CN102260897A - Titanium dioxide nanotube array film and preparation method thereof - Google Patents
Titanium dioxide nanotube array film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a titanium dioxide nanotube array film and a preparation method thereof. The technical schemes are as follows: firstly grinding and polishing a titanium-containing metal sheet to be used as an anode, placing the anode in an electrolyte and performing anodic oxidation while controlling the voltage at 10-60 V for 0.5-5 hours; then taking the anodized titanium-containing metal sheet from the electrolyte, placing the anodized titanium-containing metal sheet in a high-temperature furnace, and insulating heat at the temperature of 300-800 DEG C in the protective atmosphere for 0.5-10 hours; and then cooling along with the furnace in the protective atmosphere to room temperature, thus forming a carbon-doped or carbon-nitrogen co-doped titanium dioxide nanotube array film on the surface of the cooled titanium-containing metal sheet. The preparation method provided by the invention has the characteristics of no need for external carbon source or nitrogen source, low reaction temperature, simple and reliable method and controllable contents of doping elements; and the prepared carbon-doped or carbon-nitrogen co-doped titanium dioxide nanotube array film has uniform distribution of the doping elements.
Description
Technical field
The invention belongs to titanium nano-pipe array thin film technical field, relate in particular to a kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
Background technology
The environment in recent years pollution problems is serious day by day, and photocatalytic degradation is to handle most important and one of the most potential method of organic pollutant at present.Light-catalyzed reaction is under the condition of illumination, the chemical reaction that can facilitate by photocatalyst.Semiconductor light-catalyst produces electron-hole pair under the illumination greater than its energy gap width, photohole has strong oxidizing property, can fast organic pollutant be oxidized to CO
2And H
2O utilizes light-catalyzed reaction almost can decompose all to human body and the deleterious organic pollutant of environment.At numerous photocatalysts that are used for the photocatalytic degradation environmental organic pollutant, titanium dioxide has the sensitivity of light height, oxidation activity is strong, chemical stability is high and advantage such as cheapness and be subjected to paying close attention to widely.Early stage titanium dioxide mainly is synthetic by chemical vapour deposition and hydrothermal method, mostly is the powder shaped material greatly, and the powder catalystic material is unfavorable for recycling.
Owing to have big specific surface area and good electron conductive performance, it is firm etc. that nanotube and substrate are sticked, and is beneficial to recycling by the prepared titanium dioxide nano-pipe array thin film of anonizing.But titania nanotube still is subjected to all multifactor influences in actual applications, topmost restraining factors have: 1) the titanium dioxide broad stopband is 3.0～3.2eV, can only absorbing wavelength less than the UV-light of 380nm, and the ratio of UV-light in sunlight little (＜7%) is low to the utilization ratio of sunlight; 2) light induced electron-hole is to the compound photochemical catalysis effect that causes is relatively poor easily.Therefore, widen the spectral absorption scope of titanium dioxide and to reduce the right recombination probability in light induced electron-hole be of paramount importance research topic in current photochemical catalysis and the opto-electronic conversion field.A large amount of studies show that, improve its absorption in visible-range by titanium dioxide is mixed and be considered to one of a kind of effective means, the metal-doped element of report mainly contains Fe at present, Cr etc., non-metallic element mainly contains C, N, (Schmuki P. such as S and P, et al.Chem.Phys.Chem.2010,11,2698), wherein the doping effect of nonmetallic substance C and N element is particularly evident, after C or N are doped in the titanium dioxide lattice, in the energy gap of titanium dioxide, form doped energy-band, reduced the energy gap of titanium dioxide, simultaneously the titanium dioxide that makes of adulterated carbon species produces lattice imperfection and O room, can effectively stop right compound in light induced electron-hole.
At present, the preparation method of carbon doped titanic oxide nano tube utilizes anonizing to prepare unbodied titania nanotube, after the annealing crystallizationization, calcines down and gets at carbon-containing atmosphere (carbon monoxide, acetylene etc.) again in air atmosphere.People such as Bard are with titania nanotube 500～800 ℃ of following thermal treatments in CO atmosphere of anneal in the air, obtained the adulterated titania nanotube of carbon, the energy gap of titania nanotube has been reduced to 2.2eV, light absorbing wavelength is extended to above (the Bard A.J.et al.Nano Lett. of 420nm, 2006,6,24).People such as Schmuk P are in the method that adopts high temperature annealing, and the titania nanotube 800 ℃ of thermal treatments in acetylene atmosphere with the anodizing preparation have obtained TiO
xC
2-xNano tube structure (Schmuk P.et al.Angew.Chem.Int.Ed., 2009,48,7236).Though these methods can realize that titania nanotube is carried out carbon to mix, but technology is complicated, all need to introduce external carbon source, because the carbon-containing atmosphere of introducing is not easy to be diffused into the bottom of nanotube, cause the doping of carbon inhomogeneous, can only realize doping mostly, and the doping of carbon is lower to the nanotube top layer, limited to the photocatalysis performance improvement of titania nanotube; In addition, some thermal treatment temps are higher, and the structure of nanotube is destroyed to a certain extent.The present invention proposes a kind of external carbon-containing atmosphere that need not; preparing the organic electrolyte that titania nanotube remained in the nanotube with anodic oxidation is carbon source; directly calcining under protective atmosphere can be at the synthetic carbon doped titanium dioxide nanotube array film of original position under the lesser temps (300 ℃).It is good that the pattern of nanotube and structure keep, and the dopant profiles of carbon is even, and the carbon doping content can effectively be controlled by heat-treat condition.The carbon doping is carried out to titanium dioxide in the result of study surface can effectively improve its photocatalysis performance in visible-range.
It is the another kind of effective ways that another kind improves titania nanotube photochemical catalysis effect that nitrogen mixes, and also has several different methods can realize that titanium dioxide is carried out nitrogen to mix at present." a kind of elder generation carries out nitriding by the ionitriding technology at titanium plate surface and handles " be patented technology (CN201010291804.3), prepare the adulterated titania nanotube of nitrogen with anonizing at the titanium sheet of nitriding, this method is faced with the relatively thinner and few problem of the adulterated amount of nitrogen of nitrided case equally.In recent years the research report shows, because the synergistic effect of doped element, the codoped of two or more elements can further improve single TiO that plants element doping
2Photocatalysis performance.People such as Zhu discover and adopt sol-gel method synthetic phosphorus, nitrogen co-doped TiO
2The particulate photocatalytic activity is than single element phosphor or adulterated activity of such catalysts of nitrogen higher (Zhu Y.X., et al.Appl.Catal.B, 2007,76,196) of planting.Human sol-gel methodes such as Li are prepared boron, nitrogen co-doped TiO
2Photocatalysis performance be better than the adulterated TiO of nitrogen
2(Li Y.X., et al.Appl.Surf.Sci., 2008,254,6831).People such as Cai are embedded in titania nanotube in the mixture of polyoxyethylene glycol and uric acid, 600 ℃ of following thermal treatment obtains carbon, nitrogen co-doped titania nanotube (Cai Q.Y. in nitrogen atmosphere, et al.Electrochem.Comm., 2009,11,1748), still, also filled up carbon species in the nanotube simultaneously, photocatalysis performance is undesirable.
Summary of the invention
The present invention is intended to overcome the prior art defective, purpose provides and a kind ofly need not external carbon source or nitrogenous source, temperature of reaction is low, method is simple and reliable, doped element content is controlled in the method that contains titanium metal plate surface preparation titanium dioxide nano-pipe array thin film, is evenly distributed with the titanium dioxide nano-pipe array thin film institute doping elements of this method preparation.
For achieving the above object.The technical solution used in the present invention is: will contain the titanium metal plate grinding and buffing earlier and insert in the electrolytic solution as anode, be anodic oxidation 0.5～5 hour under 10～60V condition at control voltage; Again the titanium metal plate that contains after the anodizing is taken out from electrolytic solution, place High Temperature Furnaces Heating Apparatus, under 300～800 ℃ of conditions, in protective atmosphere, be incubated 0.5～10 hour; Furnace cooling generates carbon doping or carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film to room temperature on the cooled titanium metal plate surface that contains in protective atmosphere then.
In technique scheme: the titanium content that contains titanium metal plate is 50～99.99wt%; Polishing is that the titanium metal plate that contains after will polishing is earlier successively used ethanol, acetone and distilled water ultrasonic cleaning, again at HF: H
2NO
3: H
2The volume ratio of O is (1～3): (2～5): carry out chemical rightenning in the solution of (4～7), clean the back with distilled water then and dry up with nitrogen; Protective atmosphere is He, Ne, Ar, N
2, H
2In a kind of, or be 2～3 kinds mixed gas wherein; Electrolytic solution is the fluoride ion of 0.05～5wt%, the H of 1～50wt%
2The mixed solution of the alcohol organic solvent of O, 45～98wt% and the nitrogenous organic solvent of 0～20wt%; Fluoride ion is KF, NaF, NH
4Among F, the HF more than one; Alcohol organic solvent is more than one in methyl alcohol, ethanol, ethylene glycol, the glycerol; Nitrogenous organic solvent is more than one in acetonitrile, pyrroles, methane amide, the dimethyl formamide.
Owing to adopt technique scheme, the present invention provides carbon source and nitrogenous source with the organic electrolyte that uniform distribution remains in the nanotube, utilize the inner big pressure of nanotube to reduce the doping temperature of reaction, realized at a lower temperature that carbon to titanium dioxide nano-pipe array thin film mixes or carbon-nitrogen co-doped.In preparation process, if the nitrogenous organic solvent in the electrolytic solution is 0 o'clock, obtain the adulterated titanium dioxide nano-pipe array thin film of carbon,, obtain carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film if when the nitrogenous organic solvent in the electrolytic solution is 0.05～20wt%.
The present invention compared with prior art has following positively effect:
1, titanium dioxide nano-pipe array thin film carbon-the nitrogen co-doped or carbon uniform doping of the present invention's preparation, from the mouth of pipe of nanotube to the bottom, the content distribution of various elements is even, helps improving the photocatalytic activity and the conductivity of titanium dioxide nano-pipe array thin film.And prior art is owing to be to introduce carbon source and nitrogenous source or carbon source from the outside, carbon and nitrogen element or carbon spread to the bottom through the mouth of pipe, so doped element skewness, in the doping of nanotube opening part doping, and cause the obstruction of titania nanotube easily apparently higher than the bottom.
2, the present invention is carbon source and nitrogenous source or carbon source with the organic electrolyte that remains in the titanium dioxide nano-pipe array thin film, obtain carbon-nitrogen adulterated titanium dioxide nano-pipe array thin film of carbon altogether 300～800 ℃ of insulations, or the adulterated titanium dioxide nano-pipe array thin film of carbon, avoided introducing the processing condition complexity that external carbon source and nitrogenous source or carbon source cause.
3, the present invention regulates carbon and the doping of nitrogen or the doping of carbon in the titanium dioxide nano-pipe array thin film by the carbon in the organic electrolyte and nitrogen or carbon content, therefore is convenient to the regulation and control of doping.
4, the present invention at a lower temperature, as can obtain carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film or adulterated titanium dioxide nano-pipe array thin film of carbon 300 ℃ of insulations, the active high characteristics of titanium dioxide nano-pipe array thin film internal-response have been made full use of, help on the occasion of some non-refractories or device, carrying out carbon-nitrogen co-doped or carbon and mix, and other method just can obtain carbon-nitrogen co-doped or adulterated titanium dioxide nano-pipe array thin film of carbon carrying out thermal chemical reaction more than 500 ℃ usually.
Therefore, the present invention need not external carbon source and nitrogenous source or carbon source, and temperature of reaction is low, and method is simple and reliable, and doped element content is controlled.Adulterated titanium dioxide nano-pipe array thin film of prepared carbon or carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film institute doping elements is evenly distributed.
Description of drawings
Fig. 1 is the stereoscan photograph of a kind of carbon doped titanium dioxide nanotube array film of the present invention's preparation;
Fig. 2 is that the x-ray photoelectron of carbon doped titanium dioxide nanotube array film shown in Figure 1 can spectrogram, and stripping speed is 21.1nm/ minute;
Fig. 3 is the stereoscan photograph of a kind of carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film of the present invention's preparation;
Fig. 4 is that the x-ray photoelectron of carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film shown in Figure 3 can spectrogram, and stripping speed is 21.1nm/ minute.
Embodiment
Further specify below by with embodiment the present invention being done in conjunction with the accompanying drawings.Following examples do not constitute limitation of the invention.
For avoiding repetition, the glossing unification that contains titanium metal plate that this embodiment is involved earlier is described below:; Polishing is that the titanium metal plate that contains after will polishing is earlier successively used ethanol, acetone and distilled water ultrasonic cleaning, again at HF: H
2NO
3: H
2The volume ratio of O is (1～3): (2～5): carry out chemical rightenning in the solution of (4～7), clean the back with distilled water then and dry up with nitrogen, repeat no more among the embodiment.
Embodiment 1
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.The titanium metal plate grinding and buffing that contains that earlier with titanium content is 50～70wt% is inserted in the electrolytic solution as anode, is anodic oxidation 0.5～2 hour under 20～40V condition at control voltage; Again the titanium metal plate that contains after the anodizing is taken out from electrolytic solution, place High Temperature Furnaces Heating Apparatus, under 400～600 ℃ of conditions, in protective atmosphere, be incubated 5～8 hours; Furnace cooling generates the adulterated titanium dioxide nano-pipe array thin film of carbon to room temperature on the cooled titanium metal plate surface that contains in protective atmosphere then.
The protective atmosphere of present embodiment is Ar.
In the present embodiment: electrolytic solution is the fluoride ion of 0.8～1.5wt%, the H of 1～15wt%
2The mixed solution of the alcohol organic solvent of O and 84～98wt%; Wherein: fluoride ion is HF, and alcohol organic solvent is an ethylene glycol.
Embodiment 2
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is N
2
In the electrolytic solution of present embodiment: fluoride ion is NH
4F, alcohol organic solvent is an ethanol.
All the other are with embodiment 1.
Embodiment 3
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is N
2And Ar.
In the electrolytic solution of present embodiment: fluoride ion is NH
4F and HF, alcohol organic solvent is ethanol and ethylene glycol.
All the other are with embodiment 1.
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is H
2And Ar.
In the electrolytic solution of present embodiment: fluoride ion is NH
4F, NaF and HF, alcohol organic solvent is ethanol, glycerol and ethylene glycol.
All the other are with embodiment 1.
Embodiment 5
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.The titanium metal plate grinding and buffing that contains that earlier with titanium content is 80～95wt% is inserted in the electrolytic solution as anode, is anodic oxidation 2～3.5 hours under 10～30V condition at control voltage; Again the titanium metal plate that contains after the anodizing is taken out from electrolytic solution, place High Temperature Furnaces Heating Apparatus, under 300～450 ℃ of conditions, in protective atmosphere, be incubated 3～6 hours; Furnace cooling generates carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film to room temperature on the cooled titanium metal plate surface that contains in protective atmosphere then.
Protective atmosphere in the present embodiment is He.
Electrolytic solution in the present embodiment is the fluoride ion of 0.1～0.8wt%, the H of 30～50wt%
2The mixed solution of the alcohol organic solvent of O, 45～65wt% and the nitrogenous organic solvent of 0.5～5wt%; Wherein: fluoride ion is NaF, and alcohol organic solvent is a methyl alcohol, and nitrogenous organic solvent is an acetonitrile.
Embodiment 6
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ne.
In the electrolytic solution of present embodiment: fluoride ion is KF, and alcohol organic solvent is a glycerol, and nitrogenous organic solvent is the pyrroles.
All the other are with embodiment 5.
Embodiment 7
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is H
2
In the electrolytic solution of present embodiment: fluoride ion is NaF and NH
4F, alcohol organic solvent is methyl alcohol and ethylene glycol, nitrogenous organic solvent is a methane amide.
All the other are with embodiment 5.
Embodiment 8
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ar and N
2
In the electrolytic solution of present embodiment: fluoride ion is KF and NH
4F, alcohol organic solvent is glycerol and ethylene glycol, nitrogenous organic solvent is a dimethyl formamide.
All the other are with embodiment 5.
Embodiment 9
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.The titanium metal plate grinding and buffing that contains that earlier with titanium content is 70～80wt% is inserted in the electrolytic solution as anode, is anodic oxidation 3～4.5 hours under 40～60V condition at control voltage; Again the titanium metal plate that contains after the anodizing is taken out from electrolytic solution, place High Temperature Furnaces Heating Apparatus, under 500～700 ℃ of conditions, in protective atmosphere, be incubated 0.5～3 hour; Furnace cooling generates carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film to room temperature on the cooled titanium metal plate surface that contains in protective atmosphere then.
Protective atmosphere in the present embodiment is Ar and H
2
Electrolytic solution in the present embodiment is the fluoride ion of 0.05～0.1wt%, the H of 2～20wt%
2The mixed solution of the alcohol organic solvent of O, 70～90wt% and the nitrogenous organic solvent of 5～20wt%; Wherein: fluoride ion is KF and NaF, and alcohol organic solvent is methyl alcohol and glycerol, and nitrogenous organic solvent is acetonitrile and pyrroles.
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is He and Ar.
In the electrolytic solution of present embodiment: fluoride ion is NaF, NH
4F and HF, alcohol organic solvent is ethanol and ethylene glycol, nitrogenous organic solvent is methane amide and dimethyl formamide.
All the other are with embodiment 9.
Embodiment 11
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ar, N
2And H
2
In the electrolytic solution of present embodiment: fluoride ion is KF, NaF and HF, and alcohol organic solvent is ethanol, methyl alcohol and ethylene glycol, and nitrogenous organic solvent is acetonitrile, pyrroles and dimethyl formamide.
All the other are with embodiment 9.
Embodiment 12
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ar, N
2And Ne.
In the electrolytic solution of present embodiment: fluoride ion is KF, NaF and NH
4F, alcohol organic solvent is ethanol, glycerol and ethylene glycol, nitrogenous organic solvent is acetonitrile, methane amide and dimethyl formamide.
All the other are with embodiment 9.
Embodiment 13
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.The titanium metal plate grinding and buffing that contains that earlier with titanium content is 90～99.99wt% is inserted in the electrolytic solution as anode, is anodic oxidation 4～5 hours under 30～50V condition at control voltage; Again the titanium metal plate that contains after the anodizing is taken out from electrolytic solution, place High Temperature Furnaces Heating Apparatus, under 600～800 ℃ of conditions, in protective atmosphere, be incubated 7～10 hours; Furnace cooling generates carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film to room temperature on the cooled titanium metal plate surface that contains in protective atmosphere then.
Protective atmosphere in the present embodiment is He, Ar and N
2
Electrolytic solution in the present embodiment is the fluoride ion of 1.5～5wt%, the H of 11～35wt%
2The mixed solution of the alcohol organic solvent of O, 60～84wt% and the nitrogenous organic solvent of 0.05～0.5wt%; Wherein: fluoride ion is NH
4F and HF, alcohol organic solvent is ethanol, ethylene glycol and glycerol, nitrogenous organic solvent is acetonitrile and pyrroles.
Embodiment 14
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ar and N
2
In the electrolytic solution of present embodiment: fluoride ion is NaF and HF, and alcohol organic solvent is ethanol and glycerol, and nitrogenous organic solvent is acetonitrile and methane amide.
All the other are with embodiment 13.
Embodiment 15
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ar and H
2
In the electrolytic solution of present embodiment: fluoride ion is KF and HF, and alcohol organic solvent is ethanol and methyl alcohol, and nitrogenous organic solvent is acetonitrile, pyrroles and methane amide.
All the other are with embodiment 13.
Embodiment 16
A kind of titanium dioxide nano-pipe array thin film and preparation method thereof.
The protective atmosphere of present embodiment is Ar, He and Ne.
In the electrolytic solution of present embodiment: fluoride ion is KF, NaF, NH
4F and HF, alcohol organic solvent is methyl alcohol, ethanol, ethylene glycol and glycerol, nitrogenous organic solvent is acetonitrile, pyrroles, methane amide and dimethyl formamide.
All the other are with embodiment 13.
This embodiment provides carbon source and nitrogenous source or carbon source with the organic electrolyte that uniform distribution remains in the nanotube, utilize the inner big pressure of nanotube to reduce the doping temperature of reaction, realized at a lower temperature that carbon to titania nanotube mixes or carbon-nitrogen co-doped.In preparation process, if the nitrogenous organic solvent in the electrolytic solution is 0 o'clock, obtain carbon doped titanium dioxide nanotube array film,, obtain carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film if when the nitrogenous organic solvent in the electrolytic solution is 0.05～20wt%.
This embodiment compared with prior art has following positively effect:
1, Fig. 1 is the stereoscan photograph of the prepared adulterated titanium dioxide nano-pipe array thin film of carbon of a kind of preparation method among the embodiment 1; Fig. 2 is that the x-ray photoelectron of the prepared adulterated titanium dioxide nano-pipe array thin film of carbon of the same a kind of preparation method among the embodiment 1 can spectrum analysis figure.As can be seen from Figure 1, the diameter of nanotube is evenly distributed; As can be seen from Figure 2, to the bottom, the content distribution of various elements is even from the mouth of pipe of nanotube for adulterated carbon.Fig. 3 is the prepared carbon of a kind of preparation method among the embodiment 5-nitrogen co-doped titanium dioxide nano-pipe array thin film; Fig. 4 is that the x-ray photoelectron of the titanium dioxide nano-pipe array thin film of the prepared carbon of the same a kind of preparation method among the embodiment 5-nitrogen co-doped can spectrum analysis figure.As can be seen from Figure 3, the diameter of nanotube is evenly distributed; As can be seen from Figure 4, adulterated carbon and nitrogen element from the mouth of pipe of nanotube to the bottom.
From Fig. 1～Fig. 4 as can be seen, the titanium dioxide nano-pipe array thin film carbon of this embodiment preparation mix or carbon-nitrogen co-doped evenly.Help improving the photocatalytic activity and the conductivity of titanium dioxide nano-pipe array thin film.And prior art is owing to be to introduce carbon source and nitrogenous source or carbon source from the outside, carbon and nitrogen element or carbon spread to the bottom through the mouth of pipe, so doped element skewness, in the doping of nanotube opening part doping, and cause the obstruction of titania nanotube easily apparently higher than the bottom.
2, this embodiment is carbon source and nitrogenous source or carbon source with the organic electrolyte that remains in the titanium dioxide nano-pipe array thin film, obtain carbon-nitrogen adulterated titanium dioxide nano-pipe array thin film of carbon altogether 300～800 ℃ of insulations, or the adulterated titanium dioxide nano-pipe array thin film of carbon, avoided introducing the processing condition complexity that external carbon source and nitrogenous source or carbon source cause.
3, this embodiment is regulated carbon and the doping of nitrogen or the doping of carbon in the titanium dioxide nano-pipe array thin film by the carbon in the organic electrolyte and nitrogen or carbon content, therefore is convenient to the regulation and control of doping.
4, this embodiment at a lower temperature, as can obtain carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film or adulterated titanium dioxide nano-pipe array thin film of carbon 300 ℃ of insulations, the active high characteristics of titanium dioxide nano-pipe array thin film internal-response have been made full use of, help on the occasion of some non-refractories or device, carrying out carbon-nitrogen co-doped or carbon and mix, and other method just can obtain carbon-nitrogen co-doped or adulterated titanium dioxide nano-pipe array thin film of carbon carrying out thermal chemical reaction more than 500 ℃ usually.
Therefore, this embodiment need not external carbon source and nitrogenous source or carbon source, and temperature of reaction is low, and method is simple and reliable, and doped element content is controlled.Adulterated titanium dioxide nano-pipe array thin film of prepared carbon or carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film institute doping elements is evenly distributed.
Claims (8)
1. the preparation method of a titanium dioxide nano-pipe array thin film is characterized in that will contain the titanium metal plate grinding and buffing earlier inserts in the electrolytic solution as anode, is anodic oxidation 0.5～5 hour under 10～60V condition at control voltage; Again the titanium metal plate that contains after the anodizing is taken out from electrolytic solution, place High Temperature Furnaces Heating Apparatus, under 300～800 ℃ of conditions, in protective atmosphere, be incubated 0.5～10 hour; Furnace cooling generates carbon doping or carbon-nitrogen co-doped titanium dioxide nano-pipe array thin film to room temperature on the cooled titanium metal plate surface that contains in protective atmosphere then.
2. the preparation method of titanium dioxide nano-pipe array thin film according to claim 1 is characterized in that the described titanium content that contains titanium metal plate is 50～99.99wt%.
3. the preparation method of titanium dioxide nano-pipe array thin film according to claim 1 is characterized in that described polishing is that the titanium metal plate that contains after will polishing is earlier successively used ethanol, acetone and distilled water ultrasonic cleaning, again at HF: H
2N0
3: H
2The volume ratio of O is (1～3): (2～5): carry out chemical rightenning in the solution of (4～7), clean the back with distilled water then and dry up with nitrogen.
3, the preparation method of titanium dioxide nano-pipe array thin film according to claim 1 is characterized in that described protective atmosphere is He, Ne, Ar, N
2, H
2In a kind of, or be 2～3 kinds mixed gas wherein.
4. the preparation method of titanium dioxide nano-pipe array thin film according to claim 1 is characterized in that described electrolytic solution is the fluoride ion of 0.05～5wt%, the H of 1～50wt%
2The mixed solution of the alcohol organic solvent of O, 45～98wt% and the nitrogenous organic solvent of 0～20wt%.
5. the preparation method of titanium dioxide nano-pipe array thin film according to claim 4, its feature is KF, NaF, NH at described fluoride ion
4Among F, the HF more than one.
6. the preparation method of titanium dioxide nano-pipe array thin film according to claim 4 is characterized in that described alcohol organic solvent is more than one in methyl alcohol, ethanol, ethylene glycol, the glycerol.
7. the preparation method of titanium dioxide nano-pipe array thin film according to claim 4 is characterized in that described nitrogenous organic solvent is more than one in acetonitrile, pyrroles, methane amide, the dimethyl formamide.
8. according to the prepared titanium dioxide nano-pipe array thin film of preparation method of each described titanium dioxide nano-pipe array thin film in the claim 1～4.
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| CN106757115A (en) * | 2016-11-14 | 2017-05-31 | 中北大学 | The electrochemistry of continuous poriferous titanium dioxide powder is prepared and doping method |
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| CN108043378A (en) * | 2017-10-09 | 2018-05-18 | 华南理工大学 | A kind of nonmetal doping porous wall titanium nano-tube array visible light catalyst and preparation method and application |
| CN108043378B (en) * | 2017-10-09 | 2020-12-22 | 华南理工大学 | Nonmetal-doped porous-wall titanium nanotube array visible-light-driven photocatalyst and preparation method and application thereof |
| CN111254475A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for growing titanium dioxide nanotube on titanium substrate |
| CN109825867A (en) * | 2019-04-10 | 2019-05-31 | 东北大学 | A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array |
| CN110644034A (en) * | 2019-10-08 | 2020-01-03 | 东莞理工学院 | Preparation method of net type titanium dioxide nanotube array |
| CN113189158A (en) * | 2021-04-25 | 2021-07-30 | 武汉科技大学 | Hydrogen sulfide photoelectrochemical sensor and preparation method thereof |
| CN114457367A (en) * | 2022-03-01 | 2022-05-10 | 厦门稀土材料研究所 | Preparation method and application of vacuum carbon-doped titanium dioxide nanotube array structure |
| CN114457367B (en) * | 2022-03-01 | 2023-11-07 | 厦门稀土材料研究所 | Preparation method and application of vacuum carbon-doped titanium dioxide nanotube array structure |
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