CN101781788B - Method for preparing specially-shaped titanium dioxide nano-tube films - Google Patents
Method for preparing specially-shaped titanium dioxide nano-tube films Download PDFInfo
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- CN101781788B CN101781788B CN201010004607.9A CN201010004607A CN101781788B CN 101781788 B CN101781788 B CN 101781788B CN 201010004607 A CN201010004607 A CN 201010004607A CN 101781788 B CN101781788 B CN 101781788B
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Abstract
The invention discloses a method for preparing specially-shaped titanium dioxide nano-tube films with changeable pipe diameter along the axial direction by an anode oxidation method. The method comprises the following steps: thoroughly cleaning pure titanium serving as a substrate material, putting the cleaned pure titanium into a solution of which the solute is a fluoride and the solvent is an electrolyte prepared by adding a small amount of water into ethylene glycol or glycerol or liquid polyethylene glycol with low molecular weight, carrying out electrochemical anodic oxidation on electrodes by using non-titanic metal plate, and making the electrolytic current change periodically when electrolyzing. The method can be used to prepare stratified nodular or condyle-shaped or torose titanium dioxide nano-tube films; and the internal surface of the tube between two adjacent nodes is curved.
Description
Technical field
The present invention relates to a kind of specially-shaped titanium dioxide nano-tube films, especially its caliber changes vertically, pipe internal surface has the preparation method of the specially-shaped titanium dioxide nano-tube films compared with bigger serface, and preparation method of the present invention have employed anonizing.
Background technology
Since Japanese Fujishima in 1972 finds titanium dioxide single crystalline electrode photochemical catalyzing, see Nature, 1972,238 (5358): 37-38., photocatalysis technology obtains to be paid close attention to widely.Photocatalysis technology likely solves energy dilemma and the problem of environmental pollution of human future.Photocatalysis technology just can carry out under normal temperature, normal pressure, can thoroughly destroy organic or inorganic pollutent, and make it completely, Quick Oxidation is carbonic acid gas, the innoxious substances such as water, avoid secondary pollution, thus reach the object of environment purification.Early stage titanium dioxide, mainly by the nano particle that gas phase synthesis method and liquid phase synthesizing method prepare, is mainly used in photocatalysis technology and inorganic paint.Because titania nanotube is at dye sensitization solar battery, photocatalyst, gas sensor, bone embedded material, template electric-sedimentation is prepared the aspects such as inorganic or semiconductor nanowires and is had broad application prospects, and has become the focus competitively studied both at home and abroad.The preparation method of current titania nanotube mainly contains 3 kinds of methods: utilize porous alumina, organic polymer as the template of template, the hydrothermal method utilizing titanium dioxide powder to react in the basic conditions and utilize electrochemistry anodic oxidation.What hydrothermal method was obtained is multi-layer nano structure titanium dioxide, the Nano tube array of titanium dioxide of what template and electrochemistry anodic oxidation obtained is high-sequential.Wherein, electrochemistry anodic oxidation prepares the most effective means of titania nanotube, and this method can height of formation is orderly in substrate titanium dioxide nano-pipe array thin film, and experiment condition is controlled, working method is simple, is thus more and more subject to people's attention.
The nanotube of the titanium dioxide nano-pipe array thin film obtained by prior art is straight tube-like, its specific surface is less, analyze that to show that nanotube that surface area ratio is larger is adsorbed onto the amount of dye of tube wall in dye sensitization solar battery larger, its battery efficiency is also higher.
In order to obtain the larger titanic oxide nano tube thin-film of surface area ratio, Patrik Schmuki (J.Am.Chem.Soc., 2008,130 (49), pp 16454-16455) group carries out nano-tube film that periodic oxidation can obtain similar Bamboo-shaped, that at the pipe of adjacent two internodes be straight tube-like under utilizing the electrolysis voltage in square wave under two voltage varied in size.
Summary of the invention
The present invention is that a kind of axial caliber utilizing anonizing to prepare along pipe changes to some extent, and pipe internal surface has the specially-shaped titanium dioxide nano-tube films of the specific surface area larger compared with prior art.
Preparation method of the present invention is fluorochemical using as putting into solute after the pure titanium of base material thoroughly cleans, adds with ethylene glycol or glycerine or low-molecular-weight liquid polyethylene glycol the electrolytic solution that a small amount of water is solvent again, a small amount of water described here refers to that the water added is 1 ~ 5% of ethylene glycol or glycerine or low-molecular-weight liquid polyethylene glycol volume, do with the metal sheet of non-titanium and electrochemical anodic oxidation is carried out to electrode, make Faradaic current be periodical change constantly carrying out electrolytic oxidation.
In the preparation method of specially-shaped titanium dioxide nano-tube films of the present invention, Faradaic current can be pulse change, wherein between two impulse of current, carry out electrolysis with continuous current, the dutycycle of pulse is 1: 50 ~ 1: 500, and current density during constant-current electrolysis is 2.5 ~ 7.5mA/cm
2, pulsed current summit maximum value is 35 ~ 60mA/cm
2.
In preparation method of the present invention, its Faradaic current also can change in sawtooth waveform, its minimum electrical current density 0 ~ 5.0mA/cm
2, maximum current density 25 ~ 50mA/cm
2, rise rate of current 0.3 ~ 2.5mA/cm
2, rate of current 3 ~ 12mA/cm falls
2/ 0.5s.
Or in preparation method of the present invention, its Faradaic current can change in sinusoidal waveform, and minimum electrical current density is 0 ~ 3mA/cm
2, its maximum current density is 5 ~ 19.45mA/cm
2, the curent change cycle is 10 ~ 60/s.
Passable by method of the present invention, the axial caliber prepared along its pipe changes to some extent, makes pipe internal surface have the specially-shaped titanium dioxide nano-tube films of the specific surface area of the Guan Geng great prepared compared with prior art.The present invention is also by asking the control of distance to nanotube nodular to the control realization of Faradaic current change frequency.
The similar Bamboo-shaped prepared with existing equal diameter titanium dioxide and prior art, the nanotube being straight tube-like at the pipe of adjacent two internodes is compared, nanotube prepared by the present invention is layering nodular or joint shape or rhizoma nelumbinis shape, the curved shape of pipe internal surface between two adjacent joints, therefore the specially-shaped titanium dioxide nano-tube films that prepared by the present invention has larger specific surface area, the adsorptive power that the Guan Yougeng for preparing of comparable prior art is strong, the specially-shaped titanium dioxide nano-tube adopting method of the present invention to prepare has the special length-to-diameter ratio of three-dimensional tubular structure, end-blown, hollow duct, therefore titania nanotube is made to show more significant quantum size effect, and the performance of a series of excellence such as special surface property, be expected to the photocatalysis performance and the photoelectric transformation efficiency that improve titanium dioxide further.The amount of dye such as, being adsorbed onto tube wall in dye sensitization solar battery is larger, thus makes battery efficiency be able to further raising.
Accompanying drawing explanation
Fig. 1 is the curent change curve of the embodiment of the present invention 1 ~ 3 and the voltage change curve of monitoring.Fig. 2 is the surface sweeping Electronic Speculum figure of the titanic oxide nano tube thin-film of the embodiment of the present invention 1 ~ 3.Fig. 3 is Fig. 2 partial enlarged drawing.Fig. 4 is the curent change curve of embodiment 4 ~ 7 and the voltage change curve of monitoring, and Fig. 5 is the surface sweeping Electronic Speculum figure of the titanic oxide nano tube thin-film of the embodiment of the present invention 4 ~ 7.Fig. 6 is the partial enlarged drawing of Fig. 5.Fig. 7 is the voltage change curve of the embodiment of the present invention 8 ~ 11 curent change curve and monitoring.Fig. 8 is the scanning electron microscope (SEM) photograph of embodiment 8 ~ 11 titanic oxide nano tube thin-film.Fig. 9 is Fig. 8 partial enlarged drawing.
Embodiment
Embodiment 1:
Titanium board is cut into the substrate of 3.0cm × 1.0cm size and 250 μm of thickness, use acetone successively, Virahol, methyl alcohol and deionized water ultrasonic cleaning, then be carry out chemical rightenning in the mixing solutions of 1: 8 at hydrofluoric acid and concentrated nitric acid volume ratio, nitrogen dries up rear for subsequent use.At room temperature, make anode with titanium sheet, aluminium sheet is done electrode; With 85ml (NH
4f (0.25wt%)+H
2o (0.3vol%)+HOCH
2cH
2oH) be electrolytic solution, carry out electrolytic oxidation; Oxidation current is shown to provide by the universal source of Keithely 2400, and the program of writing with LabVIEW is by the change of conputer controlled electric current; Electric current in time change curve is pulse curve, i.e. a long continuous current oxidation, and add the process that a big current is elevated suddenly, so carry out periodic cycle, continuous current current density is 4.71mA/cm
2, continuous current oxidization time is 200s, pulsed current summit maximum value 57.65mA/cm
2, this pulse zigzag wave lifting rate of current is all 5.29mA/cm
2/ 0.5s, its electric current, voltage change are see the upper figure of Fig. 1 and figure below.
Embodiment 2 ~ 3 is similar to Example 1, and adopt same current variation pattern to carry out anodic oxidation, difference is constant current density value, the continuous current time, pulsed current minimum value, pulsed current maximum value, rate of current, falls in liter rate of current and cycle index is different.Table 1 is the relevant parameters of embodiment 2 ~ 3 Anodic Oxidation.
By embodiment 1 ~ 3 obtain titanic oxide nano tube thin-film scanning electron microscope (SEM) figure see Fig. 2 and Fig. 3.As seen from the figure, wherein titania nanotube is divided into layering nodular structure, almost soon ruptures in each joint junction, and the curved shape of tube wall of every two adjacent internodes.
Table 1
| Embodiment | Oxidation current variation pattern | Constant current density value mA/cm 2 | Continuous current time/s | Pulsed current minimum value mA/cm 2 | Pulsed current maximum value mA/cm 2 | Rise rate of current mA/cm 2/0.5s | Rate of current mA/cm falls 2/0.5s | Cycle index |
| 2 | Continuous current+pulsed current | 4.44 | 200 | 4.44 | 44.44 | 5.00 | 5.00 | 20 |
| 3 | Continuous current+pulsed current | 5.00 | 100 | 5.00 | 61.25 | 5.63 | 5.63 | 30 |
Experiment also shows, when the Faradaic current adopted is pulse change, when wherein carrying out electrolysis with continuous current between two impulse of current, the dutycycle of pulse is 1: 50 ~ 1: 500, and current density during constant-current electrolysis is 2.5 ~ 7.5mA/cm
2, pulsed current summit maximum value is 35 ~ 65mA/cm
2, all can obtain the titanic oxide nano tube thin-film of pattern shown in similar Fig. 2 and Fig. 3.
Embodiment 4: Titanium board is being cut into the substrate of 3.0cm × 1.0cm size and 250 μm of thickness, use acetone successively, Virahol, methyl alcohol and deionized water ultrasonic cleaning, then be carry out chemical rightenning in the mixing solutions of 1: 8 at hydrofluoric acid and concentrated nitric acid volume ratio, nitrogen dries up rear for subsequent use.At room temperature, make anode with titanium sheet, aluminium sheet is done electrode; With 85ml (NH
4f (0.25wt%)+H
2o (0.3vol%)+HOCH
2cH
2oH) be electrolytic solution, carry out electrolytic oxidation; Oxidation current is shown to provide by the universal source of Keithely 2400, and the program of writing with LabVIEW is by the change of conputer controlled electric current; Lifting curent change process is asymmetric, and electric current in time change curve is zig-zag, and zigzag wave minimum electrical current density is 2.78mA/cm
2, maximum current density is 33.33mA/cm
2, rising rate of current is 0.56mA/cm
2/ 0.5s, falling rate of current is 5.56mA/cm
2/ 0.5s, lifting rate of current ratio is 1: 10, and the voltage change curve in time of the electric current that the electrolysis see the upper figure of Fig. 4 the applies computer Real-Time Monitoring of change curve and Fig. 4 figure below in time, control like this is carried out periodic oxidation and circulated 30 times.
Embodiment 5 ~ 7 is similar to Example 4, and adopt same current variation pattern to carry out anodic oxidation, difference is minimum circuit density, maximum current density, rate of current, falls in liter rate of current and cycle index is different, and table 2 is the anodised correlation parameter of embodiment 5 ~ 7.
Table 2
| Embodiment | Curent change mode | Minimum electrical current density value mA/cm 2 | Maximum current density value/mA/cm 2 | Rise rate of current mA/cm 2/0.5s | Rate of current mA/cm falls 2 /0.5s | Cycle index |
| 5 | Zigzag wave | 0 | 44.44 | 1.11 | 11.11 | 50 |
| 6 | Zigzag wave | 5.56 | 27.78 | 1.13 | 2.26 | 40 |
| 7 | Zigzag wave | 5.56 | 27.78 | 1.67 | 4.17 | 50 |
The SEM figure of the titanic oxide nano tube thin-film that embodiment 4 ~ 7 obtains is shown in Fig. 5 and Fig. 6, and titania nanotube is wherein joint shape as seen from the figure, and the tube wall of every two adjacent internodes is curved.
Experiment also shows, when the Faradaic current adopted is sawtooth waveform change, and its minimum electrical current density 0 ~ 6.0mA/cm
2, maximum current density 25 ~ 50mA/cm
2, rise rate of current 0.3 ~ 2.5mA/cm
2, rate of current 2 ~ 12mA/cm falls
2/ 0.5s, all can obtain the titanic oxide nano tube thin-film of the pattern shown in similar Fig. 5 and Fig. 6.
Embodiment 8:
Titanium board is cut into the substrate of 3.0cm × 1.0cm size and 250 μm of thickness, use acetone successively, Virahol, methyl alcohol and deionized water ultrasonic cleaning, then be carry out chemical rightenning in the mixing solutions of 1: 8 at hydrofluoric acid and concentrated nitric acid volume ratio, nitrogen dries up rear for subsequent use.At room temperature, make anode with titanium sheet, aluminium sheet is done electrode; Get 85ml (NH
4f (0.25wt%)+H
2o (0.3vol%)+HOCH
2cH
2oH) electrolytic solution, carries out electrolytic oxidation; Oxidation current is shown to provide by the universal source of Keithely 2400, and the program of writing with LabVIEW is by the change of conputer controlled electric current, and electric current in time changing pattern is sinusoidal curve; Minimum current is 1.9mA/cm
2, sinusoidal amplitude is 7.5mA/cm
2; The time in each cycle is 56s, and oxidation current circulates 50 times, see the voltage curve over time that the real-time monitoring shown in figure below in the applying electric current shown in figure upper in Fig. 7 over time graphic representation and Fig. 7 obtains.
Embodiment 9 ~ 11 is similar to Example 8, and adopt same current variation pattern to carry out anodic oxidation, difference is minimum circuit density, amplitude current density, cycle time and cycle index different, table 3 is the anodised parameters of embodiment 8 ~ 11.
Table 3
| Embodiment | Curent change mode | Minimum electrical current density mA/cm 2 | Amplitude current density mA/cm 2 | Cycle/s | Cycle index |
| 9 | Sinusoidal wave | 0 | 16.67 | 10 | 50 |
| 10 | Sinusoidal wave | 0 | 15.79 | 20 | 50 |
| 11 | Sinusoidal wave | 2.78 | 5.56 | 30 | 25 |
The scanning electron microscope (SEM) photograph (SEM) of the titanic oxide nano tube thin-film that embodiment 8 ~ 11 obtains is shown in Fig. 8 and Fig. 9, as seen from the figure, the titanic oxide nano tube thin-film obtained is Bamboo-shaped, and the tube wall of every two adjacent internodes is in more obvious curve.
Experiment also shows, Faradaic current is sinusoidal waveform change, and its minimum electrical current density is 0 ~ 3mA/cm
2, its maximum current density is 5 ~ 19.45mA/cm
2, when the curent change cycle is 10 ~ 60/s, the pattern shown in the titanic oxide nano tube thin-film pattern obtained and Fig. 8 and Fig. 9 is similar.
In order to study the quantum size effect of specially-shaped titanium dioxide nano-tube, we determine sinusoidal current oxidation and continuous current oxidation nanometer pipe and they ultraviolet-visible spectrum after cadmium sulfide nano-particles sensitization.Figure 10 is measured ultraviolet-visible light spectrogram, wherein 1 and No. 2 curve is the ultraviolet-visible spectrum that sinusoidal current oxidation obtains the nanotube of titania nanotube and its sensitization respectively, and 3 and No. 4 curves are the ultraviolet-visible spectrum that continuous current oxidation obtains the nanotube of titania nanotube and its sensitization respectively.Can obviously find out, sinusoidal current is oxidized the pipe obtained has strong interference peaks at 400nm ~ 800nm.
Relevant experiment also shows, by realizing the control of nanotube nodular being asked to distance to the control of Faradaic current change frequency.
Claims (2)
1. the preparation method of specially-shaped titanium dioxide nano-tube films, to be fluorochemical as putting into solute after the pure titanium of base material thoroughly cleans, to add in electrolytic solution that a small amount of water is solvent in ethylene glycol or glycerine or low-molecular-weight liquid polyethylene glycol again, do with the metal sheet of non-titanium and electrochemical anodic oxidation is carried out to electrode, Faradaic current is made to be periodically when it is characterized in that electrolysis, pulse change, wherein between two impulse of current, carry out electrolysis with continuous current, the dutycycle of pulse is 1: 50 ~ 1: 500, current density during constant-current electrolysis is 2.5 ~ 7.5mA/cm
2, pulsed current summit maximum value is 35 ~ 65mA/cm
2.
2. the preparation method of specially-shaped titanium dioxide nano-tube films, be fluorochemical using as putting into solute after the pure titanium of base material thoroughly cleans, add with ethylene glycol or glycerine or low-molecular-weight liquid polyethylene glycol the electrolytic solution that a small amount of water is solvent again, do with the metal sheet of non-titanium and electrochemical anodic oxidation is carried out to electrode, Faradaic current is made to be periodicity, sawtooth waveform change when it is characterized in that electrolysis, its minimum electrical current density 0 ~ 6.0mA/cm
2, maximum current density 25 ~ 50mA/cm
2, rise rate of current 0.3 ~ 2.5mA/cm
2rate of current 2 ~ 12mA/cm, falls in/0.5s
2/ 0.5s.
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| CN102691087A (en) * | 2011-03-24 | 2012-09-26 | 威高集团有限公司 | Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface |
| CN102768904B (en) * | 2011-05-05 | 2015-03-11 | 中国科学院化学研究所 | Method for preparing working electrode of TiO2 nanotube array |
| CN103060879B (en) * | 2012-12-28 | 2015-04-08 | 武汉理工大学 | Conical TiO2 nanotube arrays and controllable preparation method |
| CN103590087B (en) * | 2013-10-16 | 2016-03-16 | 中国科学院合肥物质科学研究院 | Internal orifice dimension mechanical periodicity and cycle adjustable TiO 2nano-pipe array thin film and preparation method thereof |
| CN103924279B (en) * | 2014-04-10 | 2016-08-24 | 北京工业大学 | A kind of pulse anodic oxidation prepares method prepared by high-sequential titanium dioxide nano-pipe array thin film |
| CN104032355A (en) * | 2014-06-20 | 2014-09-10 | 中南大学 | Method for preparing semimetallic state conductive titanium black nano-tube array |
| CN105154955B (en) * | 2015-09-14 | 2018-04-24 | 中国科学院合肥物质科学研究院 | Cycle adjustable cycle layer structure TiO2Nano-pipe array thin film and preparation method thereof |
| JP7140329B2 (en) * | 2018-08-10 | 2022-09-21 | 地方独立行政法人山口県産業技術センター | Anodized titanium material and its manufacturing method |
| CN109825867A (en) * | 2019-04-10 | 2019-05-31 | 东北大学 | A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array |
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