CN104986797A - Preparation method of anatase TiO2 nanotube thin film - Google Patents
Preparation method of anatase TiO2 nanotube thin film Download PDFInfo
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- CN104986797A CN104986797A CN201510380960.XA CN201510380960A CN104986797A CN 104986797 A CN104986797 A CN 104986797A CN 201510380960 A CN201510380960 A CN 201510380960A CN 104986797 A CN104986797 A CN 104986797A
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Abstract
The invention discloses a preparation method of an anatase TiO2 nanotube thin film. The preparation method comprises the following main steps: immersing a metal titanium plate in a 1.0-2.0 mol/L sodium hydroxide solution to obtain a reaction substance, conducting thermal insulation on the reaction substance in a hydrothermal reaction kettle for 12-24 hours at the temperature of 200-220 DEG C, then cooling the reaction substance subjected to thermal insulation to a room temperature, and immersing the cooled reaction substance in a hydrochloric acid solution to conduct acid exchanging to obtain a titanic acid nanowire; immersing the titanic acid nanowire in a 80-DEG C sulfuric acid solution of which the pH value is 1.5-2.5 to react for 24-72 hours to obtain the anatase TiO2 nanotube thin film. A reaction template or an external electric field is not needed, the operation is simple and easy, the cost is low, the prepared anatase TiO2 nanotube thin film is uniform, good in crystallization, and firmly combined with a matrix, and the photocatalytic activity is remarkably higher than that of an anatase TiO2 nanotube thin film obtained through combination of an alkali heating method and post heat treatment. The anatase TiO2 nanotube thin film can be applied to the field of photocatalytic environment restoration.
Description
Technical field
The present invention relates to a kind of TiO
2the preparation method of film, particularly relates to a kind of anatase octahedrite TiO
2the preparation method of nano-tube film.
Background technology
TiO
2nanotube is owing to having unique tubular structure and larger specific surface area, and the application relating to surface reaction and carrier mobility at such as photochemical catalysis, photoelectrocatalysis, thin-film solar cells, gas sensor etc. possesses excellent performance.But with regard to hollow nanotube structure TiO
2, existing technology of preparing or relate to templated synthesis or need extra electric field anodic oxidation, and the nanotube that the High Temperature High Pressure arrangement of producing is unordered, industrialization cost is higher.Such as, patent of invention CN201310497349.6 discloses a kind of by TiO
2nanosphere powder and poly-hydroxy organism add in sodium hydroxide solution, and through hydro-thermal reaction, acid exchanges and subsequent calcination process obtains anatase octahedrite TiO
2the technology of nanotube; Patent of invention CN200910071457.0 discloses a kind of electrochemistry anodic oxidation and prepares TiO
2the technology of nano-tube film; Patent of invention CN201310223306.9 discloses one and utilizes Ti silk, prepares TiO by electrochemistry anodic oxidation
2nano-tube film, then at TiO
2dip rear high-temperature calcination in particle solution, obtain TiO
2nano particle/TiO
2the method of nanotube.
Summary of the invention
The invention provides a kind of without the need to reaction template and extra electric field, anatase octahedrite TiO that simple cost is low
2the preparation method of nano-tube film.
The present invention is dissolved deposition self-assembly by metatitanic acid nano wire and is prepared anatase octahedrite TiO in sulphuric acid soln
2nano-tube film, and by regulating the wall thickness of vitriolization time-controllable nanotube.Its key step is as follows:
1) cleaned up by metallic titanium plate, then immersing concentration is react 12 ~ 24 hours under 200 ~ 220 ° of C in the sodium hydroxide solution of 10 ~ 2.0mol/L;
2) reacted titanium sheet taking-up is cooled to room temperature, after deionized water rinsing, after sonic oscillation 5 ~ 10min, carries out acid with the hydrochloric acid of pH=1.0 exchange.Preferably, acid exchanges process 2 hours.
3) be then placed in 80 ° of C hot water, by sulfuric acid adjust ph to 1.5 ~ 2.5, react after 24 ~ 72 hours and take out, with deionized water rinsing, dry, anatase octahedrite TiO can be obtained
2nano-tube film.
In the present invention, be crucial by sulfuric acid adjust ph in step 3), namely final sulphuric acid soln concentration is very crucial: excessive concentration, and metatitanic acid nano wire film, based on dissolution process, can not form film at titanium plate surface; Concentration is too low, then dissolution process is not remarkable, has been not enough to dissolve regrouping process to form nano-pipe array thin film at titanium plate surface, and metatitanic acid nano wire film pattern roughly remains unchanged.Best results when sulphuric acid soln concentration is pH=2 in the present invention.
The metatitanic acid nano wire film that hot for alkali method obtains directly immerses in sulphuric acid soln after process by the present invention, and hydrogen metatitanic acid nano wire dissolves and is directly reassembled as the anatase octahedrite TiO of well-crystallized
2nano-pipe array thin film, and its photocatalytic activity is significantly higher than the anatase octahedrite TiO that the hot method of alkali obtains in conjunction with subsequent heat treatment
2nano wire film.Method of the present invention is without the need to reaction template, without the need to extra electric field, simple, reproducible, and low being convenient to of preparation cost is promoted.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope picture covering the metatitanic acid nano wire film of titanium plate surface prepared by embodiment 1;
Fig. 2 is the X-ray diffractogram covering the metatitanic acid nano wire film of titanium plate surface prepared by embodiment 1, in X-ray diffractogram, and H
2ti
5o
11h
2o, H
2ti
4o
9h
2o: hydrogen metatitanic acid, Ti: titanium;
Fig. 3 is the TiO covering titanium plate surface prepared by embodiment 1
2the low power field emission scanning electron microscope picture of nano-tube film;
Fig. 4 is the TiO covering titanium plate surface prepared by embodiment 1
2the high power field emission scanning electron microscope picture of nano-tube film;
Fig. 5 is the TiO covering titanium plate surface prepared by embodiment 2
2the low power field emission scanning electron microscope picture of nano-tube film;
Fig. 6 is the TiO covering titanium plate surface prepared by embodiment 2
2the high power field emission scanning electron microscope picture of nano-tube film;
Fig. 7 is the TiO covering titanium plate surface prepared by embodiment 2
2the X-ray diffractogram of nano-tube film, in X-ray diffractogram, H
2ti
4o
9h
2o: hydrogen metatitanic acid, A: anatase octahedrite, Ti: titanium;
Fig. 8 is the TiO covering titanium plate surface prepared by embodiment 3
2the low power field emission scanning electron microscope picture of nano-tube film;
Fig. 9 is the TiO covering titanium plate surface prepared by embodiment 3
2the high power field emission scanning electron microscope picture of nano-tube film;
Figure 10 is the TiO covering titanium plate surface prepared by embodiment 4
2the low power field emission scanning electron microscope picture of nano-tube film;
Figure 11 is the TiO covering titanium plate surface prepared by embodiment 4
2the high power field emission scanning electron microscope picture of nano-tube film;
Figure 12 is the TiO of the hot method of alkali in conjunction with follow-up 450 ° of C thermal treatments preparation in 1 hour
2the X-ray diffractogram of nano wire film, in X-ray diffractogram, A: anatase octahedrite, Ti: titanium;
Figure 13 is the concentration curve of the film light catalyzed degradation rhodamine B aqueous solution.
Embodiment
Set forth the present invention further below in conjunction with drawings and Examples and prepare TiO
2the method of nano-tube film.But the present invention is not only confined to following embodiment.
embodiment 1
Prepared by step 1 metatitanic acid nano wire film
The metallic titanium plate cleaned up (is of a size of 2.5 × 2.5 cm
2) to be immersed in 35 ml concns be in the sodium hydroxide solution of 1.25 M, react 20 hours under 220 ° of C, reaction terminates rear washed with de-ionized water titanium sheet film, and the acid through the hydrochloric acid of sonic oscillation 5 ~ 10 min and pH=1 exchanges, and obtains hydrogen metatitanic acid nano wire film.
Step 2 vitriolization
It is in the sulphuric acid soln of 2.0 that titanium sheet step 1 obtained is immersed in 12.5 ml of ph, reacts 72 hours under 80 ° of C, and reaction terminates rear washed with de-ionized water, dry, obtains nano-tube film.
The metatitanic acid nano wire film typical case pattern that Fig. 1 step display 1 obtains.The metatitanic acid nano wire phase composite that Fig. 2 description of step 1 obtains is two kinds of different hydrogen metatitanic acids mainly.Fig. 3 low power electron scanning micrograph shows, generates uniform TiO at titanium plate surface
2nano-tube film.As can be seen from Figure 4, nanotube ordered arrangement, formed by the nano-particles self assemble of diameter about 16 nm, the mean diameter of nanotube is about 100nm, wall thickness about 33 nm.
Embodiment 2
Prepared by step 1 metatitanic acid nano wire film
With embodiment 1.
Step 2 vitriolization
It is in the sulphuric acid soln of 2.0 that titanium sheet step 1 obtained is immersed in 12.5 ml of ph, reacts 48 hours under 80 ° of C, and reaction terminates rear washed with de-ionized water, dry, obtains nano-tube film.
The nanotube of Fig. 5 low power electron scanning micrograph display titanium plate surface is evenly distributed and intensive.Fig. 6 high power electron scanning micrograph shows, compares with embodiment 1, and the mean diameter of the nanotube of gained is about 125 nm, wall thickness about 41 nm.Fig. 7 shows nanotube crystalline phase and consists of Anatase and a part unconverted hydrogen completely metatitanic acid.
Embodiment 3
Prepared by step 1 metatitanic acid nano wire film
With embodiment 1.
Step 2 vitriolization
It is in the sulphuric acid soln of 2.0 that titanium sheet step 1 obtained is immersed in 12.5 ml of ph, reacts 36 hours under 80 ° of C, and reaction terminates rear washed with de-ionized water, dry, obtains nano-tube film.
Fig. 8 low power electron scanning micrograph display titanium plate surface covers more even and intensive nano-tube film, the unconverted hydrogen metatitanic acid nano wire of some lodging.Fig. 9 high power electron scanning micrograph shows, the mean diameter of nanotube is about 133 nm, wall thickness about 58 nm.
Embodiment 4
Prepared by step 1 metatitanic acid nano wire film
With embodiment 1.
Step 2 vitriolization
It is in the sulphuric acid soln of 2.0 that titanium sheet step 1 obtained is immersed in 12.5 ml of ph, reacts 24 hours under 80 ° of C, and reaction terminates rear washed with de-ionized water, dry, obtains nano-tube film.
Figure 10 low power electron scanning micrograph shows that nano-tube film is even and intensive, but compared with embodiment 3, there is the nano wire of more lodging on surface.As can be seen from Figure 11 high power electron scanning micrograph, the mean diameter of nanotube is about 141 nm, wall thickness about 66 nm.
Embodiment 5
Prepared by step 1 metatitanic acid nano wire film
The metallic titanium plate cleaned up (is of a size of 2.5 × 2.5 cm
2) to be immersed in 35 ml concns be in the sodium hydroxide solution of 1.0 M, reacts 24 hours under 200 ° of C, reaction terminates rear washed with de-ionized water titanium sheet film, and the acid through the hydrochloric acid of sonic oscillation 5 ~ 10 min and pH=1 exchanges, and obtains hydrogen metatitanic acid nano wire film.
Step 2 vitriolization
It is in the sulphuric acid soln of 2.5 that titanium sheet step 1 obtained is immersed in 12.5 ml of ph, reacts 24 hours under 80 ° of C, and reaction terminates rear washed with de-ionized water, dry, obtains nano-tube film.
Titanium plate surface covers evenly intensive nano-tube film.
Embodiment 6
Prepared by step 1 metatitanic acid nano wire film
The metallic titanium plate cleaned up (is of a size of 2.5 × 2.5 cm
2) to be immersed in 35 ml concns be in the sodium hydroxide solution of 2.0 M, reacts 12 hours under 200 ° of C, reaction terminates rear washed with de-ionized water titanium sheet film, and the acid through the hydrochloric acid of sonic oscillation 5 ~ 10 min and pH=1 exchanges, and obtains hydrogen metatitanic acid nano wire film.
Step 2 vitriolization
It is in the sulphuric acid soln of 1.5 that titanium sheet step 1 obtained is immersed in 12.5 ml of ph, reacts 48 hours under 80 ° of C, and reaction terminates rear washed with de-ionized water, dry, obtains nano-tube film.
Titanium plate surface covers evenly intensive nano-tube film.
Photocatalysis performance is tested
By embodiment 1,2,4 obtain being of a size of 1.25 × 1.25cm
2nano-tube film carry out photocatalysis performance test.Target degradation product is 12.5 milliliters, the rhodamine B aqueous solution of starting point concentration 0.005 mM.After dark absorption 1 hour, under the ultra violet lamp of 18 W, carry out the photochemical catalysis experiment of 2 hours.
Comparative sample: the metatitanic acid nano wire film that embodiment 1 step 1 obtains, thermal treatment 1 hour under 450 ° of C.The XRD result display of Figure 12, the phase composite of this nano wire film is anatase octahedrite TiO
2.
As can be seen from Figure 13, through TiO that vitriolization 24 ~ 72 h obtains
2the photocatalysis performance of nano-tube film is all obviously better than the anatase octahedrite TiO that the hot method of alkali is prepared in conjunction with subsequent heat treatment
2nano wire film.
Claims (3)
1. an anatase octahedrite TiO
2the preparation method of nano-tube film, is characterized in that, comprises the steps:
1) metallic titanium plate of cleaning is immersed in the sodium hydroxide solution that concentration is 1.0 ~ 2.0mol/L, adopts hydrothermal method to be incubated 12 ~ 24 hours under 200 ~ 220 ° of C;
2) by after the metallic titanium plate taking-up deionized water rinsing of step 1) process, immerse in the hydrochloric acid of pH=1.0, carry out acid and exchange;
3) by step 2) metallic titanium plate that processes is placed in 80 ° of C hot water, is 1.5 ~ 2.5 by sulfuric acid adjust ph, reacts after 24 ~ 72 hours and takes out, with deionized water rinsing, dry, obtains anatase octahedrite TiO
2nano-tube film.
2. anatase octahedrite TiO according to claim 1
2the preparation method of nano-tube film, is characterized in that, described step 2) in acid exchange handling duration be 2 hours.
3. anatase octahedrite TiO according to claim 1
2the preparation method of nano-tube film, is characterized in that, is 2 by sulfuric acid adjust ph in described step 3).
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Cited By (3)
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|---|---|---|---|---|
| CN105709857A (en) * | 2016-03-25 | 2016-06-29 | 上海工程技术大学 | TiO2 nano-thin-film material and preparing method thereof |
| CN112442688A (en) * | 2020-11-25 | 2021-03-05 | 成都大学 | Anatase phase TiO prepared by titanium substrate2Method for nanotube film |
| CN113600161A (en) * | 2021-08-09 | 2021-11-05 | 大连海事大学 | Preparation method of titanium dioxide nanotube network catalytic plate and application of catalytic plate in sludge antibiotic resistance gene treatment |
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| CN102115913A (en) * | 2011-01-22 | 2011-07-06 | 西北大学 | Preparation method of titanium dioxide nanotube film |
| KR20130072280A (en) * | 2011-12-21 | 2013-07-02 | 인하대학교 산학협력단 | Preparation method of lithium titanium oxide for anode active material of lithium rechargeable battery |
| CN104525167A (en) * | 2014-12-16 | 2015-04-22 | 浙江理工大学 | Titanium dioxide nano tube and preparation method thereof |
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| CN102115913A (en) * | 2011-01-22 | 2011-07-06 | 西北大学 | Preparation method of titanium dioxide nanotube film |
| KR20130072280A (en) * | 2011-12-21 | 2013-07-02 | 인하대학교 산학협력단 | Preparation method of lithium titanium oxide for anode active material of lithium rechargeable battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709857A (en) * | 2016-03-25 | 2016-06-29 | 上海工程技术大学 | TiO2 nano-thin-film material and preparing method thereof |
| CN112442688A (en) * | 2020-11-25 | 2021-03-05 | 成都大学 | Anatase phase TiO prepared by titanium substrate2Method for nanotube film |
| CN112442688B (en) * | 2020-11-25 | 2021-11-26 | 成都大学 | Anatase phase TiO prepared by titanium substrate2Method for nanotube film |
| CN113600161A (en) * | 2021-08-09 | 2021-11-05 | 大连海事大学 | Preparation method of titanium dioxide nanotube network catalytic plate and application of catalytic plate in sludge antibiotic resistance gene treatment |
| CN113600161B (en) * | 2021-08-09 | 2024-02-23 | 大连海事大学 | Preparation method of titanium dioxide nanotube network catalytic plate and application of titanium dioxide nanotube network catalytic plate in sludge antibiotic resistance gene treatment |
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