CN106906507A - One-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization - Google Patents

One-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization Download PDF

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CN106906507A
CN106906507A CN201710041950.2A CN201710041950A CN106906507A CN 106906507 A CN106906507 A CN 106906507A CN 201710041950 A CN201710041950 A CN 201710041950A CN 106906507 A CN106906507 A CN 106906507A
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thin film
pipe array
tio
array thin
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CN106906507B (en
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裘吕超
刘芳
马朝霞
杨杭生
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention discloses a kind of anatase TiO of One Dimensional Quasi monocrystalline2The method of nano-pipe array thin film preferred orientation crystallization.The method combines heat treatment for the anodic oxidation of titanium sheet.Titanium sheet is specifically placed in the electrolyte Anodic Oxidation containing ethylene glycol, ammonium fluoride and water and prepares unbodied TiO2Nano-pipe array thin film, is then cleaned using ethylene glycol and ethanol successively, and regulation and control remain in amorphous TiO2F in nano-pipe array thin film‑Ion concentration, after drying, is heat-treated at 350 650 DEG C, is incubated 0.5 20 hours, obtains one-dimensional anatase TiO2Nano-tube array preferred orientation crystallographic film.The method of the present invention passes through process control, it is possible to achieve one-dimensional anatase TiO2The preferred orientation crystallization crystallization of nano-pipe array thin film.It is expected to be widely used in numerous areas such as solar cell, lithium ion battery, photocatalysis hydrogen production and photocatalysis Decomposition organic pollutions.

Description

One-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization
Technical field
The invention belongs to energy and environment Material Field, more particularly to a kind of acquisition is along the one of different Solute Content in Grain Dimension anatase TiO2The preparation method of nano-pipe array thin film.
Background technology
Titanium dioxide (TiO2), particularly Detitanium-ore-type TiO2As a kind of excellent semiconductor catalyst, because its safety It is nontoxic, there is excellent chemical stability and with low cost, in photocatalysis organic pollution, dye sensitization of solar Battery, lithium ion battery, light decomposition water produce the aspects such as hydrogen to be with a wide range of applications.Theoretical and experiment shows in sharp titanium Ore deposit type TiO2In, { 001 } crystal face ratio { 101 } crystal face has catalysis activity higher, yet with the former surface energy (0.90J·m-2) it is more than the latter (0.44Jm-2) so that the crystal obtained in actual preparation process is most of by { 101 } Crystal face wraps up (~94%), it is impossible at utmost play TiO2Advantage.
Recently, there is substantial amounts of research to be reported in the presence of fluoride, anatase TiO can be made2{ 001 } crystal face table Face can be less than { 101 } crystal face, so as to successfully prepare with the exposed TiO of { 001 } crystal face high2Single crystal grain (Nature, 2008,453,638-641；ACS Nano, 2013,7,2532-2540), but the material prepared is mostly powdered.For powder The TiO of last shape2Monocrystalline, carries out recycling relatively difficult to catalyst under many circumstances.And porous TiO2Nano-tube array Film, can solve the problems, such as that catalyst is difficult to reclaim, and in particular by anodizing, can simply prepare TiO2Nanotube Array film, for example, patent CN200610035723.0 discloses the TiO that a kind of utilization anodizing prepares high length-diameter ratio2 The method of nano-tube array；CN20081018387.3 is disclosed and a kind of is prepared orderly porous type TiO2Nano-pipe array thin film Method；CN200880108226.6 discloses a kind of length more than 10 microns, and aspect ratio reaches 10000 closed group of self orientation The TiO of dress2Nano-pipe array thin film；CN201110138088.X discloses a kind of anodizing and prepares TiO2Nano-tube array The method of film, the more regular anodizing TiO of prepared pattern2Nano-pipe array thin film；CN103147110.A discloses one Plant multilayer TiO2The preparation scheme of nanotube；CN101969109.A discloses a kind of dendroid Nano tube array of titanium dioxide electricity The preparation technology of pole；CN10154512.9 discloses a kind of method of synthesizing crystalline titanic oxide nano-tubes. CN10118704.3 discloses the overlength TiO with photocatalysis performance2The preparation method of nano-tube array.CN105369323.A Disclose a kind of branch type TiO2The preparation method of nano-tube array.CN176011.3 discloses super amphiphilic and super-hydrophobicity The preparation method of film of Nano tube array of titanium dioxide.And successfully make TiO2Surface exposure { 001 } crystal face of nano-tube film, pole Improve TiO greatly2Performance (Scientific Reports, 2015,5,17773).But TiO2Nano-pipe array thin film is but still Light induced electron and hole so are faced in the easily compound difficulty of grain boundaries, it is suppressed that the performance of its performance.Recently, some fragmentary grind Study carefully result to show, it is possible to prepare the one-dimensional TiO of { 001 } exposed nearly monocrystalline2Nano-tube array crystal film (Nanoscale, 2015,7,20386；J.Mater.Chem.A,2014,2,11454；CrystEngComm., 2015,17,7346).For example, CN201310123460.9 discloses a kind of monocrystalline anatase TiO2Nano-tube array and preparation method；CN201310426257.9 Disclose the TiO of orientation texture2The preparation method of nano-tube array.Although method used does not have any comparativity, can not Effective Regulation is carried out to high preferred orientation, the scheme solved in crystal boundary light induced electron and hole-recombination this problem is still shown.
Based on background above, the invention discloses a kind of one-dimensional anatase TiO2Nano-pipe array thin film preferred orientation is crystallized Method, not only can simply prepare the one-dimensional anatase TiO of quasi- monocrystalline2Nano-pipe array thin film, can also regulate and control its along The preferred orientation of different crystal faces.It is expected organic in solar cell, lithium ion battery, photocatalysis hydrogen production and photocatalysis Decomposition The numerous areas such as pollutant are widely used.
The content of the invention
It is an object of the invention to provide a kind of one-dimensional anatase TiO2The method of nano-pipe array thin film crystallographic orientation.
The one-dimensional anatase TiO that the present invention is prepared2Nano-tube array crystallographic orientation crystal film, is by regulating and controlling sun Pole oxidation prepares amorphous TiO2The concentration of ammonium fluoride in electrolyte during nano-pipe array thin film, cleaning process and follow-up Heating crystallization technique realize.The one-dimensional anatase TiO of quasi- mono-crystalline structures can be obtained2Nano-tube array crystallographic orientation is brilliant Body thin film, the orientation of its { 001 } crystal face can be from parallel with nanotube tube wall surface to the model vertical with nanotube tube wall surface It is regulated in enclosing, and shows the performance of excellent photocatalysis organic pollution.
The present invention provides a kind of one-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization, its specific side Case is as follows：Titanium (Ti) piece is placed in the electrolyte containing ethylene glycol, ammonium fluoride and water and is electrolysed 5-120 minutes, prepare nothing The TiO of setting2Nano-pipe array thin film, then using the NH in electrolyte4F concentration, and ethylene glycol and ethanol scavenger Skill, regulation and control remain in amorphous TiO2F in nano-pipe array thin film-Ion concentration, and after drying under the conditions of 60-100 DEG C, It is last that 350-650 DEG C of temperature is raised to certain heating rate in air atmosphere, and 0.5-20 hours is incubated, obtain one Tie up the anatase TiO of quasi- monocrystalline2Nano-pipe array thin film, the nanotube obtained by preparation can be along different Solute Content in Grain knots It is brilliant.
In above-mentioned technical proposal, the concentration of described electrolyte reclaimed water is 1v%-5v%, and the concentration of ammonium fluoride is 0.1wt.%-2wt.%, remaining is ethylene glycol.
Described step 3) in heating rate be 2 DEG C/min to 30 DEG C/min.
Step 1) in electrolysis when use direct current constant voltage method, magnitude of voltage is 20~100V, and electrolysis time is 5-120 point Clock.
In the method for the present invention, to the NH in electrolyte4The regulation and control of F concentration, the amorphous TiO of acquisition2Adopted after nano-tube array To the control of heating rate to the knot of product in technique that spent glycol and ethanol are cleaned successively and follow-up heat treatment process Brilliant process and crystalline orientation have a major impact.
The beneficial effects of the present invention are：
The one-dimensional anatase TiO of quasi- mono-crystalline structures can be obtained using the method for the present invention2Nano-pipe array thin film, very well Ground suppression light induced electron is compound with hole, and regulates and controls high preferred orientation according to demand.Preparation method of the invention operates Dan Jian, and It is low for equipment requirements.Compared with prior art, the present invention is by simply regulating and controlling heating technique, it is possible to prepare with accurate single The one-dimensional anatase TiO of crystal structure2Nano-pipe array thin film, F when then regulating and controlling anodic oxidation-Ion concentration and matching purge work Skill, realizes the crystallographic orientation of different high preferred orientations.The one-dimensional anatase TiO that the present invention is obtained2Nanotube has accurate single well Crystalline substance, suppression light induced electron is compound with hole well, can improve it in solar cell, lithium ion battery, photocatalysis The efficiency of the numerous areas such as hydrogen manufacturing and photocatalysis Decomposition organic pollution.
Brief description of the drawings
In Fig. 1 (a), (b), the SEM that (c) and (d) is respectively the gained sample of embodiment 1 schemes, X-ray diffraction (XRD) figure, TEM schemes and HTEM figures.
In Fig. 2 (a), (b), the SEM that (c) and (d) is respectively the gained sample of embodiment 2 schemes, X-ray diffraction (XRD) figure, TEM schemes and HTEM figures.
In Fig. 3 (a), (b), the SEM that (c) and (d) is respectively the gained sample of embodiment 4 schemes, X-ray diffraction (XRD) figure, TEM schemes and HTEM figures.
Fig. 4 is the comparison diagram of the photo-catalytic degradation of methyl-orange of embodiment 1,2 and 4 gained samples.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, but does not therefore limit the present invention to Within described scope of embodiments.
Embodiment 1：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 60 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.2wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-tube film array, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (260mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 3.5cm, in 90min is electrolysed under 30V, obtains a TiO for anodic oxidation2Nanometer Pipe；Step 2：First, by being grown in the TiO of titanium plate surface in ultrasonically treated () with removal step2Nanotube, to obtain Surface has the titanium sheet base plate of the titanium deoxid film of regular hexagonal looks, and the titanium sheet base plate of acquisition then is placed in into step (1) Electrolyte in, in being electrolysed 60min under 30V, to obtain with the clean amorphous TiO in regular morphology surface2Nano-tube array Film, and with 100ml ethylene glycol and 150ml ethanol continuous wash three times, dry amorphous TiO is obtained in 60 DEG C of drying2Receive Mitron array film, is designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 5 DEG C/min of heating rate, heat treatment temperature is 500 DEG C, is protected After warm time 5h, room temperature is naturally cooled to, obtain the one-dimensional anatase TiO with quasi- mono-crystalline structures2Nano-pipe array thin film.Figure A is surface and the side view of gained ATONAs in 1, it is known that it saves nano-tube array structure well from figure.From It is known that the diffraction peak intensity of (101) crystal face of gained sample is significantly stronger than the diffraction maximum of (001) crystal face in Fig. 1 (b), and From Fig. 1 (c) and the transmission electron microscope figure of (d), it is known that the tube wall of the nanotube is a monocrystal, its (101) are brilliant Angle between face and tube wall is 80 ° or so, it is known that it is crystallized mainly along (101) Solute Content in Grain.
Embodiment 2：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 80 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.3wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (260mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 3.5cm, in 90min is electrolysed under 30V, obtains the amorphous of an anodic oxidation TiO2Nano-pipe array thin film；Step 2：First, by being grown in titanium plate surface in ultrasonically treated () with removal step TiO2Nanotube, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, the titanium that will then obtain Piece base plate is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, to obtain with the clean nothing in regular morphology surface Setting TiO2Nano-pipe array thin film, and it is secondary with 500ml ethylene glycol and 100ml ethanol continuous wash, in 80 DEG C of drying, it is designated as ATONAs。
3) ATONAs is heat-treated in air atmosphere, 4 DEG C/min of heating rate, heat treatment temperature is 500 DEG C, is protected After warm time 5h, room temperature is naturally cooled to, obtain the one-dimensional anatase TiO with quasi- mono-crystalline structures2Nano-pipe array thin film.Figure 2 (a) is surface and the side view of resulting ATONAs, it is known that it saves nano-tube array knot well from figure Structure.From the XRD results of Fig. 2 (b) it is recognised that compared with the gained sample of embodiment 1, finding the strong of its (101) crystallographic plane diffraction peak Degree weakens, the intensity enhancing of (001) crystallographic plane diffraction peak, it is known that the orientation of this sample has deflected, from Fig. 2 (c) and (d) In TEM and HRTEM figures in it can be seen that the angle of (101) crystal face and the tube wall of this sample is 60 ° or so, and from TEM figures It can be seen that continuous lattice fringe, the sample obtained by explanation has good class monocrystalline.
Embodiment 3：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 80 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.4wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (200mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 5cm, in 70min is electrolysed under 50V, obtains the amorphous TiO of an anodic oxidation2 Nano-pipe array thin film；Step 2：First, by being grown in the amorphous of titanium plate surface in ultrasonically treated () with removal step TiO2Nano-pipe array thin film, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, then will The titanium sheet base plate of acquisition is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, has regular morphology surface to obtain Clean amorphous TiO2Nano-pipe array thin film, and it is secondary with 100ml ethylene glycol and 100ml ethanol continuous wash, in 50 DEG C Drying, is designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 2 DEG C/min of heating rate, heat treatment temperature is 500 DEG C, is protected Room temperature is naturally cooled to after warm time 12h, the one-dimensional anatase TiO with quasi- mono-crystalline structures is obtained2Nano-pipe array thin film.It is logical Cross SEM observations and find its surface and side view, determine that it saves nano-tube array structure well.Understand that it is from TEM figures Quasi- mono-crystalline structures, quantitative determination (101) crystal face finds that (101) face further deflects, between tube wall with the angle of tube wall Angle become for 45 ° or so.
Embodiment 4：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 80 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.5wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (260mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 2.5cm, in 70min is electrolysed under 30V, obtains the amorphous of an anodic oxidation TiO2Nano-pipe array thin film；Step 2：First, by being grown in the nothing of titanium plate surface in ultrasonically treated () with removal step Setting TiO2Nano-pipe array thin film, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, connects And the titanium sheet base plate of acquisition is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, there is regular morphology to obtain The clean amorphous TiO in surface2Nano-pipe array thin film, and it is secondary with 150ml ethylene glycol and 200ml ethanol continuous wash, in 55 DEG C of drying, are designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 3 DEG C/min of heating rate, heat treatment temperature is 500 DEG C, is protected After warm time 5h, room temperature is naturally cooled to, obtain the one-dimensional anatase TiO with quasi- mono-crystalline structures2Nano-pipe array thin film.Figure 3 (a) is surface and the side view of gained ATONAs, it is known that it saves nano-tube array structure well from figure.From The XRD results of Fig. 3 (b) are it is recognised that the intensity of (001) diffraction maximum of the sample of the gained of embodiment 4 has been significantly stronger than (101) The intensity of diffraction maximum, Fig. 3 (c) is the TEM figures of the gained sample of embodiment 4, and (001) crystal face has been deflected into as we can see from the figure Vertically with tube wall direction, this can also be corresponding with the result of XRD, and the diffraction maximum of (001) becomes strong, the diffraction peak intensity of (101) Die down, it is known that the orientation of the sample of the gained of embodiment 4 have changed into (001) crystal face vertically with tube wall direction, and along (001) Solute Content in Grain crystallization.
Embodiment 5：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 80 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.6wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (240mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 4.0cm, in 30min is electrolysed under 40V, obtains the amorphous of an anodic oxidation TiO2Nano-pipe array thin film；Step 2：First, by being grown in the nothing of titanium plate surface in ultrasonically treated () with removal step Setting TiO2Nano-pipe array thin film, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, connects And the titanium sheet base plate of acquisition is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, there is regular morphology to obtain The clean amorphous TiO in surface2Nano-pipe array thin film, and it is secondary with 300ml ethylene glycol and 100ml ethanol continuous wash, in 55 DEG C of drying, are designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 1 DEG C/min of heating rate, heat treatment temperature is 500 DEG C, is protected After warm time 5h, room temperature is naturally cooled to, obtain the one-dimensional TiO of Detitanium-ore-type with quasi- mono-crystalline structures2Nano-pipe array thin film. Wherein the angle of (001) between crystal face and tube wall is 90 °.
Embodiment 6：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 60 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.24wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (300mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 3.8cm, in 45min is electrolysed under 35V, obtains the amorphous of an anodic oxidation TiO2Nano-pipe array thin film；Step 2：First, by being grown in the nothing of titanium plate surface in ultrasonically treated () with removal step Setting TiO2Nano-pipe array thin film, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, connects And the titanium sheet base plate of acquisition is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, there is regular morphology to obtain The clean amorphous TiO in surface2Nano-pipe array thin film, and with 100ml ethylene glycol and 200ml ethanol continuous wash three times, in 55 DEG C of drying, are designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 2 DEG C/min of heating rate, heat treatment temperature is 600 DEG C, is protected After warm time 5h, room temperature is naturally cooled to, obtain the one-dimensional anatase TiO with quasi- mono-crystalline structures2Nano-pipe array thin film.It is real The angle of (101) between crystal face and tube wall is 70 degree or so in the nanotube of the gained of example 7.
Embodiment 7：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 60 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.22wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (300mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 5cm, in 30min is electrolysed under 50V, obtains the amorphous TiO of an anodic oxidation2 Nano-pipe array thin film；Step 2：First, by being grown in the amorphous of titanium plate surface in ultrasonically treated () with removal step TiO2Nano-pipe array thin film, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, then will The titanium sheet base plate of acquisition is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, has regular morphology surface to obtain Clean amorphous TiO2Nano-pipe array thin film, and with 150ml ethylene glycol and 200ml ethanol continuous wash three times, in 60 DEG C Drying, is designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 2.5 DEG C/min of heating rate, heat treatment temperature is 600 DEG C, After soaking time 8h, room temperature is naturally cooled to, obtain the one-dimensional TiO of Detitanium-ore-type with quasi- mono-crystalline structures2Nano-tube array is thin Film.The angle of (101) between crystal face and tube wall is 75 degree or so in the nanotube of the gained of example 7.
Embodiment 8：
1) titanium sheet pretreatment and configuration electrolyte：Titanium sheet is cut into 8 × 9cm2Square piece long and successively in liquid soap, second It is cleaned by ultrasonic 2h in alcohol and deionized water, last 60 DEG C of drying are standby；Electrolyte A is configured, the composition ratio of electrolyte is：Second two Alcohol：5v%H2O：0.45wt.%NH4F。
2) amorphous TiO is prepared2Nano-pipe array thin film：Amorphous TiO is prepared by two-step method2Nano-pipe array thin film, Step one：The titanium sheet obtained in (1) is placed in the electrolyte of ethylene glycol, water and ammonium fluoride (500mL), with titanium sheet as anode, Graphite flake is negative electrode, and the spacing of the two is 3.8cm, in 65min is electrolysed under 45V, obtains the amorphous of an anodic oxidation TiO2Nano-pipe array thin film；Step 2：First, by being grown in the nothing of titanium plate surface in ultrasonically treated () with removal step Setting TiO2Nano-pipe array thin film, to obtain the titanium sheet base plate that surface has the titanium deoxid film of regular hexagonal looks, connects And the titanium sheet base plate of acquisition is placed in the electrolyte of step (1), in 60min is electrolysed under 30V, there is regular morphology to obtain The clean amorphous TiO in surface2Nano-pipe array thin film, and with 200ml ethylene glycol and 300ml ethanol continuous wash four times, in 60 DEG C of drying, are designated as ATONAs.
3) ATONAs is heat-treated in air atmosphere, 3.5 DEG C/min of heating rate, heat treatment temperature is 500 DEG C, After soaking time 20h, room temperature is naturally cooled to, obtain the one-dimensional TiO of Detitanium-ore-type with quasi- mono-crystalline structures2Nano-tube array is thin Film.The angle of (001) between crystal face and tube wall is 10 degree or so in the nanotube of the gained of example 8.
The ATONAs obtained in embodiment 1,2,4 is carried out the experiment of degraded methyl orange.The concentration of methyl orange is 6mg/L, Using the mercury lamp of 150W as lamp source, the slice, thin piece of above-mentioned material 3.5cm*3.5cm is placed in the methyl orange solution of 30mL respectively, Lamp source is away from solution 15cm.Before experiment, device is first placed in 40min under conditions of dark, mercury lamp is then opened, every 30min Take out 2mL methyl orange solutions, and with UV-vis3600 New UV Spectrophotometrics and measurement methyl orange concentration, wherein methyl orange feature suction Spectrum is received at 463nm, Therapy lasted 180min, experimental result is as shown in Figure 4.As Fig. 4 it can be found that obtained by example 4 The photocatalysis efficiency of sample is better than the gained sample of example 1 and 2, and the photocatalysis efficiency of the sample of example 4 is 1.7 times of example 1. And with the exposed anatase TiO of { 001 } crystal face of reported in literature2The performance of nano-tube film is compared, photocatalysis Decomposition methyl The performance of orange, has been respectively increased 1.9 times, 2.2 times and 3 times (Scientific Reports, 2015,5,17773).
Above-mentioned specific embodiment is only some specific implementation examples of the invention, the invention is not restricted to above example Son, in the protection domain of spirit and claims of the present invention, any modifications and changes made to the present invention are considered as It is to fall into protection scope of the present invention.

Claims (5)

1. one-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization, it is characterised in that the method is first using sun Pole oxidizing process prepares one-dimensional amorphous TiO2Nano-pipe array thin film, once purged reheating crystallizes crystallization, obtains quasi- monocrystalline knot The one-dimensional anatase TiO of structure2Nano-pipe array thin film, its crystalline orientation controllable.
2. one-dimensional anatase TiO according to claim 12The method of nano-pipe array thin film preferred orientation crystallization, its feature It is that the method comprises the following steps：
1) with titanium sheet as anode, metallic copper or graphite are negative electrode, with ethylene glycol and water as double solvents, with ammonium fluoride as electrolyte It is configured to electrolyte；One-dimensional amorphous TiO is prepared in titanium sheet using anodizing2Nano-pipe array thin film；
2) after being washed using ethylene glycol washing, ethanol successively, dried at 60-100 DEG C；
3) in air atmosphere, to the one-dimensional amorphous TiO after the treatment of upper step at a temperature of 350-650 DEG C2Nano-tube array is thin Film is heat-treated, and soaking time is 0.5-20h, obtains the one-dimensional anatase TiO of quasi- mono-crystalline structures2Nano-pipe array thin film.
3. one-dimensional anatase TiO according to claim 22The method of nano-pipe array thin film preferred orientation crystallization, its feature It is that the concentration of described electrolyte reclaimed water is 1v%-5v%, and the concentration of ammonium fluoride is 0.1wt.%-2wt.%, and remaining is second Glycol.
4. one-dimensional anatase TiO according to claim 22The method of nano-pipe array thin film preferred orientation crystallization, its feature Be, described step 3) in heating rate be 2 DEG C/min to 30 DEG C/min.
5. one-dimensional anatase TiO according to claim 22The method of nano-pipe array thin film preferred orientation crystallization, its feature Be, step 1) in electrolysis when using DC constant voltage method, magnitude of voltage is 20~100V, and electrolysis time is 5-120 minutes.
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