CN102021551A - Method for preparing single-layer high-activity titanium dioxide thin film - Google Patents
Method for preparing single-layer high-activity titanium dioxide thin film Download PDFInfo
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- CN102021551A CN102021551A CN2009101875654A CN200910187565A CN102021551A CN 102021551 A CN102021551 A CN 102021551A CN 2009101875654 A CN2009101875654 A CN 2009101875654A CN 200910187565 A CN200910187565 A CN 200910187565A CN 102021551 A CN102021551 A CN 102021551A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 58
- 230000000694 effects Effects 0.000 title claims abstract description 11
- 239000002356 single layer Substances 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title abstract description 9
- 239000010409 thin film Substances 0.000 title abstract 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010936 titanium Substances 0.000 claims abstract description 75
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 75
- 239000013078 crystal Substances 0.000 claims abstract description 71
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 238000007704 wet chemistry method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 6
- 229910001093 Zr alloy Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910010169 TiCr Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- UMUXBDSQTCDPJZ-UHFFFAOYSA-N chromium titanium Chemical compound [Ti].[Cr] UMUXBDSQTCDPJZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000246 schorl Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention relates to a preparation method for forming single-layer high-activity (001) crystal surface dominating titanium dioxide thin films on different substrates, in particular to the method for growing the (001) crystal surface dominating titanium dioxide thin film consisting of single-layer titanium dioxide particles on a metallic titanium or titanium alloy substrate by a wet chemical process, which solves the problems that (001) dominating titanium dioxide powder difficultly forms a (001) plane totally positioned on a surface and that a compact thin film is difficult to form. In the method, the substrate is placed into a reaction kettle containing the aqueous solution of hydrofluoric acid, and heating treatment is performed at 100 to 200 DEG C for 6 to 24 h to obtain the single-layer (001) crystal surface dominating titanium dioxide thin film. The single-layer (001) crystal surface dominating titanium dioxide thin film consists of anatase and rutile in the radio of 95:5 to 80:20, has the thickness of 10 to 1,000 nm, the controllable (001) crystal surface ratio of 20 to 91 percent and high photoelectrochemical decomposition of water, and is expected to be widely and effectively applied to photocatalytic devices.
Description
Technical field
The present invention relates on different matrix to form the preparation method of the titanium deoxid film that individual layer high reactivity (001) crystal face is dominant, be specially kind at titanium alloy-based the end by wet-chemical process the be dominant method of titanium deoxid film of (001) crystal face of forming by the individual layer titanium dioxide granule of growing at metal titanium or.
Background technology
Find that from Fujishima in 1972 titanium dioxide can produce the phenomenon of hydrogen at water of decomposition under the light action, the semiconductor compound that titanium dioxide and other can be used for photocatalytic hydrogen production by water decomposition has caused to be paid close attention to and deep research widely.Titanium dioxide is because nontoxic environmentally friendly and low price, except being applied to photochemical catalyzing, also be widely used in fields such as photodegradation, dye sensitization solar battery, photoelectrochemistry, biological chemistry and automatically cleaning, but optically catalytic TiO 2 efficient still can not satisfy the needs of application.People constantly carry out modification by methods such as doping, finishing, morphology control to titanium dioxide, thereby further improve the photocatalysis efficiency of titanium dioxide.
Because light-catalyzed reaction is mainly carried out on the surface of catalyzer, and surface atom arrangement difference causes the catalytic activity of titanium dioxide to depend on the surface atom composition.Theoretical investigation finds that titanium dioxide (001) crystal face has higher catalytic activity than other crystal face.How can prepare titanium dioxide that (001) crystal face is dominant becomes the emphasis of research, has reported with TiF recently
4For presoma prepares the titanium dioxide crystal that (001) crystal face is dominant, but the titanium dioxide that (001) crystal face of this method preparation is dominant is that powder and particle size are greater than 1 μ m, therefore this (001) titania powder of being dominant is difficult to be made into fine and close and firm film, effectively uses at aspects such as optoelectronic pole, dye sensitization solar battery, self-cleaning surfaces thereby limited it.Therefore, be grown directly upon on the titanium matrix as the titanium dioxide that (001) crystal face is dominant, not only can solve titanium deoxid film and matrix bond problem, simultaneously more a high proportion of (001) crystal face can be positioned at the surface, thus excellent specific property that can more abundant effective utilization (001) crystal face.Simultaneously, (001) titanium deoxid film that is dominant of crystal face can be widely used in assembling optoelectronic pole and dye sensitization solar battery, and pass through at various material surfaces after metallize titanium or titanium alloy processing, reaction forms the surface of the titanium deoxid film with (001) crystal face again, thereby can obtain having antibiotic and the self-cleaning function material.
Summary of the invention
The object of the present invention is to provide a kind of be dominant preparation method of titanium deoxid film of individual layer high reactivity (001) crystal face that on different matrix, forms, prepared the titanium deoxid film that individual layer high reactivity (001) crystal face is dominant by effective design and use wet-chemical process, and it is assembled into optoelectronic pole, show excellent photoelectrochemistry and separated the water-based energy, solving (001) titanium dioxide powder that is dominant is difficult to form (001) face and all is positioned at the surface and is difficult to form fine and close in the tight problem of film, thereby this film is expected extensively and effectively to be applied to photocatalytic device, the titanium deoxid film that is dominant as (001) crystal face can more effectively be applied to fields such as dye sensitization solar battery, optoelectronic pole and antibacterial surface and automatically cleaning.
Technical scheme of the present invention is:
The invention provides the preparation method of a kind of individual layer high reactivity (001) crystal face titanium deoxid film, the surface is contained on the matrix of metal titanium or titanium alloy, obtain the presoma of surperficial non-oxidation layer with dehydrated alcohol and deionized water ultrasonic cleaning final vacuum evaporate to dryness.Precursor samples is put into the reactor that the certain density diluted hydrofluoric acid aqueous solution is housed, after the reactor sealing, put into baking oven in the certain temperature heat treated regular hour, take out response sample, with washed with de-ionized water and oven dry, just can generate and form the titanium deoxid film that (001) crystal face is dominant by monolayer of particles at matrix surface.Wherein, concrete being characterised in that:
1, the matrix of metal titanium or titanium alloy is contained on the surface, and can be the titanium sheet, scribble the layer of titanium metal matrix, various pattern titanium pieces and titanium alloy (as TiAl, TiZr or TiCr etc.), or the surface has a kind of of the metal titanium of 1～50 μ m thickness or titanium alloy substrate.
2, the reactor material is a kind of of stainless steel, aluminium alloy, copper and tantalum, and inner bag is a kind of of tetrafluoroethylene and high density polyethylene(HDPE).
3, the concentration of hydrofluoric acid is 4～20mM.
4, in the presoma or in the sample, the ratio between the volume of the quality of metal titanium or titanium alloy substrate and the diluted hydrofluoric acid aqueous solution is 1g/100mL～1g/500mL.
5, Heating temperature is 100～200 ℃, and be 6h～24h heat-up time.
6, bake out temperature is 50～120 ℃.
7, the gained film is a titanium dioxide crystal, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the crystalline phase ratio was from 95: 5 to 80: 20, and its thickness is that (be preferably 400～700nm), particle size is that 50～200nm (is preferably 100～180nm) to 10～1000nm.The crystal face ratio is controlled, (001) crystal face ratio 20～91% (being preferably 60～91%).
Advantage of the present invention and beneficial effect are:
1, the present invention is a kind of individual layer high reactivity (001) crystal face titanium deoxid film preparation method that forms on different matrix, on can the matrix with the titanium dioxide growth surface titaniferous of (001) crystal face or titanium alloy, obtaining the titanium deoxid film outermost layer be highly active (001) crystal face that helps light-catalyzed reaction.
2, the inventive method can form the titanium deoxid film that is dominant of (001) crystal face on the surface of any pattern titaniferous or titanium alloy substrate.
3, the inventive method forms on the film direct growth matrix, and titanium dioxide and matrix bond are very firm, and light-catalyzed reaction generation excitation electron is passed on the titanium body easily derives, thereby helps strengthening the transfer efficiency of optical excitation electronics.
4, the titanium deoxid film of the inventive method acquisition is an individual layer, and whole film is made up of individual layer fern leaf crystal titanium dioxide, and (001) face ratio is controlled, and film thickness is controlled.
Description of drawings
Fig. 1. SEM, the TEM of the titanium deoxid film of individual layer (001) and HRTEM photo; Wherein, (a) figure is a bottom SEM photo; (b) figure is a film section S EM photo; (c) figure is the SEM photo of single particle; (d) figure is the particulate diffraction spot photo of film; (e) figure is a particulate HETEM photo.
Fig. 2. the titanium deoxid film of individual layer (001) surface and with the SEM photo of substrate contact surface.
Fig. 3. the XPS curve of the titanium deoxid film of individual layer (001).
Fig. 4. the XRD of the titanium deoxid film of individual layer (001) and Raman curve; Wherein, (a) figure is the XRD figure spectrum; (b) figure is the Raman collection of illustrative plates.
Fig. 5. the photoelectrochemical behaviour test of the titanium deoxid film of individual layer (001)
The SEM photo of the titanium deoxid film of the individual layer (001) of Fig. 6 .120 ℃ preparation.
The SEM photo of the titanium deoxid film of the individual layer (001) of Fig. 7 .12mM hydrofluoric acid solution preparation.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.25mm * 10mm * 30mm titanium sheet respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium sheet of surperficial non-oxidation layer.Then, clean titanium sheet is inserted the 10mM diluted hydrofluoric acid aqueous solution that 40mL is housed, be in the 80mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into baking oven, take out the titanium sheet that reacted,, obtain forming the titanium sheet of individual layer (001) crystal face titanium deoxid film on the surface with washed with de-ionized water and 80 ℃ of oven dry at 140 ℃ of heat treated 10h.
As shown in Figure 1, the exposure of the titanium deoxid film that forms on the titanium sheet is highly active (001) crystal face, and film is by detiform titanium dioxide crystal granulometric composition, and particle size is 130nm, and the degree of crystallinity height of film.The thickness of film is about 600nm, and the ratio of (001) crystal face reaches 83%.
As shown in Figure 2, the SEM picture of the part that contacts with the base of film cross section and film confirms that the titanium deoxid film of preparation is an individual layer.
As shown in Figure 3, the film of the titanium dioxide that is dominant at (001) crystal face of fluorion forms and has vital role.
As shown in Figure 4, XRD and Raman spectrum show that film is made up of anatase octahedrite and red schorl phase titanium dioxide, and the crystalline phase ratio of anatase octahedrite and rutile is 90: 10.
As shown in Figure 5, the titanium deoxid film of individual layer highly active (001) crystal face has high photoelectrochemistry water of decomposition ability.
Embodiment 2
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.25mm * 10mm * 30mm titanium sheet respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium sheet of surperficial non-oxidation layer.Then, clean titanium sheet is inserted the 8mM diluted hydrofluoric acid aqueous solution that 40mL is housed, be in the 80mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into baking oven, take out the titanium sheet that reacted,, obtain forming the titanium sheet of individual layer (001) crystal face titanium deoxid film on the surface with washed with de-ionized water and 80 ℃ of oven dry at 120 ℃ of heat treated 10h.
As shown in Figure 6, synthetic titanium dioxide (001) crystal face film with this understanding, the gained film is a titanium dioxide crystal, the titanium dioxide crystal particulate is of a size of 300nm, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the ratio of anatase octahedrite and rutile is 19: 1, and the ratio of (001) crystal face reaches 91%, and the thickness of film is about 500nm.
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.2g titanium piece respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium piece of surperficial non-oxidation layer.Then, clean titanium piece is inserted the 15mM diluted hydrofluoric acid aqueous solution that 40mL is housed, be in the 80mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into baking oven, take out the titanium piece that reacted,, obtain forming the titanium piece of individual layer (001) crystal face titanium deoxid film on the surface with washed with de-ionized water and 100 ℃ of oven dry at 140 ℃ of heat treated 15h.
As shown in Figure 7, synthetic titanium dioxide (001) crystal face film with this understanding, the gained film is a titanium dioxide crystal, the titanium dioxide crystal particulate is of a size of 120nm, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the ratio of anatase octahedrite and rutile is 10: 1, and the ratio of (001) crystal face reaches 20%, and the thickness of film is about 850nm.
Embodiment 4
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.4g titanium piece respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium piece of surperficial non-oxidation layer.Then, clean titanium piece is inserted the 14mM diluted hydrofluoric acid aqueous solution that 80mL is housed, be in the 160mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into 120 ℃ of heat treated 8h of baking oven, take out the titanium piece that reacted,, obtain forming the titanium piece of individual layer (001) crystal face titanium deoxid film on the surface with washed with de-ionized water and 80 ℃ of oven dry.
Synthetic titanium dioxide (001) crystal face film with this understanding, the gained film is a titanium dioxide crystal, the titanium dioxide crystal particulate is of a size of 140nm, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the ratio of anatase octahedrite and rutile is 10: 1, (001) ratio of crystal face reaches 75%, and the thickness of film is about 550nm.
Embodiment 5
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.2g titanium-zirconium alloy (in the present embodiment, the weight ratio of titanium zirconium is 4: 1) piece respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium-zirconium alloy piece of surperficial non-oxidation layer.Then, clean titanium-zirconium alloy piece is inserted the 10mM diluted hydrofluoric acid aqueous solution that 40mL is housed, be in the 80mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into baking oven, take out the titanium-zirconium alloy piece that reacted,, obtain forming the titanium-zirconium alloy piece of the Zirconium doped titanium dioxide film of individual layer (001) crystal face on the surface with washed with de-ionized water and 80 ℃ of oven dry at 120 ℃ of heat treated 15h.
Synthetic titanium dioxide (001) crystal face film with this understanding, the gained film is a titanium dioxide crystal, the titanium dioxide crystal particulate is of a size of 110nm, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the ratio of anatase octahedrite and rutile is 12: 1, (001) ratio of crystal face reaches 24%, and the thickness of film is about 750nm.
Embodiment 6
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.2g titanium aluminum alloy (in the present embodiment, the weight ratio of titanium aluminium is 10: 1) piece respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium aluminum alloy piece of surperficial non-oxidation layer.Then, clean titanium aluminum alloy piece is inserted the 10mM diluted hydrofluoric acid aqueous solution that 40mL is housed, be in the 80mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into baking oven, take out the titanium aluminum alloy piece that reacted,, obtain forming the titanium aluminum alloy piece of the aluminum doped titanium dioxide film of individual layer (001) crystal face on the surface with washed with de-ionized water and 80 ℃ of oven dry at 120 ℃ of heat treated 15h.
Synthetic titanium dioxide (001) crystal face film with this understanding, the gained film is a titanium dioxide crystal, titanium dioxide crystal particulate size is about 150nm, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the ratio of anatase octahedrite and rutile is 9: 1, (001) ratio of crystal face reaches 35%, and the thickness of film is about 400nm.
Embodiment 7
Dehydrated alcohol and deionized water be ultrasonic cleaning 0.2g titanium chrome alloy (in the present embodiment, the weight ratio of titanium chromium is 9: 1) piece respectively, after 80 ℃ of vacuum drying treatment, obtains the clean titanium chrome alloy piece of surperficial non-oxidation layer.Then, clean titanium chrome alloy piece is inserted the 10mM diluted hydrofluoric acid aqueous solution that 40mL is housed, be in the 80mL stainless steel cauldron of liner with the tetrafluoroethylene.After the reactor sealing, put into baking oven, take out the titanium chrome alloy piece that reacted,, obtain forming the titanium chrome alloy piece of the chromium doped titanium dioxide film of individual layer (001) crystal face on the surface with washed with de-ionized water and 80 ℃ of oven dry at 120 ℃ of heat treated 15h.
Synthetic titanium dioxide (001) crystal face film with this understanding, the gained film is a titanium dioxide crystal, titanium dioxide crystal particulate size is about 100nm, film is made up of with rutile titanium dioxide mutually anatase octahedrite, the ratio of anatase octahedrite and rutile is 10: 1, (001) ratio of crystal face reaches 27%, and the thickness of film is about 450nm.
Claims (8)
1. the preparation method of an individual layer high-activity titanium dioxide film is characterized in that: at first, the surface is contained on the matrix of metal titanium or titanium alloy with dehydrated alcohol and deionized water ultrasonic cleaning final vacuum evaporate to dryness, obtained the presoma of surperficial non-oxidation layer; Then, precursor samples is put into the reactor that the diluted hydrofluoric acid aqueous solution is housed, after the reactor sealing, putting into baking oven for heating handles, take out response sample,, just can generate and form the titanium deoxid film that (001) crystal face is dominant by monolayer of particles at matrix surface with washed with de-ionized water and oven dry.
2. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: the matrix of metal titanium or titanium alloy is contained on described surface, for the titanium sheet, scribble the layer of titanium metal matrix, various pattern titanium pieces and titanium alloy, or the surface has a kind of of the metal titanium of 1～50 μ m thickness or titanium alloy substrate.
3. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: the material of described reactor is a kind of of stainless steel, aluminium alloy, copper and tantalum, and inner bag is a kind of of tetrafluoroethylene and high density polyethylene(HDPE).
4. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: in the described diluted hydrofluoric acid aqueous solution, the concentration of hydrofluoric acid is 4～20mM.
5. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: in the described presoma or in the sample, the ratio between the volume of the quality of metal titanium or titanium alloy substrate and the diluted hydrofluoric acid aqueous solution is 1g/100mL～1g/500mL.
6. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: described heat treated, Heating temperature are 100～200 ℃, and be 6h～24h heat-up time.
7. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: the oven dry after the described washed with de-ionized water, bake out temperature are 50～120 ℃.
8. according to the preparation method of the described individual layer high-activity titanium dioxide film of claim 1, it is characterized in that: the gained film is a titanium dioxide crystal, film is made up of with rutile titanium dioxide mutually anatase octahedrite, ratio was from 95: 5 to 80: 20, its thickness is 10～1000nm, and particle size is 50～200nm; The crystal face ratio is controlled, and (001) crystal face ratio is 20～91%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407109A (en) * | 2011-10-12 | 2012-04-11 | 西北有色金属研究院 | Preparation method for TiO2 photochemical catalyst with visible-light-activity exposed crystal face |
| CN102515270A (en) * | 2011-12-13 | 2012-06-27 | 武汉大学 | Preparation method of mixed crystal-type nanoscale TiO2 having exposed (001) crystal faces |
| CN104190452A (en) * | 2014-07-30 | 2014-12-10 | 中国矿业大学 | Preparation method of silver phosphate/titanium dioxide composite membrane |
| CN108950532A (en) * | 2017-11-17 | 2018-12-07 | 中国科学院深圳先进技术研究院 | The preparation method and preparation evaporation jig of single crystal titanium dioxide film |
| CN110655106A (en) * | 2019-10-08 | 2020-01-07 | 浙江工业大学 | Method for in-situ preparation of high-energy crystal face exposed titanium dioxide film |
| CN111647880A (en) * | 2019-03-04 | 2020-09-11 | 中国科学院宁波材料技术与工程研究所 | Method for growing titanium dioxide nanoparticles on surface of titanium or titanium alloy substrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101481137A (en) * | 2008-12-16 | 2009-07-15 | 中国科学院电工研究所 | TiO2 nano materials of multiple regular geometric shapes and preparation thereof |
| CN101508463B (en) * | 2009-03-19 | 2010-11-10 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407109A (en) * | 2011-10-12 | 2012-04-11 | 西北有色金属研究院 | Preparation method for TiO2 photochemical catalyst with visible-light-activity exposed crystal face |
| CN102515270A (en) * | 2011-12-13 | 2012-06-27 | 武汉大学 | Preparation method of mixed crystal-type nanoscale TiO2 having exposed (001) crystal faces |
| CN104190452A (en) * | 2014-07-30 | 2014-12-10 | 中国矿业大学 | Preparation method of silver phosphate/titanium dioxide composite membrane |
| CN108950532A (en) * | 2017-11-17 | 2018-12-07 | 中国科学院深圳先进技术研究院 | The preparation method and preparation evaporation jig of single crystal titanium dioxide film |
| CN108950532B (en) * | 2017-11-17 | 2020-09-18 | 中国科学院深圳先进技术研究院 | Preparation method of single crystal titanium dioxide film and evaporation frame for preparation |
| CN111647880A (en) * | 2019-03-04 | 2020-09-11 | 中国科学院宁波材料技术与工程研究所 | Method for growing titanium dioxide nanoparticles on surface of titanium or titanium alloy substrate |
| CN110655106A (en) * | 2019-10-08 | 2020-01-07 | 浙江工业大学 | Method for in-situ preparation of high-energy crystal face exposed titanium dioxide film |
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