CN102644111A - Preparation method of titanium dioxide hierarchical nano-tube ordered array consisting of controllable-morphology anatase single-crystal particles - Google Patents
Preparation method of titanium dioxide hierarchical nano-tube ordered array consisting of controllable-morphology anatase single-crystal particles Download PDFInfo
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- CN102644111A CN102644111A CN2012101068229A CN201210106822A CN102644111A CN 102644111 A CN102644111 A CN 102644111A CN 2012101068229 A CN2012101068229 A CN 2012101068229A CN 201210106822 A CN201210106822 A CN 201210106822A CN 102644111 A CN102644111 A CN 102644111A
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Abstract
The invention discloses a preparation method of a titanium dioxide hierarchical nano-tube ordered array consisting of controllable-morphology anatase single-crystal particles. The method comprises the following steps of: firstly synthesizing an anodic-oxidation titanium dioxide nano-tube; and then performing hydro-thermal treatment on the anodic-oxidation titanium dioxide nano-tube by use of hydrofluoric acids with different concentrations to obtain the controllable-morphology hierarchical titanium dioxide nano-tube array consisting of anatase titanium dioxide single-crystal nano particles. The method is simple to operate and has low cost; and a hierarchical anatase titanium dioxide nano-structure with a titanium plate on the back and an ordered porous channel array on the front can be formed simply by performing hydro-thermal treatment on the amorphous anodic-oxidation titanium dioxide nano-tube array.
Description
Technical field
The invention belongs to hydro-thermal reaction method field, relate in particular to the preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of a kind of pattern.
Background technology
Titanium oxide receives a large amount of concerns of people for many years as a kind of well-known semiconductor material with wide forbidden band always.Titanium oxide has anatase octahedrite, rutile, three kinds of crystal formations of brookite; Other two kinds of crystal formations are compared, and Detitanium-ore-type particularly anatase type nano structure has more outstanding photoelectricity and photochemical properties in many-sided practical applications such as photochemical catalysis, solar energy converting, water-splitting hydrogen production, chemical sensitisation.At present people are through can the be synthesized titanium dioxide nanostructure of multiple patterns such as comprising particle, line, band, pipe, ball of multiple means.In recent years, the classification titanium dioxide nanostructure of hollow, anodic oxidation nanotube for example, alkaline earth solution metatitanic acid nanotube etc. are because its big specific surface area and tubular structure receive people's special concern.Yet the former is the amorphous attitude, and poor-performing need be converted into the anatase octahedrite polycrystalline structure by high temperature annealing (500 ℃) in air.The latter equally also needs s.t. ability crystallization, and the structure crystallization degree that forms is lower.Good crystallinity is one of key factor that improves material property.Also can obtain simple titanium dioxide single crystalline structure at present, for example the single crystal particle of octahedra shape (these particles are compared with hollow structure, and specific surface area is less) through hydrothermal method or sol-gel method.But special appearance, for example complicated single crystal structure such as hollow hierarchy still is difficult to synthetic.Therefore, probe into a kind of easy, effective compound method, the preparation structural parameter are controlled, and the classification hollow titanium dioxide nanostructure of existing high specific surface area and well-crystallized property has great importance simultaneously.
Summary of the invention
The present invention is intended to develop a kind of preparation cheap device, the preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of the simple pattern of working method.
The present invention adopts following technical scheme to achieve these goals:
The preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of a kind of pattern is characterized in that:
May further comprise the steps:
(1) with pure titanium sheet in volume ratio be in the mixing solutions of ethanol and acetone of 0.8-1.2: 0.8-1.2 ultrasonic cleaning about 30 minutes removing the organism on surface, and then with deionized water ultrasonic cleaning repeatedly, nitrogen gas stream dries up under the normal temperature; Then the titanium sheet behind the cleaning-drying is inserted in the electrolyzer of terepthaloyl moietie electrolyte solution of the hydrofluoric acid that contains 0.2M; Apply constant 100V voltage and carry out anodic oxidation, oxidization time is about 1 hour, then the titanium sheet after the anodic oxidation is taken out; Place the absolute ethyl alcohol sonic oscillation; Remove the unordered anodic oxidation titania nanotube on surface, stay orderly anodic oxidation titanium dioxide nanotube array layer, at last after using deionized water to wash repeatedly; In air, dry, obtain having the Nano tube array of titanium dioxide of titanium substrate;
The Nano tube array of titanium dioxide that (2) will have the titanium substrate is put into 60mL tetrafluoroethylene hydrothermal reaction kettle, adds 0.2-2mL concentration again and be about 1% hydrofluoric acid, adds deionized water and makes reaction soln volume in the hydrothermal reaction kettle reach 50mL to end; With hydrothermal reaction kettle put into about 120 ℃ baking oven, be warming up to about 180 ℃ and be incubated about 3 hours, and then take out hydrothermal reaction kettle; Naturally cool to room temperature; The classifying nano pipe array that taking-up prepares is used washed with de-ionized water, places about 2 hours in the baking oven in about 100 ℃ again; To remove residual fluorion in the sample, promptly get product.
The preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of described a kind of pattern; It is characterized in that: described pure titanium sheet is that purity reaches 99.9% titanium sheet, and the volume ratio of ethanol and acetone is 1: 1 in the mixing solutions of described ethanol and acetone.
The preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of described a kind of pattern is characterized in that: the hydrofluoric acid concentration that step (2) adds is 1%.
Principle of the present invention is: core thinking of the present invention is to use the titanium oxide amorphous nano pipe array of hydrofluoric acid antianode oxidation style preparation to carry out hydrothermal treatment consists, the classification Nano tube array of titanium dioxide that the controlled anatase titanium dioxide nanometer monocrystalline particle of preparation appearance structure assembles.This preparation method was divided into for two steps; At first synthetic anodic oxidation titania nanotube; Use the hydrofluoric acid antianode ferric oxide/titanium dioxide nano pipe of different concns to carry out hydrothermal treatment consists then, prepare the classification Nano tube array of titanium dioxide that the controlled anatase titanium dioxide nanometer monocrystalline particle of appearance structure assembles.
Beneficial effect of the present invention: the present invention relates to a kind of pervasive template hydro-thermal reaction method; Be used to prepare the controlled novel classification Nano tube array of titanium dioxide of a kind of pattern; The porous tubular structured oldered array that is assembled into that promptly constitutes, and the nano particle pattern and the controllable size of this tubular structure and component units thereof by anatase titanium dioxide nanometer monocrystalline particle.This method is simple to operate, with low cost, only carries out hydrothermal treatment consists through the anodic oxidation Nano tube array of titanium dioxide to amorphous and can form the back side and be the titanium sheet, positive be the classification anatase titanium dioxide nanostructure of ordered porous channel array.This anatase titanium dioxide hierarchy is expected at photolysis water hydrogen, the circulation photocatalysis to degrade organic matter, and aspects such as dye sensitization solar battery, gas sensor are widely used.
Description of drawings
(a) prepares amorphous Nano tube array of titanium dioxide device synoptic diagram for anonizing among Fig. 1, (b) is equipped with the classification titania nanotube oldered array device synoptic diagram of anatase single crystal titania nanoparticles assembling for the hydro-thermal reaction legal system;
Fig. 2 wherein schemes the amorphous anodic oxidation Nano tube array of titanium dioxide inside that (a) inserts in the hydrothermal reaction kettle for hydrofluoric acid gets into for the process synoptic diagram that the present invention prepares the classification titania nanotube oldered array of anatase single crystal titania nanoparticles assembling; Figure (b) forms titanium tetrafluoride for the titania nanotube wall of amorphous is partly dissolved by hydrofluoric acid; Figure (c) is the inner titanium tetrafluoride hydrolysis of titania nanotube of amorphous, generates the titanium oxide nucleus, on residual tube wall; Scheme (d) for the amorphous titania nanotube of remainder is all dissolved by hydrofluoric acid, produced simultaneously titanium tetrafluoride complete hydrolysis, the titanium oxide nuclei growth of generation becomes the anatase single crystal titania nanoparticles;
Fig. 3 is equipped with the typical microstructure and the characterization result of the classification titania nanotube oldered array that the anatase single crystal nano particle is assembled into for the present invention utilizes hydrofluoric acid through the hydro-thermal reaction legal system, and wherein figure (a) is the top field emission scanning electron microscope picture of classifying nano pipe array; Figure (b) is the side scanning electron microscope diagram sheet of classifying nano pipe array; Figure (c) for through the sonic oscillation method with the classifying nano pipe broken with disperse after anatase titania nanometer monocrystalline particulate transmission electron micrograph; Figure (d) is the corresponding high resolution lattice fringe phase in red circle place among the figure (c); Inserting figure is the corresponding SEAD photo of figure (d);
The Raman spectrogram of the classification titania nanotube oldered array that Fig. 4 assembles for typical anatase single crystal nano particle;
Fig. 5 is the classification titania nanotube oldered array that the anatase single crystal nano particle of synthetic different-shape under different concns hydrofluoric acid hydrothermal treatment consists is formed, and wherein figure (a) is the top stereoscan photograph of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 0.2mL hydrofluoric acid hydrothermal treatment consists; Figure (b) is the side stereoscan photograph of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 0.2mL hydrofluoric acid hydrothermal treatment consists; Figure (c) is the transmission electron microscope photo of synthetic anatase single crystal nano particle after the 0.2mL hydrofluoric acid hydrothermal treatment consists, and insertion figure is corresponding particulate electron diffraction pattern; Figure (d) is the top SEM photo of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 1.2mL hydrofluoric acid hydrothermal treatment consists; Figure (e) is the side SEM photo of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 1.2mL hydrofluoric acid hydrothermal treatment consists; Figure (f) is the TEM photo of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 1.2mL hydrofluoric acid hydrothermal treatment consists, insertion figure be red circle place choose electron diffraction ring style.
Embodiment,
The preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of a kind of pattern may further comprise the steps:
(1) with 99.9% pure titanium sheet in volume ratio be in 1: 1 the mixing solutions of ethanol and acetone ultrasonic cleaning about 30 minutes to remove the organism on surface; And then with deionized water ultrasonic cleaning repeatedly, nitrogen gas stream dries up under the normal temperature, then the titanium sheet behind the cleaning-drying is inserted in the electrolyzer of terepthaloyl moietie electrolyte solution of the hydrofluoric acid that contains 0.2M; Apply constant 100V voltage and carry out anodic oxidation; Oxidization time is about 1 hour, then the titanium sheet after the anodic oxidation is taken out, and places the absolute ethyl alcohol sonic oscillation; Remove the unordered anodic oxidation titania nanotube on surface, stay orderly anodic oxidation titanium dioxide nanotube array layer.Using deionized water to wash repeatedly, dry in the air at last.
(2) Nano tube array of titanium dioxide that has the titanium substrate of preceding method preparation is put into 60mL tetrafluoroethylene hydrothermal reaction kettle, 0.2-2mL concentration is 1% hydrofluoric acid respectively, adds deionized water and makes reaction soln only reach 50mL.Hydrothermal reaction kettle is put into 120 ℃ baking oven, be warming up to 180 ℃ and be incubated 3 hours.And then the taking-up hydrothermal reaction kettle, naturally cool to room temperature, take out the classifying nano pipe array for preparing, use washed with de-ionized water, in 100 ℃ baking oven, placed 2 hours again, to remove residual fluorion in the sample, promptly get product.
(a) prepares amorphous Nano tube array of titanium dioxide device synoptic diagram for anonizing among Fig. 1, (b) is equipped with the classification titania nanotube oldered array device synoptic diagram of anatase single crystal titania nanoparticles assembling for the hydro-thermal reaction legal system;
Fig. 2 wherein schemes the amorphous anodic oxidation Nano tube array of titanium dioxide inside that (a) inserts in the hydrothermal reaction kettle for hydrofluoric acid gets into for the process synoptic diagram that the present invention prepares the classification titania nanotube oldered array of anatase single crystal titania nanoparticles assembling; Figure (b) forms titanium tetrafluoride for the titania nanotube wall of amorphous is partly dissolved by hydrofluoric acid; Figure (c) is the inner titanium tetrafluoride hydrolysis of titania nanotube of amorphous, generates the titanium oxide nucleus, on residual tube wall; Scheme (d) for the amorphous titania nanotube of remainder is all dissolved by hydrofluoric acid, produced simultaneously titanium tetrafluoride complete hydrolysis, the titanium oxide nuclei growth of generation becomes the anatase single crystal titania nanoparticles;
Fig. 3 is equipped with the typical microstructure and the characterization result of the classification titania nanotube oldered array that the anatase single crystal nano particle is assembled into for the present invention utilizes hydrofluoric acid through the hydro-thermal reaction legal system, and wherein figure (a) is the top field emission scanning electron microscope picture of classifying nano pipe array; Figure (b) is the side scanning electron microscope diagram sheet of classifying nano pipe array; Figure (c) for through the sonic oscillation method with the classifying nano pipe broken with disperse after anatase titania nanometer monocrystalline particulate transmission electron micrograph; Figure (d) is the corresponding high resolution lattice fringe phase in red circle place among the figure (c); Inserting figure is the corresponding SEAD photo of figure (d).Can learn mutually with the high resolution striped that from electron diffraction pattern the component units of classification titania nanotube oldered array is the single crystal particle of Detitanium-ore-type really;
The Raman spectrogram of the classification titania nanotube oldered array that Fig. 4 assembles for typical anatase single crystal nano particle, the Raman diaphragm of from figure, being demarcated can know that institute's synthetic classification Nano tube array of titanium dioxide is Detitanium-ore-type really.
Fig. 5 is the classification titania nanotube oldered array that the anatase single crystal nano particle of synthetic different-shape under different concns hydrofluoric acid hydrothermal treatment consists is formed, and wherein figure (a) is the top stereoscan photograph of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 0.2mL hydrofluoric acid hydrothermal treatment consists; Figure (b) is the side stereoscan photograph of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 0.2mL hydrofluoric acid hydrothermal treatment consists; Figure (c) is the transmission electron microscope photo of synthetic anatase single crystal nano particle after the 0.2mL hydrofluoric acid hydrothermal treatment consists, and insertion figure is corresponding particulate electron diffraction pattern; Figure (d) is the top SEM photo of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 1.2mL hydrofluoric acid hydrothermal treatment consists; Figure (e) is the side SEM photo of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 1.2mL hydrofluoric acid hydrothermal treatment consists; Figure (f) is the TEM photo of synthetic anatase single crystal nano particle classification titania nanotube oldered array after the 1.2mL hydrofluoric acid hydrothermal treatment consists, insertion figure be red circle place choose electron diffraction ring style.Should be noted that; Forming similar polycrystalline diffraction ring among the figure (f) is because the nanoparticle size of synthetic classifying nano tubular construction component units is less and assembling is good, even long-time sonic oscillation also is difficult to destroy tubular structure to obtain dispersive nanometer monocrystalline particle.Electron diffraction pattern is corresponding to the corresponding crystal face of anatase titanium dioxide among figure (c) and the figure (f).
Claims (3)
1. the preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of pattern is characterized in that:
May further comprise the steps:
(1) with pure titanium sheet in volume ratio be in the mixing solutions of ethanol and acetone of 0.8-1.2:0.8-1.2 ultrasonic cleaning about 30 minutes removing the organism on surface, and then with deionized water ultrasonic cleaning repeatedly, nitrogen gas stream dries up under the normal temperature; Then the titanium sheet behind the cleaning-drying is inserted in the electrolyzer of terepthaloyl moietie electrolyte solution of the hydrofluoric acid that contains 0.2 M; Apply constant 100 V voltages and carry out anodic oxidation, oxidization time is about 1 hour, then the titanium sheet after the anodic oxidation is taken out; Place the absolute ethyl alcohol sonic oscillation; Remove the unordered anodic oxidation titania nanotube on surface, stay orderly anodic oxidation titanium dioxide nanotube array layer, at last after using deionized water to wash repeatedly; In air, dry, obtain having the Nano tube array of titanium dioxide of titanium substrate;
The Nano tube array of titanium dioxide that (2) will have the titanium substrate is put into 60mL tetrafluoroethylene hydrothermal reaction kettle, adds 0.2-2 mL concentration again and be about 1% hydrofluoric acid, adds deionized water and makes reaction soln volume in the hydrothermal reaction kettle reach 50 mL to end; With hydrothermal reaction kettle put into about 120 ℃ baking oven, be warming up to about 180 ℃ and be incubated about 3 hours, and then take out hydrothermal reaction kettle; Naturally cool to room temperature; The classifying nano pipe array that taking-up prepares is used washed with de-ionized water, places about 2 hours in the baking oven in about 100 ℃ again; To remove residual fluorion in the sample, promptly get product.
2. the preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of a kind of pattern according to claim 1; It is characterized in that: described pure titanium sheet is that purity reaches 99.9% titanium sheet, and the volume ratio of ethanol and acetone is 1:1 in the mixing solutions of described ethanol and acetone.
3. the preparation method of the titanium oxide classifying nano pipe oldered array of the controlled anatase single crystal granulometric composition of a kind of pattern according to claim 1 is characterized in that: the hydrofluoric acid concentration that step (2) adds is 1%.
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| CN103225104A (en) * | 2013-04-10 | 2013-07-31 | 华南理工大学 | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof |
| 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 |
| CN105463364A (en) * | 2015-12-04 | 2016-04-06 | 中山大学 | Orientated super-hydrophilic anatase TiO2 array and manufacturing method and application of orientated super-hydrophilic anatase TiO2 array |
| CN109621943A (en) * | 2018-12-24 | 2019-04-16 | 南昌航空大学 | A kind of preparation method and applications of 1T phase molybdenum disulfide carried titanium dioxide nano-tube array |
| CN110577238A (en) * | 2019-09-11 | 2019-12-17 | 安徽大学 | Titanium dioxide nanofiber-nanotube with hierarchical structure and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225104A (en) * | 2013-04-10 | 2013-07-31 | 华南理工大学 | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof |
| 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 |
| CN105463364A (en) * | 2015-12-04 | 2016-04-06 | 中山大学 | Orientated super-hydrophilic anatase TiO2 array and manufacturing method and application of orientated super-hydrophilic anatase TiO2 array |
| CN105463364B (en) * | 2015-12-04 | 2018-01-19 | 中山大学 | Super hydrophilic anatase tio2 array of the ＞ orientations of ＜ 001 and preparation method and application |
| CN109621943A (en) * | 2018-12-24 | 2019-04-16 | 南昌航空大学 | A kind of preparation method and applications of 1T phase molybdenum disulfide carried titanium dioxide nano-tube array |
| CN109621943B (en) * | 2018-12-24 | 2021-06-29 | 南昌航空大学 | Preparation method and application of 1T-phase molybdenum disulfide-loaded titanium dioxide nanotube array |
| CN110577238A (en) * | 2019-09-11 | 2019-12-17 | 安徽大学 | Titanium dioxide nanofiber-nanotube with hierarchical structure and preparation method thereof |
| CN110577238B (en) * | 2019-09-11 | 2021-09-17 | 安徽大学 | Titanium dioxide nanofiber-nanotube with hierarchical structure and preparation method thereof |
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