CN107841777A - 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
- Publication number
- CN107841777A CN107841777A CN201711053050.6A CN201711053050A CN107841777A CN 107841777 A CN107841777 A CN 107841777A CN 201711053050 A CN201711053050 A CN 201711053050A CN 107841777 A CN107841777 A CN 107841777A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nano tube
- tube array
- electrolyte
- witch culture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 29
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 16
- 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
- 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
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract 2
- 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
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 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
- 238000004140 cleaning Methods 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
- 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
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 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
- 238000005516 engineering process 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
- 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
- 238000004458 analytical method Methods 0.000 description 1
- 238000003491 array Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying 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
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 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
Landscapes
- 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)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of preparation method of witch culture Nano tube array of titanium dioxide, belong to nano material environmental photocatlytsis technical field.1st, titanium sheet pre-processes：2nd, it is 0.8wt% ammonium fluorides mass percent to be added in 35vol% deionized water, fully dissolving, obtains ammonium fluoride solution, standby；3rd, the Disodium tungstate (Na2WO4) dihydrate that mass percent is 0.04~1wt% is added in the good ammonium fluoride solution of above-mentioned configuration, then adds the glycerine that percent by volume is 65vol%, 50 DEG C of constant temperature simultaneously stirs 30~60 minutes, obtains electrolyte；4th, pretreated titanium sheet in step 1 is connect into the positive level of power supply, graphite flake or platinized platinum connect power cathode, be placed in the electrolyte of step 3, in 30~40V constant pressure anodic oxygenization 3~5 hours, nanometer tube composite materials are obtained, are cleaned successively with ethanol and deionized water, are dried standby；5th, gained nanometer tube composite materials are placed in Muffle furnace, 450 DEG C is warming up to 5 DEG C/min of speed, and keep constant temperature 2 hours, be cooled to room temperature and obtain witch culture Nano tube array of titanium dioxide.
Description
Technical field
The invention belongs to nano material environmental photocatlytsis technical field.
Background technology
Since 1972, TiO2Photocatalysis technology decomposition water H is used by report first2And O2Afterwards, TiO2The light of semiconductor
Prelude has just been pulled open in catalysis technique research.TiO2As a kind of semi-conducting 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 that specific surface area is big, it is the advantages that immobilized performance is good, particularly suitable to 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 ultraviolet light of the wavelength less than 385nm, and to accounting for the visible light part of sunshine 95% all
Efficiently it can not absorb and utilize, this have impact on TiO to a certain extent2Catalytic efficiency of the nanotube as photochemical catalyst.And
Extend TiO2Spectral response range to can by light area then be improve its photocatalytic activity a kind of effective means.
W element dopings can effectively improve TiO2Photocatalytic activity because W elements doping on the one hand can be formed
WO3/TiO2Heterojunction structure, suppress Carrier recombination；On the other hand, W6+With Ti4+With approximate ionic radius, can enter
TiO2Intracell substitutes Ti4+Position, so as to forming new doped energy-band in forbidden band, the forbidden band for reducing composite is wide
Degree so that material have can by photoresponse activity.
At present in TiO2The method that W doping is carried out in nanotube is mainly infusion process, hydro-thermal method, electro-deposition and oxide alloy
Method.Although these methods can realize doping vario-property of the W elements to nanotube to a certain extent, certain lack all be present
Fall into, as infusion process and electrodeposition process are difficult to control on the distributing homogeneity of W elements；Hydro-thermal method needs the operation of HTHP,
Condition is harsh；The more difficult preparation of Ti-W alloys in alloy oxidation method, and the W dopings in alloy can not it is convenient regulate and control.Therefore originally
Invention proposes a kind of anodizing in situ to realize W elements to TiO2The doping vario-property of nanotube, i.e., in metal Ti anodic oxygens
During change forms nanotube, the W in electrolyte injects TiO simultaneously in the presence of electric field force2, so as to disposably form W
TiO2 nano-tube arrays are adulterated, doping is controlled by the regulation and control to W salinity in electrolyte, are that a kind of effective doping changes
Property method.
The content of the invention
It is an object of the invention to provide a kind of preparation method of witch culture Nano tube array of titanium dioxide, it can effectively be solved
Certainly W elements are 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, cleaning are standby；
Step 2: it is 0.8wt% fluorinations that mass percent is added in the deionized water that percent by volume is 35vol%
Ammonium, stir 10 minutes, fully dissolving, obtain ammonium fluoride solution, it is standby；
Step 3: the Disodium tungstate (Na2WO4) dihydrate that mass percent is 0.04~1wt% is added into the good ammonium fluoride of above-mentioned configuration
In solution, the glycerine that dissolving in 10 minutes is complete, and then addition percent by volume is 65vol% is stirred, in 50 DEG C of conditions of constant temperature
Descend and stir 30~60 minutes, obtain electrolyte；
Step 4: pretreated titanium sheet in step 1 is connect into the positive level of power supply, graphite flake or platinized platinum connect power cathode, are placed in
In the electrolyte of step 3, in 30~40V constant pressure anodic oxygenization 3~5 hours, nanotube sample is obtained, with ethanol and is gone
Ionized water cleans successively, dries standby；
Step 5: gained nanotube sample in step 4 is placed in Muffle furnace, 450 are warming up to 5 DEG C/min of speed
DEG C, and keep constant temperature 2 hours, then naturally cool to room temperature and obtain witch culture Nano tube array of titanium dioxide composite.
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 invention provides a kind of preparation method of witch culture Nano tube array of titanium dioxide, due to W doping process be
Anodic oxidation is carried out simultaneously during forming nanotube, W elements more uniformly spreading in whole nanotube layer.By changing
The concentration of sodium tungstate in transformation electrolytic liquid, can be with the content of W elements in Effective Regulation nanotube.The W doping TiO being prepared2Receive
Mitron array is perpendicular to substrate, and adhesion is good, and for nanotube caliber between 100~150nm, 4-8 μm of pipe range is adjustable, is applied to
The field such as energy conversion and photocatalytic pollutant degradation.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) compare and first prepare TiO at present2Nanotube introduces the preparation method of W elements by other technologies again, and the present invention is
W adulterates process and TiO2The formation of nanotube is carried out simultaneously, and the constant concentration of sodium tungstate in the electrolytic solution, can ensure W members
It can be uniformly distributed in element nanotube layer whole from the mouth of pipe to ttom of pipe.
(2) W doping process is only once to be formed with common titanium sheet original position anodic oxidation, without the conjunction that early stage is special
Golden preparation process, without the complex process program in later stage, simplify technological process.
(3) W doping by control sodium tungstate in electrolyte concentration can it is convenient regulate and control, it is easy to operate.
Brief description of the drawings
Fig. 1 is the FE-SEM surface topography maps of the present invention
Fig. 2 is ESEM cross-section morphologies figure of the present invention
Fig. 3 is the section power spectrum Surface scan figure (a of the present invention:Surface scan corresponds to section；b：The distribution of W elements on section)
Fig. 4 is the XRD spectrum of the present invention
Embodiment
With reference to example, the invention will be further described；In described below, each reagent is that analysis is pure；To avoid
Repeat, the pretreatment of titanium sheet is all unified for：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, ethanol and deionized water, then with mixed acid solution (6.0mol/L HNO3, 1.0mol/L HF)
Chemical polishing, last deionized water cleaning, drying are standby.
Embodiment one
Step 1: titanium sheet pre-processes；
It is dissolved in Step 2: weighing the ammonium fluoride (about 0.92g) that mass percent is 0.8wt% in 35mL water, stirs 10 points
Clock, fully dissolve to obtain ammonium fluoride aqueous solution.
Step 3: in the ammonium fluoride aqueous solution of step 2, addition mass percent is the two of 0.04wt% (about 0.05g)
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 positive pole of constant-voltage DC source, graphite flake or platinized platinum connect power supply
Negative pole, and immerse simultaneously in the electrolyte of step 3, constant pressure 30V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.During 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 ethanol and gone
Ionized water, which is cleaned by ultrasonic, to be dried, and obtains nanotube sample.
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 and naturally cool to room temperature, obtain witch culture nano titania
Pipe array composite material.
SEM test results show that witch culture Nano tube array of titanium dioxide is perpendicular to titanium substrate, and nanotube caliber is about
100nm, about 4 μm of pipe range, nanotube surface regular appearance.Except anatase titania and titanium substrate in XRD spectra
Outside characteristic diffraction peak, the obvious 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 results show that wolfram element is uniformly distributed in whole nanotube layer, wherein wolfram element
Content about 0.3at%.
Embodiment two
Preparation process and embodiment one are essentially identical, except that：
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is 0.08wt% (about 0.10g) two hydrations
Sodium tungstate, magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 30 minutes at 50 DEG C, and solution is well mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the positive pole of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And immerse simultaneously in electrolyte, constant pressure 35V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.Anodizing time is set as that 3 is small
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethanol and deionized water ultrasound
Wash and dry, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and be 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 and naturally cool to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite.
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 composition is mainly anatase crystal titanium dioxide, and wolfram element is with original
Sub horizontal doping is entered in the lattice of titanium dioxide.Wolfram element is uniformly distributed in whole nanotube layer, wherein wolfram element
Content about 0.5at%.
Embodiment three
Preparation process and embodiment one are essentially identical, except that：
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is 0.16wt% (about 0.20g) two hydrations
Sodium tungstate, magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 40 minutes at 50 DEG C, and solution is well mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the positive pole of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And immerse simultaneously in electrolyte, constant pressure 35V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.Anodizing time is set as that 4 is small
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethanol and deionized water ultrasound
Wash and dry, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and be 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 and naturally cool to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite.
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 composition is mainly anatase crystal titanium dioxide, and wolfram element is with original
Sub horizontal doping is entered in the lattice of titanium dioxide.Wolfram element is uniformly distributed in whole nanotube layer, wherein wolfram element
Content about 0.8at%.
Example IV
Preparation process and embodiment one are essentially identical, except that：
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is 0.32wt% (about 0.40g) two hydrations
Sodium tungstate, magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 50 minutes at 50 DEG C, and solution is well mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the positive pole of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And immerse simultaneously in electrolyte, constant pressure 35V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.Anodizing time is set as that 4 is small
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethanol and deionized water ultrasound
Wash and dry, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and be 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 and naturally cool to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite.
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 composition is mainly anatase crystal titanium dioxide, and wolfram element is with atomic level
Doping is entered in the lattice of titanium dioxide.Wolfram element is uniformly distributed (see Fig. 3) in whole nanotube layer, wherein wolfram element
Content about 1.0at%.
Embodiment five
Preparation process and embodiment one are essentially identical, except that：
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is 0.64wt% (about 0.80g) two hydrations
Sodium tungstate, magnetic agitation 10 minutes, adds 65mL glycerine, magnetic agitation 60 minutes at 50 DEG C, and solution is well mixed
To electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the positive pole of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And immerse simultaneously in electrolyte, constant pressure 40V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.Anodizing time is set as that 5 is small
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethanol and deionized water ultrasound
Wash and dry, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and be 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 and naturally cool to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite.
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 composition is mainly anatase crystal titanium dioxide (see Fig. 4), and wolfram element is with original
Sub horizontal doping is entered in the lattice of titanium dioxide.Wolfram element is uniformly distributed in whole nanotube layer, wherein wolfram element
Content about 1.3at%.
Embodiment six
Preparation process and embodiment one are essentially identical, except that：
(1) in the ammonium fluoride aqueous solution of step 2, addition mass percent is hydrated tungsten for the two 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 well mixed to be obtained
Electrolyte.
(2) the pretreated titanium sheet of step 1 is connect to the positive pole of constant-voltage DC source, graphite flake or platinized platinum connect power cathode
And immerse simultaneously in electrolyte, constant pressure 40V, electrode spacing 3cm, 25 DEG C of electrolyte constant temperature.Anodizing time is set as that 5 is small
When, with magnetic agitation in whole process.Sample is taken out after the completion of anode oxidation process, it is clear with ethanol and deionized water ultrasound
Wash and dry, obtain nanotube sample.
(3) nanotube sample obtained by (2) is put into temperature programmed control Muffle furnace and be 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 and naturally cool to room temperature, obtain witch culture Nano tube array of titanium dioxide
Composite.
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 composition is mainly anatase crystal titanium dioxide, and wolfram element is with atomic level
Doping is entered in the lattice of titanium dioxide.Wolfram element is uniformly distributed in whole 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 are：
Step 1: titanium sheet pre-processes：Metallic titanium surface sand paper sanding and polishing, and chemical polishing step by step, cleaning are standby；
Step 2: it is 0.8wt% ammonium fluorides that mass percent is added in the deionized water that percent by volume is 35vol%, stir
Mix 10 minutes, fully dissolving, obtain ammonium fluoride solution, it is standby；
Step 3: the Disodium tungstate (Na2WO4) dihydrate that mass percent is 0.04~1wt% is added into the good ammonium fluoride solution of above-mentioned configuration
In, stir that dissolving in 10 minutes is complete, then add the glycerine that percent by volume is 65vol%, under the conditions of 50 DEG C of constant temperature simultaneously
Stirring 30~60 minutes, obtains electrolyte；
Step 4: pretreated titanium sheet in step 1 is connect into the positive level of power supply, graphite flake or platinized platinum connect power cathode, are placed in step
In three electrolyte, in 30~40V constant pressure anodic oxygenization 3~5 hours, nanotube sample is obtained, with ethanol and deionization
Water cleans successively, dries standby；
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 speed,
And keep constant temperature 2 hours, room temperature is then naturally cooled to, obtains witch culture Nano tube array of titanium dioxide composite.
A kind of 2. 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 for 0.04~
1wt%.
A kind of 3. preparation method of witch culture Nano tube array of titanium dioxide according to claim 1, it is characterised in that：Institute
It is containing 35vol%H to state electrolyte2The binary organic system of O~65vol% glycerine.
A kind of 4. 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%.
A kind of 5. preparation method of witch culture Nano tube array of titanium dioxide according to claim 1, it is characterised in that：It is logical
The dosage for crossing control sodium tungstate controls the doping of wolfram element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711053050.6A CN107841777B (en) | 2017-11-01 | 2017-11-01 | A kind of preparation method of witch culture Nano tube array of titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711053050.6A CN107841777B (en) | 2017-11-01 | 2017-11-01 | A kind of preparation method of witch culture Nano tube array of titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107841777A true CN107841777A (en) | 2018-03-27 |
| CN107841777B CN107841777B (en) | 2019-11-01 |
Family
ID=61680910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711053050.6A Expired - Fee Related CN107841777B (en) | 2017-11-01 | 2017-11-01 | A kind of preparation method of witch culture Nano tube array of titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107841777B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382083A (en) * | 2018-11-30 | 2019-02-26 | 内蒙古工业大学 | Carbon nano tube-doped titania nanotube catalysis material and preparation method thereof |
| CN110918088A (en) * | 2019-12-27 | 2020-03-27 | 重庆市科学技术研究院 | Preparation method of titanium dioxide photocatalyst |
| CN115814780A (en) * | 2022-11-18 | 2023-03-21 | 海南大学 | Preparation method of lithium-doped titanium dioxide nanowire array |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1515705A (en) * | 2003-08-29 | 2004-07-28 | 哈尔滨工业大学 | Method for in situ growing high-hardness wear resistant ceramic coating layer on titanium alloy surface |
| CN101109096A (en) * | 2007-06-22 | 2008-01-23 | 湖南大学 | Method for producing titanium dioxide nano tube array with molybdenum tungsten doped anodizing method |
| CN102509625A (en) * | 2011-11-14 | 2012-06-20 | 复旦大学 | In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film |
| CN103011346A (en) * | 2011-09-20 | 2013-04-03 | 同济大学 | Titanium-tungsten alloy oxide nano-tube electrode with characteristic of in-situ vertical growth, preparation method and applications thereof |
| CN105051253A (en) * | 2012-11-14 | 2015-11-11 | 格但斯克大学 | Method of production of a material with photocatalytic and biocidal properties containing spatially oriented titanium dioxide nanotubes modified with metals, particularly precious metals |
-
2017
- 2017-11-01 CN CN201711053050.6A patent/CN107841777B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1515705A (en) * | 2003-08-29 | 2004-07-28 | 哈尔滨工业大学 | Method for in situ growing high-hardness wear resistant ceramic coating layer on titanium alloy surface |
| CN101109096A (en) * | 2007-06-22 | 2008-01-23 | 湖南大学 | Method for producing titanium dioxide nano tube array with molybdenum tungsten doped anodizing method |
| CN103011346A (en) * | 2011-09-20 | 2013-04-03 | 同济大学 | Titanium-tungsten alloy oxide nano-tube electrode with characteristic of in-situ vertical growth, preparation method and applications thereof |
| CN102509625A (en) * | 2011-11-14 | 2012-06-20 | 复旦大学 | In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film |
| CN105051253A (en) * | 2012-11-14 | 2015-11-11 | 格但斯克大学 | Method of production of a material with photocatalytic and biocidal properties containing spatially oriented titanium dioxide nanotubes modified with metals, particularly precious metals |
Non-Patent Citations (2)
| Title |
|---|
| JIANYU GONG: "Novel one-step preparation of tungsten loaded TiO2 nanotube arrays with enhanced photoelectrocatalytic activity for pollutant degradation and hydrogen production", <CATALYSIS COMMUNICATIONS> * |
| M. M. MOMENI ET AL: "Easy synthesis of titania–tungsten trioxide nano omposite films by anodising method solar water splitting", <MATERIALS SCIENCE AND TECHNOLOGY> * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382083A (en) * | 2018-11-30 | 2019-02-26 | 内蒙古工业大学 | Carbon nano tube-doped titania nanotube catalysis material and preparation method thereof |
| CN109382083B (en) * | 2018-11-30 | 2021-07-20 | 内蒙古工业大学 | Carbon nanotube-doped titanium dioxide nanotube photocatalytic material and preparation method thereof |
| CN110918088A (en) * | 2019-12-27 | 2020-03-27 | 重庆市科学技术研究院 | Preparation method of titanium dioxide photocatalyst |
| CN115814780A (en) * | 2022-11-18 | 2023-03-21 | 海南大学 | Preparation method of lithium-doped titanium dioxide nanowire array |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107841777B (en) | 2019-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107723777B (en) | The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot | |
| CN104835648B (en) | The preparation method of bismuth oxide nanoparticles/Nano tube array of titanium dioxide | |
| CN108525667A (en) | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide | |
| CN108842169A (en) | A kind of metal oxide-loaded pucherite composite material and its preparation and application | |
| CN101653728A (en) | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst | |
| CN108479806A (en) | A kind of hetero-junction thin-film being made of same metal and oxygen group elements and its preparation and application | |
| CN107841777B (en) | A kind of preparation method of witch culture Nano tube array of titanium dioxide | |
| CN102240550A (en) | Low-concentration copper-doped titanium dioxide nanotube photocatalyst and preparation method thereof | |
| CN102173449A (en) | Method for preparing nanometer lead dioxide electrode | |
| CN105597784A (en) | MoS2-doped iron oxide photocatalytic thin film and preparation method as well as application thereof to treatment of phenolic waste water | |
| CN105177671B (en) | A kind of preparation method of silver Nano granule/titanium dioxide nano-tube array | |
| CN103320839B (en) | Go the preparation method of the titanium dioxide nanotube array photoelectrode of removal organic polluter | |
| CN105044180A (en) | Preparation method and application of heterojunction photoelectrode | |
| CN102509625A (en) | In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film | |
| CN108611653A (en) | A kind of pucherite composite material of carried magnetic nano particle and its preparation and application | |
| CN108675382A (en) | One kind being based on TiO2The integrated catalytic system and its degradation process method of nano pipe light catalyst | |
| CN106431005A (en) | Strontium titanate-titanium dioxide composite nanotube array film and preparation method and application thereof | |
| CN108505098B (en) | Preparation method of Pt-loaded sulfur-rich molybdenum disulfide boundary site modified titanium dioxide nanotube array | |
| CN108842168A (en) | A kind of two-step electrochemical method preparation g-C3N4/ MMO compound film optoelectronic pole | |
| CN101508417A (en) | Double-layer nanostructured anatase titanium dioxide photoelectric film and method for preparing the same | |
| CN106978619A (en) | A kind of enhancing titania nanotube is to visible light-responded preparation method | |
| CN108273486B (en) | Carbon nano tube/secondary anode oxidized TiO2Nanotube photocatalyst material and preparation method and application thereof | |
| CN105350068A (en) | Preparation method of porous monocrystalline TiO2 thin film | |
| CN103285843B (en) | TiO2 nano particle/TiO2 nanotube array and application thereof | |
| CN103436942B (en) | A kind of CuInSe 2and TiO 2the preparation method of composite heterogenous junction film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191101 |