium dioxide nano pipe array of pipe diameter size sudden change;
Fig. 5 be by the present invention prepare the fissureless anodic oxidation Nano tube array of titanium dioxide of overlarge area smooth surface of final gained top view;
Fig. 6 be in Fig. 5 the fissureless anodic oxidation Nano tube array of titanium dioxide of the overlarge area smooth surface of sample under lower magnification top view electromicroscopic photograph;
Fig. 7 be in Fig. 5 the fissureless anodic oxidation Nano tube array of titanium dioxide of the overlarge area smooth surface of sample under lower magnification top view electromicroscopic photograph; The top view electromicroscopic photograph of the low power magnification of insertion figure to be scale be anodic oxidation Nano tube array of titanium dioxide prepared by the common anonizing of 20 μm.
embodiment,
Embodiment 1,
A preparation method for the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of wide area surface, is characterized in that:
Comprise the following steps:
(1), first pure titanium sheet ultrasonic cleaning 30 min in volume ratio is the ethanol of 1:1 and acetone mixing solutions, to remove the organism on surface, is then used deionized water repeatedly to clean, dries up, obtain the titanium sheet after cleaning-drying under nitrogen gas stream;
(2), the titanium sheet after step (1) gained cleaning-drying is carried out first time anodic oxidation in the ethylene glycol solution of the hydrofluoric acid containing 0.2 M, wherein oxidation voltage is 30 V, oxidization time is 3 h, after carry out second time anodic oxidation again, voltage is raised to 100 V, direct continuation carries out second time anodic oxidation in the ethylene glycol solution of the hydrofluoric acid containing 0.2 M, and oxidization time is 1 h;
(3), the anodic oxidation titania nanotube sample after two-step anodization is inserted in the ultrasonic container of the sonification medium filling with thickness vibrate, the anodic titanium dioxide nanotube array layer that the caliber that first time anodic oxidation is formed is less and the anodic oxidation titanium dioxide nanotube array layer that two-step anodization is formed depart from, and obtain the fissureless anodic oxidation titanium dioxide nano-pipe array thin film of overlarge area smooth surface;
(4), by fissureless for the overlarge area smooth surface of step 4 gained anodic oxidation titanium dioxide nano-pipe array thin film use deionized water rinsing clean, nitrogen atmosphere is dried, and obtains product.
The preparation method of the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of described a kind of wide area surface, it is characterized in that: described pure titanium sheet is the titanium sheet of purity >96%, and the sonification medium of described thickness refers to ethylene glycol.
Fig. 1 is the device schematic diagram that anonizing prepares super-large dimension area smooth surface leakless anodic titanium dioxide nanotube array;
Fig. 2 is the process schematic that the present invention prepares overlarge area smooth surface leakless anodic titanium dioxide nanotube array.Figure (a) is cleaned titanium sheet; Figure (b) is the anodic oxidation Nano tube array of titanium dioxide formed after an anodic oxidation; The bilayer anode ferric oxide/titanium dioxide nano pipe array that figure (c) is the pipe diameter size great disparity after two-step anodization; Figure (d) is for after sonic oscillation process, and the bilayer anode ferric oxide/titanium dioxide nano pipe array of pipe diameter size great disparity is separated in interface, forms the process of the fissureless anodic oxidation Nano tube array of titanium dioxide of overlarge area smooth surface.
Fig. 3 is the scanning electron microscopic picture that a common anonizing prepares the anodic oxidation Nano tube array of titanium dioxide of gained.Figure (a) is the top view of the anodic oxidation Nano tube array of titanium dioxide prepared through an anonizing of sonic oscillation process, and visible surface piles with unordered impurity layer; The top view of the anodic oxidation Nano tube array of titanium dioxide that figure (b) is prepared for time anonizing of after sonic oscillation process, its surface is filled with crack as seen; The electron microscopic picture of the anodic oxidation Nano tube array of titanium dioxide that figure (c) is prepared for a common anonizing that sonic oscillation causes and the titanium substrate separation of conduction, and the existence of usual conductive substrate can use as electrode in the photovoltaic applications of reality.
Fig. 4 is the scanning electron microscopic picture of the bilayer anode ferric oxide/titanium dioxide nano pipe array by pipe diameter size great disparity prepared in step 2 of the present invention and 3.The side-view of the bilayer anode ferric oxide/titanium dioxide nano pipe array that figure (a) is pipe diameter size great disparity; Figure (b) is the side-view of the bilayer anode ferric oxide/titanium dioxide nano pipe array of the pipe diameter size great disparity be separated; Insert the interface cohesion place scanning electron microscope side view picture that figure is the bilayer anode ferric oxide/titanium dioxide nano pipe array of pipe diameter size sudden change.
Fig. 5 be by the present invention prepare the fissureless anodic oxidation Nano tube array of titanium dioxide of overlarge area smooth surface of final gained top view, this array is smooth at 2 μm of scale range internal surfaces as seen from the figure, without any crack.
Fig. 6 be in Fig. 5 the fissureless anodic oxidation Nano tube array of titanium dioxide of the overlarge area smooth surface of sample under lower magnification top view electromicroscopic photograph, in 30 μm of range scales, these array surface are smooth as seen from the figure, without any crack.
Fig. 7 be in Fig. 5 the fissureless anodic oxidation Nano tube array of titanium dioxide of the overlarge area smooth surface of sample under lower magnification top view electromicroscopic photograph, be greater than this array surface in 60 μm of range scales as seen from the figure smooth, without any crack.The top view electromicroscopic photograph of the low power magnification of insertion figure to be scale be anodic oxidation Nano tube array of titanium dioxide prepared by the common anonizing of 20 μm, its surface is full of zigzag cracks as seen.
Embodiment 2,
A preparation method for the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of wide area surface, comprises the following steps:
(1), first pure titanium sheet ultrasonic cleaning 30 min in volume ratio is the ethanol of 1:1 and acetone mixing solutions, to remove the organism on surface, is then used deionized water repeatedly to clean, dries up, obtain the titanium sheet after cleaning-drying under nitrogen gas stream;
(2), the titanium sheet after step (1) gained cleaning-drying is carried out first time anodic oxidation in the ethylene glycol solution of the hydrofluoric acid containing 0.2 M, wherein oxidation voltage is 30 V, oxidization time is 3 h, after carry out second time anodic oxidation again, be about to first time oxidation after titanium sheet put into containing NH
4in the ethylene glycol solution of F, then voltage is adjusted to 60 V, is oxidized 1 h.
(3), the anodic oxidation titania nanotube sample after two-step anodization is inserted in the ultrasonic container of the sonification medium filling with thickness vibrate, the anodic titanium dioxide nanotube array layer that the caliber that first time anodic oxidation is formed is less and the anodic oxidation titanium dioxide nanotube array layer that two-step anodization is formed depart from, and obtain the fissureless anodic oxidation titanium dioxide nano-pipe array thin film of overlarge area smooth surface;
(4), by fissureless for the overlarge area smooth surface of step 4 gained anodic oxidation titanium dioxide nano-pipe array thin film use deionized water rinsing clean, nitrogen atmosphere is dried, and obtains product.
Described pure titanium sheet is the titanium sheet of purity >96%, and the sonification medium of described thickness refers to glycerol.
Described contains NH
4the collocation method of the ethylene glycol solution of F is by the NH of 1 g
4f is dissolved in the deionized water of 6 mL, then adds the ethylene glycol of 300 mL, is mixed by solution.
Claims (2)
1. a preparation method for the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of wide area surface, is characterized in that: comprise the following steps:
(1), first pure titanium sheet ultrasonic cleaning 30 min in volume ratio is the ethanol of 1:0.8-1.2 and acetone mixing solutions, to remove the organism on surface, is then used deionized water repeatedly to clean, dries up, obtain the titanium sheet after cleaning-drying under nitrogen gas stream;
(2), by the titanium sheet after step (1) gained cleaning-drying containing 0.2 M hydrofluoric acid ethylene glycol solution in carry out first time anodic oxidation, wherein oxidation voltage is 30 V, and oxidization time is 3 h, after carry out second time anodic oxidation again; Described second time anodic oxidation has two kinds of methods to realize: first method is: voltage is raised to 100 V, directly continues to carry out second time anodic oxidation in the ethylene glycol solution of the hydrofluoric acid containing 0.2 M, and oxidization time is 1 h; Second method is: put into the titanium sheet after first time oxidation containing NH
4in the ethylene glycol solution of F, then voltage is adjusted to 60 V, is oxidized 1 h, described contains NH
4the collocation method of the ethylene glycol solution of F is by the NH of 1 g
4f is dissolved in the deionized water of 6 mL, then adds the ethylene glycol of 300 mL, is mixed by solution;
(3), the anodic oxidation titania nanotube sample after two-step anodization is inserted in the ultrasonic container of the sonification medium filling with thickness vibrate, the anodic titanium dioxide nanotube array layer that the caliber that first time anodic oxidation is formed is less and the anodic oxidation titanium dioxide nanotube array layer that two-step anodization is formed depart from, and obtain the fissureless anodic oxidation titanium dioxide nano-pipe array thin film of overlarge area smooth surface;
(4), by fissureless for the overlarge area smooth surface of step (3) gained anodic oxidation titanium dioxide nano-pipe array thin film use deionized water rinsing clean, nitrogen atmosphere is dried, and obtains product.
2. the preparation method of the smooth fissureless anodic oxidation Nano tube array of titanium dioxide of a kind of wide area surface according to claim 1, it is characterized in that: described pure titanium sheet is the titanium sheet of purity >96%, the sonification medium of described thickness refers to ethylene glycol or glycerol.
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| CN103390744B (en) * | 2013-07-22 | 2016-01-20 | 苏州大学 | A kind of preparation method of micro cell membrane electrode and membrane electrode and micro cell |
| CN103436937A (en) * | 2013-07-25 | 2013-12-11 | 四川大学 | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure |
| CN104032354A (en) * | 2014-05-27 | 2014-09-10 | 华南理工大学 | Preparation method of density-controllable titanium nanorod arrays |
| CN105883715B (en) * | 2016-05-06 | 2018-06-26 | 同济大学 | With high degree of periodicity Ti-Au alloy nanotube photonic crystal electrodes and its construction method |
| CN107268061B (en) * | 2017-05-08 | 2019-01-25 | 武汉理工大学 | A kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof |
| CN111634941A (en) * | 2020-07-27 | 2020-09-08 | 南开大学 | Self-peeling titanium dioxide nanotube |
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| US20100187172A1 (en) * | 2007-07-26 | 2010-07-29 | The Penn State Research Foundation | Highly-ordered titania nanotube arrays |
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| US20100187172A1 (en) * | 2007-07-26 | 2010-07-29 | The Penn State Research Foundation | Highly-ordered titania nanotube arrays |
| 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 |
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