CN106906507B - 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 PDFInfo
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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Abstract
The invention discloses a kind of anatase TiO of one-dimensional quasi- monocrystalline2The method of nano-pipe array thin film preferred orientation crystallization.This method is that the anodic oxidation of titanium sheet combines heat treatment.Titanium sheet is specifically placed in the electrolyte Anodic Oxidation containing ethylene glycol, ammonium fluoride and water, unbodied TiO is prepared2Then nano-pipe array thin film is successively cleaned using ethylene glycol and ethyl alcohol, regulation remains in amorphous TiO2F in nano-pipe array thin film‑Ion concentration is heat-treated after dry at 350-650 DEG C, is kept the temperature 0.5-20 hours, is obtained one-dimensional anatase TiO2Nano-tube array preferred orientation crystallographic film.One-dimensional anatase TiO may be implemented by process control in method of the invention2The preferred orientation of nano-pipe array thin film crystallizes crystallization.It is expected to be widely used in numerous areas such as solar battery, lithium ion battery, photocatalysis hydrogen production and photocatalysis Decomposition organic pollutants.
Description
Technical field
The invention belongs to energy and environment Material Field, in particular to a kind of acquisition is along the one of different Solute Content in Grain
Tie up anatase TiO2The preparation method of nano-pipe array thin film.
Background technique
Titanium dioxide (TiO2), especially Detitanium-ore-type TiO2As a kind of excellent semiconductor catalyst, because of its safety
It is nontoxic, have many advantages, such as excellent chemical stability and low in cost, in photocatalysis organic pollutant, dye sensitization of solar
Battery, lithium ion battery, photodegradation water generate hydrogen etc. and are with a wide range of applications.Theoretical and experiment shows in rutile titania
Mine type TiO2In, { 001 } crystal face ratio { 101 } crystal face has higher catalytic activity, however due to the former surface energy
(0.90J·m-2) it is greater 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%), cannot utmostly play TiO2Advantage.
Recently, there is a large amount of research to be reported under the action of fluoride, anatase TiO can be made2{ 001 } crystal face
Surface can be lower than { 101 } crystal face, to successfully prepare the TiO with high { 001 } crystal face exposure2Single 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 shape2It is relatively difficult to carry out recycling and reusing to catalyst in many cases for monocrystalline.And porous TiO2Nano-tube array
Film can solve catalyst and be difficult to the problem of recycling, and in particular by anodizing, can simply prepare TiO2Nanotube
Array film, for example, patent CN200610035723.0 discloses a kind of TiO for preparing high length-diameter ratio using anodizing2
The method of nano-tube array；CN20081018387.3, which is disclosed, a kind of prepares orderly porous type TiO2Nano-pipe array thin film
Method；It is more than 10 microns that CN200880108226.6, which discloses a kind of length, and the self orientation that aspect ratio reaches 10000 is closed
The TiO of assembling2Nano-pipe array thin film；CN201110138088.X discloses a kind of anodizing preparation TiO2Nanotube battle array
The more regular anodizing TiO of pattern is made in the method for column film2Nano-pipe array thin film；CN103147110.A is disclosed
A kind of multilayer TiO2The preparation method of nanotube；CN101969109.A discloses a kind of dendroid Nano tube array of titanium dioxide
The preparation process of electrode；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
TiO is improved greatly2Performance (Scientific Reports, 2015,5,17773).But TiO2Nano-pipe array thin film is but still
So face light induced electron and the hole difficulty easily compound in grain boundaries, it is suppressed that the performance of its performance.Recently, some fragmentary to grind
Study carefully as the result is shown, it is possible to prepare the one-dimensional TiO of the nearly monocrystalline of { 001 } exposure2Nano-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 discloses the TiO of orientation texture2The preparation method of nano-tube array.Although method used is not appointed
What comparativity can not carry out Effective Regulation to high preferred orientation, still show solution in crystal boundary light induced electron and hole-recombination
The scheme of this problem.
Based on background above, the invention discloses a kind of one-dimensional anatase TiO2The crystallization of nano-pipe array thin film preferred orientation
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 battery, lithium ion battery, photocatalysis hydrogen production and photocatalysis Decomposition
The numerous areas such as pollutant are widely used.
Summary of the invention
The object of the present invention is 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 regulation sun
Pole oxidation prepares amorphous TiO2The concentration, cleaning process of ammonium fluoride and subsequent in electrolyte when nano-pipe array thin film
Heating crystallization technique realize.The one-dimensional anatase TiO of quasi- monocrystalline structure can be made2Nano-tube array crystallographic orientation
The orientation of crystal film, { 001 } crystal face can be from parallel with nanotube tube wall surface to vertical with nanotube tube wall surface
It is regulated in range, and shows the performance of excellent photocatalysis organic pollutant.
The present invention provides a kind of one-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization, specific side
Case is as follows: titanium (Ti) piece being placed in the electrolyte containing ethylene glycol, ammonium fluoride and water and is electrolysed 5-120 minutes, nothing is prepared
The TiO of setting2Then nano-pipe array thin film utilizes the NH in electrolyte4The scavenger of F concentration and ethylene glycol and ethyl alcohol
Skill, regulation remain in amorphous TiO2F in nano-pipe array thin film-Ion concentration, and under the conditions of 60-100 DEG C after drying,
Finally in air atmosphere, it is raised to 350-650 DEG C of temperature with certain heating rate, and keep the temperature 0.5-20 hours, obtains one
Tie up the anatase TiO of quasi- monocrystalline2Nano-pipe array thin film, preparing resulting nanotube can be along different Solute Content in Grain
Crystallization.
In above-mentioned technical proposal, the concentration of water is 1v%-5v% in the electrolyte, and the concentration of ammonium fluoride is
0.1wt.%-2wt.%, remaining is ethylene glycol.
Heating rate is 2 DEG C/min to 30 DEG C/min in the step 3).
Direct current constant voltage method is used in step 1) when electrolysis, voltage value is 20~100V, and electrolysis time is 5-120 points
Clock.
In method of the invention, to the NH in electrolyte4The regulation of F concentration obtains amorphous TiO2It is adopted after nano-tube array
To the control of heating rate to the knot of product in the technique and follow-up heat treatment process that spent glycol and ethyl alcohol successively clean
Brilliant process and crystalline orientation have a major impact.
The beneficial effects of the present invention are:
The one-dimensional anatase TiO of quasi- monocrystalline structure can be obtained using method of the invention2Nano-pipe array thin film, very well
Ground inhibits the compound of light induced electron and 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 process, so that it may which preparing has quasi- list
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 obtains2Nanotube has quasi- single well
Crystalline substance inhibits the compound of light induced electron and hole well, it can be improved in solar battery, lithium ion battery, photocatalysis
The efficiency of the numerous areas such as hydrogen manufacturing and photocatalysis Decomposition organic pollutant.
Detailed description of the invention
In Fig. 1 (a), (b), (c) and (d) be respectively 1 gained sample of embodiment SEM figure, X-ray diffraction (XRD) figure,
TEM figure and HTEM figure.
In Fig. 2 (a), (b), (c) and (d) be respectively 2 gained sample of embodiment SEM figure, X-ray diffraction (XRD) figure,
TEM figure and HTEM figure.
In Fig. 3 (a), (b), (c) and (d) be respectively 4 gained sample of embodiment SEM figure, X-ray diffraction (XRD) figure,
TEM figure and HTEM figure.
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 the scope of the embodiment described.
Embodiment 1:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 60 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (260mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 3.5cm, is electrolysed 90min under 30V, obtains the TiO of an anodic oxidation2Nanometer
Pipe；Step 2: firstly, by ultrasonic treatment to remove the TiO for being grown in titanium plate surface in step (1)2Nanotube, to obtain
Surface has the titanium sheet bottom plate of the titanium deoxid film of regular hexagonal looks, and the titanium sheet bottom plate of acquisition is then placed in step (1)
Electrolyte in, 60min is electrolysed under 30V, to obtain the amorphous TiO for having regular morphology surface clean2Nano-tube array
Film, and three times with 100ml ethylene glycol and 150ml ethyl alcohol continuous wash, dry amorphous TiO is obtained in 60 DEG C of drying2It receives
Mitron array film, is denoted 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, obtains the one-dimensional anatase TiO with quasi- monocrystalline structure2Nano-pipe array thin film.Figure
Surface and the side view that a is 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
And from the transmission electron microscope figure of Fig. 1 (c) and (d), it is known that the tube wall of the nanotube is a monocrystal, (101)
Angle between crystal 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 titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 80 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (260mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 3.5cm, is electrolysed 90min under 30V, obtains the amorphous of an anodic oxidation
TiO2Nano-pipe array thin film；Step 2: firstly, being grown in titanium plate surface in step (1) by ultrasonic treatment to remove
TiO2Nanotube, to obtain the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks, then by the titanium of acquisition
Piece bottom plate is placed in the electrolyte of step (1), is electrolysed 60min under 30V, to obtain the nothing for having regular morphology surface clean
Shape TiO2Nano-pipe array thin film, and it is secondary with 500ml ethylene glycol and 100ml ethyl alcohol continuous wash, it dries, is denoted as in 80 DEG C
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, obtains the one-dimensional anatase TiO with quasi- monocrystalline structure2Nano-pipe array thin film.Figure
2 (a) surface and side view for obtained ATONAs, it is known that it saves nano-tube array knot well from figure
Structure.From the XRD result of Fig. 2 (b) it is recognised that finding the strong of its (101) crystallographic plane diffraction peak compared with 1 gained sample of embodiment
Degree weakens, the enhanced strength 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 figure in it can be seen that (101) crystal face and the angle of tube wall of this sample are 60 ° or so, and from TEM
Figure illustrates that resulting sample has good class monocrystalline it can be seen that continuous lattice fringe.
Embodiment 3:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 80 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (200mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 5cm, is electrolysed 70min under 50V, obtains the amorphous TiO of an anodic oxidation2
Nano-pipe array thin film；Step 2: firstly, being grown in the amorphous of titanium plate surface in step (1) by ultrasonic treatment to remove
TiO2Nano-pipe array thin film then will with obtaining the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks
The titanium sheet bottom plate of acquisition is placed in the electrolyte of step (1), is electrolysed 60min 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 ethyl alcohol continuous wash, in 50 DEG C
Drying, is denoted 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, obtains the one-dimensional anatase TiO with quasi- monocrystalline structure2Nano-pipe array thin film.
It is observed by SEM and finds its surface and side view, determine that it saves nano-tube array structure well.It is known from TEM figure
Subject to mono-crystalline structures, the angle for quantitative determining (101) crystal face and tube wall finds, the deflection of (101) face further occurrence, with tube wall it
Between angle become 45 ° or so.
Embodiment 4:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 80 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (260mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 2.5cm, is electrolysed 70min under 30V, obtains the amorphous of an anodic oxidation
TiO2Nano-pipe array thin film；Step 2: firstly, by ultrasonic treatment to remove the nothing for being grown in titanium plate surface in step (1)
Shape TiO2Nano-pipe array thin film is connect with obtaining the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks
The titanium sheet bottom plate of acquisition is placed in the electrolyte of step (1), be electrolysed 60min under 30V, with obtain have regular morphology
The clean amorphous TiO in surface2Nano-pipe array thin film, and it is secondary with 150ml ethylene glycol and 200ml ethyl alcohol continuous wash, in
55 DEG C of drying, are denoted 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, obtains the one-dimensional anatase TiO with quasi- monocrystalline structure2Nano-pipe array thin film.Figure
3 (a) surface and side view for gained ATONAs, it is known that it saves nano-tube array structure well from figure.From
The XRD result of Fig. 3 (b) is it is recognised that the intensity of (001) diffraction maximum of the resulting sample of embodiment 4 has been significantly stronger than
(101) intensity of diffraction maximum, Fig. 3 (c) are the TEM figures of 4 gained sample of embodiment, and (001) crystal face has been as we can see from the figure
It deflects into 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 of (101)
Peak intensity dies down, it is known that the orientation of the resulting sample of embodiment 4 have changed into (001) crystal face vertically with tube wall direction, and
And it is crystallized along (001) Solute Content in Grain.
Embodiment 5:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 80 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (240mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 4.0cm, is electrolysed 30min under 40V, obtains the amorphous of an anodic oxidation
TiO2Nano-pipe array thin film；Step 2: firstly, by ultrasonic treatment to remove the nothing for being grown in titanium plate surface in step (1)
Shape TiO2Nano-pipe array thin film is connect with obtaining the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks
The titanium sheet bottom plate of acquisition is placed in the electrolyte of step (1), be electrolysed 60min under 30V, with obtain have regular morphology
The clean amorphous TiO in surface2Nano-pipe array thin film, and it is secondary with 300ml ethylene glycol and 100ml ethyl alcohol continuous wash, in
55 DEG C of drying, are denoted 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, obtains that there is the one-dimensional TiO of the Detitanium-ore-type of quasi- monocrystalline structure2Nano-pipe array thin film.
Wherein the angle of (001) between crystal face and tube wall is 90 °.
Embodiment 6:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 60 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (300mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 3.8cm, is electrolysed 45min under 35V, obtains the amorphous of an anodic oxidation
TiO2Nano-pipe array thin film；Step 2: firstly, by ultrasonic treatment to remove the nothing for being grown in titanium plate surface in step (1)
Shape TiO2Nano-pipe array thin film is connect with obtaining the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks
The titanium sheet bottom plate of acquisition is placed in the electrolyte of step (1), be electrolysed 60min under 30V, with obtain have regular morphology
The clean amorphous TiO in surface2Nano-pipe array thin film, and three times with 100ml ethylene glycol and 200ml ethyl alcohol continuous wash, in
55 DEG C of drying, are denoted 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, obtains the one-dimensional anatase TiO with quasi- monocrystalline structure2Nano-pipe array thin film.It is real
The angle of (101) between crystal face and tube wall is 70 degree or so in the resulting nanotube of example 7.
Embodiment 7:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 60 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (300mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 5cm, is electrolysed 30min under 50V, obtains the amorphous TiO of an anodic oxidation2
Nano-pipe array thin film；Step 2: firstly, being grown in the amorphous of titanium plate surface in step (1) by ultrasonic treatment to remove
TiO2Nano-pipe array thin film then will with obtaining the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks
The titanium sheet bottom plate of acquisition is placed in the electrolyte of step (1), is electrolysed 60min under 30V, has regular morphology surface to obtain
Clean amorphous TiO2Nano-pipe array thin film, and three times with 150ml ethylene glycol and 200ml ethyl alcohol continuous wash, in 60 DEG C
Drying, is denoted as ATONAs.
3) ATONAs being 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, obtains that there is the one-dimensional TiO of the Detitanium-ore-type of quasi- monocrystalline structure2Nano-tube array is thin
Film.The angle of (101) between crystal face and tube wall is 75 degree or so in the resulting nanotube of example 7.
Embodiment 8:
1) titanium sheet titanium sheet pretreatment and configuration electrolyte: is cut into 8 × 9cm2Long square piece and successively in liquid soap, second
It is cleaned by ultrasonic 2h in pure and mild deionized water, last 60 DEG C of drying are spare；Configure electrolyte A, the ingredient ratio of electrolyte are as follows: 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 1: being placed in the electrolyte of ethylene glycol, water and ammonium fluoride (500mL) for the titanium sheet obtained in (1), using titanium sheet as anode,
Graphite flake is cathode, and the spacing of the two is 3.8cm, is electrolysed 65min under 45V, obtains the amorphous of an anodic oxidation
TiO2Nano-pipe array thin film；Step 2: firstly, by ultrasonic treatment to remove the nothing for being grown in titanium plate surface in step (1)
Shape TiO2Nano-pipe array thin film is connect with obtaining the titanium sheet bottom plate of titanium deoxid film of the surface with regular hexagonal looks
The titanium sheet bottom plate of acquisition is placed in the electrolyte of step (1), be electrolysed 60min under 30V, with obtain have regular morphology
The clean amorphous TiO in surface2Nano-pipe array thin film, and with 200ml ethylene glycol and 300ml ethyl alcohol continuous wash four times, in
60 DEG C of drying, are denoted as ATONAs.
3) ATONAs being 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, obtains that there is the one-dimensional TiO of the Detitanium-ore-type of quasi- monocrystalline structure2Nano-tube array is thin
Film.The angle of (001) between crystal face and tube wall is 10 degree or so in the resulting nanotube of example 8.
The ATONAs obtained in embodiment 1,2,4 is carried out to the experiment of degradation methyl orange.The concentration of methyl orange is 6mg/L,
Use the mercury lamp of 150W as lamp source, piece of above-mentioned material 3.5cm*3.5cm be 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 solution, and with UV-vis3600 New UV Spectrophotometric and the concentration of measurement methyl orange, the wherein feature of methyl orange
Absorption spectra is located at 463 nm, Therapy lasted 180min, and experimental result is as shown in Figure 4.By Fig. 4 it can be found that 4 institute of example
The photocatalysis efficiency of the sample obtained is better than the gained sample of example 1 and 2, and the photocatalysis efficiency of 4 sample of example is example 1
1.7 again.And the anatase TiO with the exposure of { 001 } crystal face of reported in literature2The performance of nano-tube film is compared, photocatalysis point
1.9 times, 2.2 times and 3 times (Scientific Reports, 2015,5,17773) have been respectively increased in the performance for solving methyl orange.
Above-mentioned specific embodiment is only some specific embodiments of the present invention, and present invention is not limited to the above embodiments
Son to any modifications and changes that the present invention makes, is considered as within the spirit of the invention and the scope of protection of the claims
It is to fall into protection scope of the present invention.
Claims (2)
1. a kind of one-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization, which is characterized in that this method includes
Following steps:
1) using titanium sheet as anode, metallic copper or graphite are cathode, are electrolysis with ammonium fluoride using ethylene glycol and water as double solvents
Matter is configured to electrolyte；One-dimensional amorphous TiO is prepared in titanium sheet using anodizing2Nano-pipe array thin film；Institute
The concentration of water is 1 v%-5 v% in the electrolyte stated, and the concentration of ammonium fluoride is 0.1 wt.%-, 2 wt.%, remaining is ethylene glycol；
2) it is successively washed using ethylene glycol, after ethanol washing, in 60-100oIt is dried under C；
3) in air atmosphere, in 350-650oTo upper step treated one-dimensional amorphous TiO at a temperature of C2Nano-tube array is thin
Film is heat-treated, and heating rate is 2 DEG C/min to 30 DEG C/min, and soaking time is 0.5-20 h, obtains quasi- monocrystalline structure
One-dimensional anatase TiO2Nano-pipe array thin film.
2. one-dimensional anatase TiO according to claim 12The method of nano-pipe array thin film preferred orientation crystallization, feature
It is, DC constant voltage method is used when being electrolysed in step 1), and voltage value is 20 ~ 100 V, and electrolysis time is 5-120 minutes.
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| CN102995091A (en) * | 2012-11-26 | 2013-03-27 | 北京大学 | Method for preparing titanium dioxide nano tip array film for field emission |
| CN103320856A (en) * | 2013-06-19 | 2013-09-25 | 电子科技大学 | Preparation method of fluoride-free single-crystal TiO2 nanometer thin film |
| CN103498182A (en) * | 2013-09-18 | 2014-01-08 | 上海大学 | Preparation method of titanium dioxide nanotube array with orientation structure |
| CN103614761A (en) * | 2013-12-02 | 2014-03-05 | 天津大学 | Method for preparing highly-ordered titanium dioxide nanotube and application in dye-sensitized solar cell |
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| CN102995091A (en) * | 2012-11-26 | 2013-03-27 | 北京大学 | Method for preparing titanium dioxide nano tip array film for field emission |
| CN103320856A (en) * | 2013-06-19 | 2013-09-25 | 电子科技大学 | Preparation method of fluoride-free single-crystal TiO2 nanometer thin film |
| CN103498182A (en) * | 2013-09-18 | 2014-01-08 | 上海大学 | Preparation method of titanium dioxide nanotube array with orientation structure |
| CN103614761A (en) * | 2013-12-02 | 2014-03-05 | 天津大学 | Method for preparing highly-ordered titanium dioxide nanotube and application in dye-sensitized solar cell |
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