CN107841777B - A kind of preparation method of witch culture Nano tube array of titanium dioxide - Google Patents
A kind of preparation method of witch culture Nano tube array of titanium dioxide Download PDFInfo
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- CN107841777B CN107841777B CN201711053050.6A CN201711053050A CN107841777B CN 107841777 B CN107841777 B CN 107841777B CN 201711053050 A CN201711053050 A CN 201711053050A CN 107841777 B CN107841777 B CN 107841777B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000002071 nanotube Substances 0.000 title claims abstract description 78
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 241001481828 Glyptocephalus cynoglossus Species 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 235000011187 glycerol Nutrition 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 238000010792 warming Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 25
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000007743 anodising Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation methods of witch culture Nano tube array of titanium dioxide, belong to nano material environmental photocatlytsis technical field.1, titanium sheet pre-processes: 2, it is 0.8wt% ammonium fluoride that mass percent is added in the deionized water of 35vol%, sufficiently dissolves, obtains ammonium fluoride solution, spare；3, the Disodium tungstate (Na2WO4) dihydrate that mass percent is 0.04~1wt% is added in above-mentioned configured ammonium fluoride solution, the glycerine that percent by volume is 65vol% is then added, 50 DEG C of constant temperature simultaneously stirs 30~60 minutes, obtains electrolyte；4, titanium sheet pretreated in step 1 is connect into the positive grade of power supply, graphite flake or platinized platinum connect power cathode, be placed in the electrolyte of step 3, at constant pressure anodic oxygenization 3~5 hours of 30~40V, nanometer tube composite materials are obtained, are successively cleaned with ethyl alcohol and deionized water, are dried spare；5, gained nanometer tube composite materials are placed in Muffle furnace, are warming up to 450 DEG C with 5 DEG C/min of rate, and keep constant temperature 2 hours, be cooled to room temperature to obtain witch culture Nano tube array of titanium dioxide.
Description
Technical field
The invention belongs to nano material environmental photocatlytsis technical fields.
Background technique
Since 1972, TiO2Water H is decomposed using photocatalysis technology by report for the first time2And O2Afterwards, TiO2The light of semiconductor
Prelude has just been pulled open in catalysis technique research.TiO2As a kind of semiconductor material with excellent physicochemical property, in solar-electricity
Pond, various sensors, body implanting material and photocatalytic pollutant degradation etc. all have broad application prospects.TiO2Nanometer
Pipe array is TiO2A kind of special appearance, have many advantages, such as large specific surface area, immobilized performance is good, it is particularly suitable be used as solar energy
Battery light anode and photocatalytic pollutant degradation.Then energy gaps (anatase 3.2eV, the golden red of constrained material inherently
Stone 3.0eV), TiO2It can only be excited by wavelength less than the ultraviolet light of 385nm, and to accounting for the visible light part of sunlight 95% all
Efficiently it can not absorb and utilize, this affects TiO to a certain extent2Catalytic efficiency of the nanotube as photochemical catalyst.And
Extend TiO2Spectral response range to can be then by light area improve its photocatalytic activity a kind of effective means.
W element doping can effectively improve TiO2Photocatalytic activity, this is because W element doping on the one hand can be formed
WO3/TiO2Heterojunction structure inhibits Carrier recombination；On the other hand, W6+With Ti4+With approximate ionic radius, it is able to enter
TiO2Intracell replaces Ti4+Position, to form new doped energy-band in forbidden band, the forbidden band for reducing composite material is wide
Degree, so that having material can be by photoresponse activity.
At present in TiO2It is mainly infusion process, hydro-thermal method, electro-deposition and oxide alloy that the method for W doping is carried out in nanotube
Method.Although these methods can realize W element to the doping vario-property of nanotube to a certain extent, all there is certain lack
It falls into, as infusion process and electrodeposition process are difficult to control on the distributing homogeneity of W element；Hydro-thermal method needs the operation of high temperature and pressure,
Condition is harsh；The more difficult preparation of Ti-W alloy in alloy oxidation method, and the W doping in alloy can not it is convenient regulate and control.Therefore originally
Invention proposes a kind of anodizing in situ to realize W element to TiO2The doping vario-property of nanotube, i.e., in metal Ti anodic oxygen
During change forms nanotube, the W in electrolyte injects TiO simultaneously under the action of electric field force2, to disposably form W
TiO2 nano-tube array is adulterated, doping is controlled by the regulation to W salinity in electrolyte, is that a kind of effectively adulterate changes
Property method.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of witch culture Nano tube array of titanium dioxide, it can effectively be solved
Certainly W element is distributed and the controllable problem of doping in nanotube.
The purpose of the present invention is achieved through the following technical solutions: a kind of witch culture Nano tube array of titanium dioxide
Preparation method, specific practice are:
Step 1: titanium sheet pre-processes: metallic titanium surface sand paper sanding and polishing, and chemical polishing step by step cleans spare；
Step 2: it is 0.8wt% fluorination that mass percent is added in the deionized water that percent by volume is 35vol%
Ammonium stirs 10 minutes, sufficiently dissolves, obtains ammonium fluoride solution, spare；
Step 3: above-mentioned configured ammonium fluoride is added in the Disodium tungstate (Na2WO4) dihydrate that mass percent is 0.04~1wt%
In solution, dissolution in 10 minutes is stirred completely, the glycerine that percent by volume is 65vol% is then added, in 50 DEG C of conditions of constant temperature
It descends and stirs 30~60 minutes, obtain electrolyte；
Step 4: titanium sheet pretreated in step 1 is connect the positive grade of power supply, graphite flake or platinized platinum connect power cathode, are placed in
In the electrolyte of step 3, at constant pressure anodic oxygenization 3~5 hours of 30~40V, nanotube sample is obtained, with ethyl alcohol and is gone
Ionized water successively cleans, and dries spare；
Step 5: gained nanotube sample in step 4 is placed in Muffle furnace, 450 are warming up to 5 DEG C/min of rate
DEG C, and keep constant temperature 2 hours, then cooled to room temperature obtains witch culture Nano tube array of titanium dioxide composite material.
The mass percent of ammonium fluoride content is 0.8wt% in the electrolyte, and the mass percent of wolframic acid sodium content is
0.04~1wt%.
The electrolyte is containing 35vol%H2The binary organic system of O~65vol% glycerine.
Tungsten atom percentage composition is 0.3~1.5at% in obtained tungsten doping nano pipe array material.
The doping of wolfram element is controlled by controlling the dosage of sodium tungstate.
The present invention provides a kind of preparation method of witch culture Nano tube array of titanium dioxide, due to W doping process be
Anodic oxidation carries out simultaneously during forming nanotube, W element more uniformly spreading in entire nanotube layer.By changing
The concentration of sodium tungstate in transformation electrolytic liquid, can be with the content of W element in Effective Regulation nanotube.The W doping TiO being prepared2It receives
For mitron array perpendicular to substrate, binding force is good, and for nanotube caliber between 100~150nm, 4-8 μm of pipe range adjustable, is suitable for
The fields such as energy conversion and photocatalytic pollutant degradation.
Compared with prior art, the beneficial effects of the present invention are:
(1) TiO is first prepared compared to current2Nanotube introduces the preparation method of W element by other technologies again, and the present invention is
W adulterates process and TiO2The formation of nanotube carries out simultaneously, and the constant concentration of sodium tungstate in the electrolytic solution, can guarantee W member
Element can be uniformly distributed in entire nanotube layer from nozzle to tube bottom.
(2) the doping process of W is only once to be formed with common titanium sheet original position anodic oxidation, without the conjunction that early period is special
Golden preparation process simplifies process flow without the complex process program in later period.
(3) doping of W by control electrolyte in sodium tungstate concentration can it is convenient regulate and control, it is easy to operate.
Detailed description of the invention
Fig. 1 is FE-SEM surface topography map of the invention
Fig. 2 is ESEM cross-section morphology figure of the present invention
Fig. 3 is that (a: Surface scan corresponds to section to section power spectrum Surface scan figure of the invention；B: the distribution of W element on section)
Fig. 4 is XRD spectrum of the invention
Specific embodiment
Below with reference to example, the invention will be further described；In described below, each reagent is that analysis is pure；To avoid
It repeats, the pretreatment of titanium sheet is all unified are as follows: is polished step by step with the SiC sand paper of 240 mesh, 400 mesh, 800 mesh, 1000 mesh and 1500 mesh
Afterwards, it is cleaned by ultrasonic respectively with acetone, ethyl alcohol and deionized water, then with mixed acid solution (6.0mol/L HNO3, 1.0mol/L HF)
Chemical polishing, last deionized water cleaning, dries up spare.
Embodiment one
Step 1: titanium sheet pre-processes；
It is dissolved in 35mL water Step 2: weighing the ammonium fluoride (about 0.92g) that mass percent is 0.8wt%, stirs 10 points
Clock sufficiently dissolves to obtain ammonium fluoride aqueous solution.
Step 3: addition mass percent is the two of 0.04wt% (about 0.05g) in the ammonium fluoride aqueous solution of step 2
Tungstic acid hydrate sodium magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 30 minutes at 50 DEG C, and solution mixing is equal
It is even to obtain electrolyte.
Step 4: the pretreated titanium sheet of step 1 to be connect to the anode of constant-voltage DC source, graphite flake or platinized platinum connect power supply
Cathode, and immersed in the electrolyte of step 3 simultaneously, constant pressure 30V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.When anodic oxidation
Between be set as 3 hours, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, with ethyl alcohol and is gone
Ionized water ultrasonic cleaning is dried, and nanotube sample is obtained.
It is heat-treated Step 5: nanotube sample obtained by step 4 is put into temperature programmed control Muffle furnace, heating rate 5
DEG C/min.Constant temperature 2 hours after being warming up to 450 DEG C take out sample cooled to room temperature, obtain witch culture nano titania
Pipe array composite material.
SEM test result shows witch culture Nano tube array of titanium dioxide perpendicular to titanium substrate, and nanotube caliber is about
100nm, about 4 μm of pipe range, nanotube surface regular appearance.In addition to anatase titania and titanium substrate in XRD spectra
Outside characteristic diffraction peak, the apparent characteristic diffraction peak of other materials is not observed, illustrates that wolfram element is entered with atomic level doping
In the lattice of titanium dioxide.EDS and XPS the result shows that, wolfram element is uniformly distributed in entire nanotube layer, wherein wolfram element
Content about 0.3at%.
Embodiment two
Preparation process is basically the same as the first embodiment, except that:
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is two hydrations of 0.08wt% (about 0.10g)
Sodium tungstate magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 30 minutes at 50 DEG C, and solution is uniformly mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the anode of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And it immerses in electrolyte simultaneously, constant pressure 35V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.It is small that anodizing time is set as 3
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethyl alcohol and deionized water ultrasound
It washes and dries, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and is heat-treated, 5 DEG C/minute of heating rate
Clock.Constant temperature 2 hours after being warming up to 450 DEG C take out sample cooled to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite material.
Test result, witch culture Nano tube array of titanium dioxide is perpendicular to titanium substrate, and nanotube caliber about 120nm is (see figure
1), about 4 μm of pipe range, nanotube surface regular appearance.Nanotube ingredient is mainly anatase crystal titanium dioxide, and wolfram element is with original
Sub horizontal doping enters in the lattice of titanium dioxide.Wolfram element is uniformly distributed in entire nanotube layer, wherein wolfram element
Content about 0.5at%.
Embodiment three
Preparation process is basically the same as the first embodiment, except that:
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is two hydrations of 0.16wt% (about 0.20g)
Sodium tungstate magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 40 minutes at 50 DEG C, and solution is uniformly mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the anode of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And it immerses in electrolyte simultaneously, constant pressure 35V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.It is small that anodizing time is set as 4
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethyl alcohol and deionized water ultrasound
It washes and dries, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and is heat-treated, 5 DEG C/minute of heating rate
Clock.Constant temperature 2 hours after being warming up to 450 DEG C take out sample cooled to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite material.
Test result, witch culture Nano tube array of titanium dioxide is perpendicular to titanium substrate, nanotube caliber about 120nm, pipe range
About 6 μm (see Fig. 2), nanotube surface regular appearance.Nanotube ingredient is mainly anatase crystal titanium dioxide, and wolfram element is with original
Sub horizontal doping enters in the lattice of titanium dioxide.Wolfram element is uniformly distributed in entire nanotube layer, wherein wolfram element
Content about 0.8at%.
Example IV
Preparation process is basically the same as the first embodiment, except that:
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is two hydrations of 0.32wt% (about 0.40g)
Sodium tungstate magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 50 minutes at 50 DEG C, and solution is uniformly mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the anode of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And it immerses in electrolyte simultaneously, constant pressure 35V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.It is small that anodizing time is set as 4
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethyl alcohol and deionized water ultrasound
It washes and dries, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and is heat-treated, 5 DEG C/minute of heating rate
Clock.Constant temperature 2 hours after being warming up to 450 DEG C take out sample cooled to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite material.
Test result, witch culture Nano tube array of titanium dioxide is perpendicular to titanium substrate, nanotube caliber about 120nm, pipe range
About 6 μm, nanotube surface regular appearance.Nanotube ingredient is mainly anatase crystal titanium dioxide, and wolfram element is with atomic level
Doping enters in the lattice of titanium dioxide.Wolfram element is uniformly distributed (see Fig. 3) in entire nanotube layer, wherein wolfram element
Content about 1.0at%.
Embodiment five
Preparation process is basically the same as the first embodiment, except that:
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is two hydrations of 0.64wt% (about 0.80g)
Sodium tungstate magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 60 minutes at 50 DEG C, and solution is uniformly mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the anode of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And it immerses in electrolyte simultaneously, constant pressure 40V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.It is small that anodizing time is set as 5
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethyl alcohol and deionized water ultrasound
It washes and dries, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and is heat-treated, 5 DEG C/minute of heating rate
Clock.Constant temperature 2 hours after being warming up to 450 DEG C take out sample cooled to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite material.
Test result, witch culture Nano tube array of titanium dioxide is perpendicular to titanium substrate, nanotube caliber about 150nm, pipe range
About 8 μm, nanotube surface regular appearance.Nanotube ingredient is mainly anatase crystal titanium dioxide (see Fig. 4), and wolfram element is with original
Sub horizontal doping enters in the lattice of titanium dioxide.Wolfram element is uniformly distributed in entire nanotube layer, wherein wolfram element
Content about 1.3at%.
Embodiment six
Preparation process is basically the same as the first embodiment, except that:
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is the two hydration tungsten of 1.0wt% (about 1.2g)
Sour sodium magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 60 minutes at 50 DEG C, and solution is uniformly mixed and obtains
Electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the anode of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And it immerses in electrolyte simultaneously, constant pressure 40V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.It is small that anodizing time is set as 5
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethyl alcohol and deionized water ultrasound
It washes and dries, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and is heat-treated, 5 DEG C/minute of heating rate
Clock.Constant temperature 2 hours after being warming up to 450 DEG C take out sample cooled to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite material.
Test result, witch culture Nano tube array of titanium dioxide is perpendicular to titanium substrate, nanotube caliber about 150nm, pipe range
About 8 μm, nanotube surface regular appearance.Nanotube ingredient is mainly anatase crystal titanium dioxide, and wolfram element is with atomic level
Doping enters in the lattice of titanium dioxide.Wolfram element is uniformly distributed in entire nanotube layer, and wherein the content of wolfram element is about
1.5at%.
Claims (5)
1. a kind of preparation method of witch culture Nano tube array of titanium dioxide, specific practice is:
Step 1: titanium sheet pre-processes: metallic titanium surface sand paper sanding and polishing, and chemical polishing step by step cleans spare；
Step 2: it is 0.8wt% ammonium fluoride that mass percent is added in the deionized water that percent by volume is 35vol%, stir
It mixes 10 minutes, sufficiently dissolves, obtain ammonium fluoride solution, it is spare；
Step 3: above-mentioned configured ammonium fluoride solution is added in the Disodium tungstate (Na2WO4) dihydrate that mass percent is 0.04~1wt%
In, it stirs dissolution in 10 minutes completely, the glycerine that percent by volume is 65vol% is then added, under the conditions of 50 DEG C of constant temperature simultaneously
Stirring 30~60 minutes, obtains electrolyte；
Step 4: titanium sheet pretreated in step 1 is connect the positive grade of power supply, graphite flake or platinized platinum connect power cathode, are placed in step
In three electrolyte, at constant pressure anodic oxygenization 3~5 hours of 30~40V, nanotube sample is obtained, with ethyl alcohol and deionization
Water successively cleans, and dries spare；
Step 5: gained nanotube sample in step 4 is placed in Muffle furnace, 450 DEG C are warming up to 5 DEG C/min of rate,
And keep constant temperature 2 hours, then cooled to room temperature, obtains witch culture Nano tube array of titanium dioxide composite material.
2. a kind of preparation method of witch culture Nano tube array of titanium dioxide according to claim 1, it is characterised in that: institute
The mass percent for stating ammonium fluoride content in electrolyte is 0.8wt%, the mass percent of wolframic acid sodium content is 0.04~
1wt%.
3. a kind of preparation method of witch culture Nano tube array of titanium dioxide according to claim 1, it is characterised in that: institute
Stating electrolyte is containing 35vol%H2The binary organic system of O~65vol% glycerine.
4. a kind of preparation method of witch culture Nano tube array of titanium dioxide according to claim 1, it is characterised in that:
To tungsten doping nano pipe array material in tungsten atom percentage composition be 0.3~1.5at%.
5. a kind of preparation method of witch culture Nano tube array of titanium dioxide according to claim 1, it is characterised in that: logical
The dosage of control sodium tungstate is crossed to control the doping of wolfram element.
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