CN103614759A - Preparation method and application of N-doped titanium dioxide nano-composite structure - Google Patents
Preparation method and application of N-doped titanium dioxide nano-composite structure Download PDFInfo
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Abstract
The invention provides a preparation method and application of an N-doped titanium dioxide nano-composite structure. The preparation method comprises the following steps: cleaning a titanium sheet with acetone, absolute ethyl alcohol and deionized water sequentially; mixing hydrofluoric acid and concentrated hydrochloric acid to obtain a mixed solution; carrying out chemical polishing on the titanium sheet; enabling a titanium dioxide nanotube array film to grow on the surface of the titanium sheet subjected to chemical polishing at the room temperature by using a constant-pressure direct-current anode oxidation method, thereby obtaining amorphous state ordered titanium dioxide nanotube arrays; preparing aqueous ammonia; immersing the amorphous ordered titanium dioxide nanotube arrays into aqueous ammonia, heating, and naturally cooling to prepare the N-doped titanium dioxide nano-composite structure. The composite structure is used as a photocatalyst. As nitrogen in the aqueous ammonia is doped into the amorphous ordered titanium dioxide nanotube arrays, the preparation method has the characteristics of large specific surface area, high photocatalytic efficiency, good stability, high repeatability and the like. By adopting the preparation method, a visible light photocatalyst with low cost can be prepared, and the visible light photocatalyst has better application prospect in the aspect of degrading pollutants.
Description
Technical field
The invention belongs to photocatalyst material technical field, the preparation method who relates to a kind of nitrogen-doped titanium dioxide nano material, be particularly related to a kind of preparation method of nitrogen-doped titanium dioxide nano composite structure, i.e. nitrogen doping bigger serface titania nanometer worm/nanotube composite structure light method for preparing catalyst.
Background technology
In recent years, the advantages such as semiconductor nano titanium dioxide is high with its catalytic performance, oxidation capacity strong, good stability, non-toxic inexpensive, enjoy favor in photocatalysis field.Yet titanium dioxide nano material has wider energy gap (3.0～3.2eV), can only in near-ultraviolet light district, there is light-catalyzed reaction, solar energy utilization ratio is lower.Therefore people attempt spectral response range compound or that other material that adulterates expands titanium dioxide nano material to improve its photocatalysis efficiency.Research shows, the photoresponse scope that nitrogen doping can be widened titanium dioxide nano material, to visible region, has improved the utilising efficiency of visible ray greatly.But the material of nitrogen doping is at present mainly nano TiO 2 powder and titanium dioxide nano-film, although nano-powder has very large specific surface area, is difficult to recycling; Nano thin-film is coated in and in substrate, is easy to reclaim, and has but reduced the contact area with reactant, and photocatalysis efficiency is not high.Comparatively speaking, titania nanotube ratio nano film has larger specific surface area, thereby and can be fixed in substrate, to reclaim repeatedly and utilize, therefore may there is very large advantage in photocatalysis field.
Summary of the invention
The object of the present invention is to provide a kind of simple, efficient, stable method of preparing nitrogen-doped titanium dioxide nano composite structure, saved conventional high-temperature annealing crystallization process.
Another object of the present invention is to provide a kind of application of the nano composite structure making with aforesaid method.
For achieving the above object, the technical solution used in the present invention is: a kind of nitrogen-doped titanium dioxide nano composite structure preparation method, it is characterized in that, and this preparation method specifically carries out according to the following steps:
Step 1: titanium sheet is cleaned successively in acetone, dehydrated alcohol and deionized water;
Be 1 ︰ 4～8 by volume, get respectively the dense hydrofluoric acid of concentration >=40% and the concentrated hydrochloric acid that concentration is 36%, be made into mixing solutions;
Step 2: with the titanium sheet after the mixed chemical solution polished and cleaned in step 1;
Step 3: adopt constant voltage DC anodizing method, the titanium plate surface growth film of Nano tube array of titanium dioxide under room temperature after chemical rightenning: graphite is negative electrode, and titanium sheet is anode, and the distance of two interpolars is 3～5cm; Electrolytic solution is for containing 0.20～0.50wt.% Neutral ammonium fluoride and the hydrofluoric ethylene glycol solution of 0.01～0.05wt.%, oxidation voltage 40～60V, oxidization time 5～600min, and use magnetic stirrer electrolytic solution, after being oxidized, with deionized water, clean titanium sheet, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state;
1 ︰ 1～10 by volume, gets respectively concentration and is 25% ammoniacal liquor and deionized water, is made into ammonia soln;
Step 4: the orderly Nano tube array of titanium dioxide of amorphous state is immersed in ammonia soln, and the temperature environment that is placed in 80～100 ℃ heats 3～15 hours, naturally cooling, deionized water rinsing, nitrogen dries up, and makes nitrogen-doped titanium dioxide nano composite structure.
Another technical solution used in the present invention is: the application of the nitrogen-doped titanium dioxide nano composite structure that the above-mentioned preparation method of a kind of use makes, this nitrogen-doped titanium dioxide nano composite structure photocatalyst.
Preparation method of the present invention is immersed in the amorphous state Nano tube array of titanium dioxide making in ammonia soln, heat at a certain temperature 3～15 hours, nitrogen element in ammonia soln is mixed into amorphous state Nano tube array of titanium dioxide, form the nano titania worm/nano-tube array of nitrogen doping, it is large that this array has specific surface area, photocatalysis efficiency is high, and good stability and repeatable high, show excellent photocatalysis performance.Because this array grows in fixing titanium substrate, be convenient to direct recycling, this preparation method can be used for suitability for industrialized production simultaneously, can make cheap visible-light photocatalyst, has good application prospect aspect degradation of contaminant.
Accompanying drawing explanation
Fig. 1 is the SEM surface topography map of the nitrogen-doped titanium dioxide nano composite structure that makes of embodiment 1.
Fig. 2 makes the orderly Nano tube array of titanium dioxide of amorphous state by embodiment 1 to put into the XRD spectra after different concns ammonia soln soaks.
Fig. 3 is the XPS spectrum figure after the orderly Nano tube array of titanium dioxide of amorphous state that embodiment 1 is made soaks in water.
Fig. 4 is the orderly Nano tube array of titanium dioxide of amorphous state that in the present invention, embodiment 1 the makes XPS spectrum figure after ammoniacal liquor soaks.
Fig. 5 is the narrow spectrum XPS peak position that in the present invention, ammoniacal liquor soaks the N peak position of titanium dioxide appearance.
Fig. 6 is the ultraviolet-visible absorbance spectrogram that makes sample in embodiment 1, embodiment 2, embodiment 3 and comparative example.
Fig. 7 is the energy gap graphic representation calculating corresponding to Fig. 6.
Fig. 8 is that nitrogen-doped titanium dioxide nanometer worm/nanotube composite structure electric current of preparing in the present invention is schemed with the relation curve (I-V curve) of voltage change.
Fig. 9 is that nitrogen-doped titanium dioxide nanometer worm/nanotube composite structure of preparation in embodiment 1, embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2 declines and separates the graphic representation of methyl orange solution and nitrogen-doped titanium dioxide nanometer worm/nanotube composite structure of embodiment 1 preparation is carried out after anneal again at radiation of visible light, at radiation of visible light, declines and separates the graphic representation of methyl orange solution.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
In recent years, people attempt spectral response range compound or that other material that adulterates expands titanium dioxide nano material to improve its photocatalysis efficiency.Research shows, the photoresponse scope that nitrogen doping can be widened titanium dioxide nano material, to visible region, improves the utilising efficiency of visible ray greatly.But the material of nitrogen doping is mainly nano TiO 2 powder and titanium dioxide nano-film.Although nano TiO 2 powder has very large specific surface area, is difficult to recycling; Titanium dioxide nano-film is coated in and in substrate, is easy to reclaim, and has but reduced the contact area with reactant, and photocatalysis efficiency is not high.Comparatively speaking, titania nanotube ratio nano film has larger specific surface area, thereby and can be fixed in substrate, to reclaim repeatedly and utilize, therefore, in photocatalysis field, there is very large advantage.
Traditional doping process, will adopt high temperature annealing mode mostly, needs to consume compared with multiple-energy-source.There is report
[1] [2]title soaks anodised amorphous state Nano tube array of titanium dioxide in water can be made it crystallization and become Anatase, and the method is simple to operate, can save conventional high-temperature annealing crystallization process, reduces energy loss.But adopt the method can only make amorphous state Nano tube array of titanium dioxide crystallization, the anatase titania of broadband system still can not absorb visible ray.
For this reason, we have proposed anodised amorphous state Nano tube array of titanium dioxide to be immersed in ammonia soln, both can provide above-mentioned water surrounding to make the crystallization of amorphous state titania nanotube, and nitrogenous source is provided simultaneously, when structural remodeling, mix into nitrogen element.When anodised amorphous state Nano tube array of titanium dioxide is immersed in ammonia soln, unsettled TiO in amorphous state Nano tube array of titanium dioxide
6 2-octahedra by surface hydroxyl adsorbed water molecule, form the Ti (OH) of indissoluble
6 2-, Ti in ammonia environment (OH)
6 2-the Ti (OH) that can form with another the same manner
6 2-with a suitable angle, share octahedral one side, deviate from a water molecules simultaneously, thereafter, other octahedra Ti (OH)
6 2-can select suitable angle to share octahedral the other side with same dewatering type, in this process, there is a large amount of nitrogen in due to ammonia soln, nitrogen-atoms is due to Ti (OH)
6 2-the many dangling bonds in surface can be easy to be brought into the crystalline substance bag of this restructuring.So just form the crystalline substance bag of a nitrogen-doped titanium dioxide.Numerous brilliant bags share crystal face and finally form Anatase nitrogen-doped titanium dioxide.Not needing the high temperature anneal, is a kind of method of less energy-consumption, simple, efficient nitrogen-doped titanium dioxide nanotube array.
This research not only has scientific value, and has practical value, has considerable application prospect aspect catalyzing and degrading pollutant by visible light.
Preparation method of the present invention specifically carries out according to the following steps:
Step 1: industrial titanium sheet is respectively cleaned to 10～15min successively in acetone, dehydrated alcohol and deionized water;
Be 1 ︰ 4～8 by volume, get respectively the concentrated hydrochloric acid that the dense hydrofluoric acid of concentration >=40% and concentration are 36%, be made into mixing solutions;
Step 2: the titanium sheet 100～180s with after the mixed chemical solution polished and cleaned in step 1, then with deionized water, to rinse well, nitrogen dries up;
Step 3: adopt constant voltage DC anodizing method, the titanium plate surface growth film of Nano tube array of titanium dioxide under room temperature after chemical rightenning: graphite is negative electrode, and titanium sheet is anode, and the distance of two interpolars is 3～5cm; Electrolytic solution is for containing 0.20～0.50wt.% Neutral ammonium fluoride (NH
4the ethylene glycol solution of F) and 0.01～0.05wt.% hydrogen fluoride (HF), oxidation voltage 40～60V, oxidization time 5～600min, and use magnetic stirrer electrolytic solution, after being oxidized, with deionized water, clean titanium sheet, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state;
1 ︰ 1～10 by volume, gets respectively concentration and is 25% ammoniacal liquor and deionized water, is made into ammonia soln;
Step 4: the orderly Nano tube array of titanium dioxide of amorphous state is immersed in the autoclave that fills ammonia soln, the temperature environment that this autoclave is placed in to 80～100 ℃ heats 3～15 hours, after naturally cooling, with deionized water lavage specimens product, nitrogen dries up, and makes Anatase nitrogen-doped titanium dioxide nanometer worm/nanotube composite structure.
By nitrogen-doped titanium dioxide nanometer worm/nano tube structure photocatalyst of preparation, be placed in the methyl orange solution that 5mL concentration is 0.5mmol/L, ice-water bath keeps 0 ℃, in the dark standing 30min, reach after adsorption equilibrium, move under simulated solar radiant and irradiate 0～150min.
Nitrogen-doped titanium dioxide nanometer worm/nano tube structure prepared by the inventive method has that specific surface area is large, photocatalysis efficiency is high, good stability, lower-price characteristic, shows excellent photocatalysis performance.And preparation method is simple, be beneficial to industrialized mass production, have great practical value.
Reference
[1] under normal temperature, in water, process spontaneous topographical transition and the phase transformation that anodised titania nanotube causes, kingly way love etc., < < nanometer wall bulletin > > 2011, o. 11th, the 3649th page.
[2] a kind of method of simple low temperature crystallized anodic oxidation amorphous state titania nanotube, Liao Yulong etc., < < ACS application material and interface > >, 2011, the 3rd phase, the 2800th page.
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15min in acetone, dehydrated alcohol and deionized water; 1 ︰ 8 gets respectively the concentrated hydrochloric acid that the dense hydrofluoric acid of concentration >=40% and concentration are 36% by volume, is made into mixing solutions, with the titanium sheet 180s after this mixed chemical solution polished and cleaned; Adopt constant voltage DC anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under room temperature after polishing: graphite is negative electrode, titanium sheet is anode, the distance 3cm of two interpolars, electrolytic solution is the ethylene glycol solution (analytical pure) containing 0.30wt.% Neutral ammonium fluoride and 0.03wt.% hydrofluoric acid, oxidation voltage 40V, oxidization time is 5min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, be oxidized rear taking-up titanium sheet, deionized water rinsing, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state; 1 ︰ 1 by volume, gets respectively concentration and is 25% ammoniacal liquor and deionized water, is made into ammonia soln; The orderly Nano tube array of titanium dioxide of this amorphous state is immersed in the autoclave that fills this ammonia soln, autoclave is heated 9 hours at the temperature of 90 ℃, after naturally cooling, take out sample, with deionized water, rinse well, nitrogen dries up, and obtains nitrogen-doped titanium dioxide nano composite structure.
The SEM surface topography map of the nitrogen-doped titanium dioxide nano composite structure that embodiment 1 makes, as shown in Figure 1, the interior illustration in Fig. 1 is corresponding section SEM figure, the long 200nm of scale.Titania nanotube surface and tube wall all grow the vermiform titanium dioxide of the about 50nm of length as seen from Figure 1.Illustrate that this composite structure can improve the specific surface area of titanium dioxide greatly, is conducive to the raising of photocatalysis efficiency.
Nano titania worm/nanotube composite structure that embodiment 1 is made carries out XRD test, its result as shown in Figure 2, untreated anodised titania nanotube is amorphous state, after ammonia soln immersion treatment, make it change Anatase into, this is effective to improving photo-catalysis capability.
comparative example 1
By the method for embodiment 1, obtain the orderly Nano tube array of titanium dioxide of amorphous state; The orderly Nano tube array of titanium dioxide of this amorphous state is immersed in deionized water, makes unadulterated nano titania worm/nanotube composite structure.
Fig. 3 to Fig. 5 is that the XPS of nano titania worm/nanotube composite structure of making characterizes.Fig. 3 is the XPS spectrum figure of nano titania worm/nanotube composite structure of making of comparative example 1, as can be seen from Figure 3, has only occurred the characteristic peak of Ti and O in XPS spectrum.Fig. 4 has shown with ammonia soln (1 ︰ 1 by volume, the ammoniacal liquor and the deionized water that by concentration, are 25% are made into) XPS spectrum of nano titania worm/nanotube composite structure of making of immersion treatment embodiment 1, by Fig. 4, found out, after ammonia soln immersion treatment, in XPS spectrum, go out except the characteristic peak of Ti and O, also occurred the characteristic peak of N.In Fig. 5, the narrow spectrum scanning of the XPS of N peak position can be found out again, and N peak position, in 399.7eV, is the doping of interval type nitrogen, illustrates and adopts preparation method of the present invention successfully to make nitrogen-doped titanium dioxide nanometer worm/nanotube composite structure.
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 10min in acetone, dehydrated alcohol and deionized water; 1 ︰ 4 gets respectively the dense hydrofluoric acid of concentration >=40% and the concentrated hydrochloric acid of concentration 36% by volume, is made into mixing solutions, with the titanium sheet 120s after this mixed chemical solution polished and cleaned; Adopt constant voltage DC anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under room temperature after polishing: graphite is negative electrode, titanium sheet is anode, the distance 4cm of two interpolars, electrolytic solution is the ethylene glycol solution (analytical pure) containing 0.50wt.% Neutral ammonium fluoride and 0.05wt.% hydrofluoric acid, oxidation voltage 60V, oxidization time 180min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, be oxidized rear taking-up titanium sheet, with deionized water rinsing, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state; To get respectively concentration be 25% ammoniacal liquor and deionized water to 1 ︰ 5 by volume, is made into ammonia soln; The orderly Nano tube array of titanium dioxide of this amorphous state is immersed in this ammonia soln, is placed at 100 ℃ of temperature and heats 3 hours, after naturally cooling, take out sample, with deionized water, rinse well, nitrogen dries up, and obtains nitrogen-doped titanium dioxide nano composite structure.
embodiment 3
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 12.5min in acetone, dehydrated alcohol and deionized water; 1 ︰ 6, gets respectively the dense hydrofluoric acid of concentration >=40% and the concentrated hydrochloric acid of concentration 36% by volume, is made into mixing solutions, with the titanium sheet 150s after this mixed chemical solution polished and cleaned; Adopt the titanium plate surface growth film of Nano tube array of titanium dioxide after polishing under constant voltage DC anodizing method room temperature: graphite is negative electrode, titanium sheet is anode, the distance 3.5cm of two interpolars, electrolytic solution is the ethylene glycol solution (analytical pure) containing 0.40wt.% Neutral ammonium fluoride and 0.04wt.% hydrofluoric acid, oxidation voltage 50V, oxidization time 400min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, be oxidized rear taking-up titanium sheet, with deionized water rinsing, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state; To get respectively concentration be 25% ammoniacal liquor and deionized water to 1 ︰ 10 by volume, is made into ammonia soln; The orderly Nano tube array of titanium dioxide of this amorphous state is immersed in the autoclave that fills this ammonia soln, autoclave is heated 15 hours at the temperature of 80 ℃, after naturally cooling, take out sample, with deionized water, rinse well, nitrogen dries up, and obtains nitrogen-doped titanium dioxide nanometer worm/nano pipe light catalyst.
The sample making in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 is carried out respectively to the test of ultraviolet-visible absorbance, obtain the graphic representation shown in Fig. 6.As seen from Figure 6, along with soaking the increase gradually of the ammonia concn of the orderly Nano tube array of titanium dioxide of amorphous state, the light absorpting ability of the nitrogen-doped titanium dioxide nano composite structure making strengthens gradually, there is red shift and be extended to visible region in ABSORPTION EDGE simultaneously, this is to improving the utilization ratio of the visible ray of sample, and it is favourable realizing visible light catalytic.
The energy gap graphic representation calculating corresponding to Fig. 6, as Fig. 7, (X-coordinate of Fig. 7 represents photon energy, and unit is eV; The ordinate zou of Fig. 7 be uptake factor and photon energy product square, unit is (eV/cm)
2).As can be seen from Figure 7, along with for soaking the increase of the ammonia soln concentration of the orderly Nano tube array of titanium dioxide of amorphous state, samples band-gap narrows down gradually.Like this, the visible ray that energy is less also can form electron-hole pair by the electron excitation of titanium dioxide valence band to conduction band, and electronics has strong reducing power, and hole meeting and water or oxygen reaction form hydroxyl.Hydroxyl has strong oxidation capacity, thereby the stronger radical oxidation reduction of the activity that pollutent is generated is degraded.
The nitrogen-doped titanium dioxide nano composite structure making in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 is carried out to I – V test; The orderly Nano tube array of titanium dioxide of amorphous state is carried out to I – V test, also the orderly Nano tube array of titanium dioxide of amorphous state after processing by existing annealing process is carried out to I – V test simultaneously, obtain graphic representation as shown in Figure 8, Fig. 8 demonstration, the specific conductivity of unannealed amorphous state titania nanotube is lower, when passing through embodiment 1,2, after 3 processing, specific conductivity obviously strengthens, and along with the increase of ammonia soln concentration, the specific conductivity of sample increases gradually.Although adopt the specific conductivity of the titania nanotube of the direct annealing of traditional method to increase to some extent than unannealed sample, but be less than the specific conductivity of the sample of preparing in the present invention.Specific conductivity increase is conducive to light induced electron transmission, thereby is favourable to improving photocatalysis efficiency.
embodiment 4
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 10min in acetone, dehydrated alcohol and deionized water, be 1 ︰ 5 by volume, get respectively the dense hydrofluoric acid of concentration >=40% and the concentrated hydrochloric acid of concentration 36%, be made into mixing solutions, with the titanium sheet 100s after this mixed chemical solution polished and cleaned, adopt the titanium plate surface growth film of Nano tube array of titanium dioxide after polishing under constant voltage DC anodizing method room temperature: graphite is negative electrode, titanium sheet is anode, the distance of two interpolars remains on 4.5cm, electrolytic solution is the ethylene glycol solution (analytical pure) containing 0.20wt.% Neutral ammonium fluoride and 0.01wt.% hydrofluoric acid, oxidation voltage 45V, oxidization time 600min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, be oxidized rear taking-up titanium sheet, with deionized water rinsing, nitrogen dries up, obtain the orderly Nano tube array of titanium dioxide of amorphous state, to get respectively concentration be 25% ammoniacal liquor and deionized water to 1 ︰ 2 by volume, is made into ammonia soln, the orderly Nano tube array of titanium dioxide of this amorphous state is immersed in the autoclave that fills ammonia soln, this autoclave is placed at the temperature of 85 ℃ and heats 12 hours, after naturally cooling, take out sample, with deionized water, rinse well, nitrogen dries up, and obtains nitrogen-doped titanium dioxide nanometer worm/nano pipe light catalyst.
Comparative example 2
By the method for embodiment 3, obtain the orderly Nano tube array of titanium dioxide of amorphous state; Adopt existing annealing process to anneal to the orderly Nano tube array of titanium dioxide of this amorphous state, make crystallizing titanium dioxide nano pipe.
Comparative example 3
By the method for embodiment 1, make nitrogen-doped titanium dioxide nano composite structure, then adopt existing annealing process to carry out anneal to this nitrogen-doped titanium dioxide nano composite structure.
By the sample obtaining in embodiment 1, embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2 and comparative example 3 Photodegradation of Methyl Orange solution under radiation of visible light, obtain graphic representation as shown in Figure 9.Fig. 9 ordinate zou is the ratio of concentration with the initial tropeolin-D concentration of remaining tropeolin-D after illumination, and ordinate zou, more close to 1, illustrates that the tropeolin-D of degraded is fewer, and effect is poorer.As seen from the figure, the degradation effect of each embodiment is obviously better than comparative example 1.In order to contrast, the sample that embodiment 1 is made is again in 3 hours (comparative example 3) of 500 ℃ of annealing, then under equal conditions test its photocatalysis performance, its photo-catalysis capability is almost suitable with embodiment 1 effect, this just explanation again, through ammoniacal liquor immersion treatment, titania nanotube is well-crystallized, without anneal again.
From application prospect aspect, nitrogen-doped titanium dioxide nanometer worm/nano-tube array of the present invention is except can be used for photocatalyst, because it has characteristic of semiconductor, high specific conductivity and the large characteristics such as specific surface area, also can be used for solar cell, super capacitor, the devices such as field emmision material.Take nitrogen-doped titanium dioxide nanometer worm/film of Nano tube array as basis, be expected to realize the compound of these functional devices, thereby realize the integrated of multifunction device.
Therefore, nitrogen-doped titanium dioxide nanometer worm/film of Nano tube array has more excellent performance and more wide application prospect.
Claims (4)
1. a nitrogen-doped titanium dioxide nano composite structure preparation method, is characterized in that, this preparation method specifically carries out according to the following steps:
Step 1: titanium sheet is cleaned successively in acetone, dehydrated alcohol and deionized water;
Be 1 ︰ 4～8 by volume, get respectively the dense hydrofluoric acid of concentration >=40% and the concentrated hydrochloric acid that concentration is 36%, be made into mixing solutions;
Step 2: with the titanium sheet after the mixed chemical solution polished and cleaned in step 1;
Step 3: adopt constant voltage DC anodizing method, the titanium plate surface growth film of Nano tube array of titanium dioxide under room temperature after chemical rightenning: graphite is negative electrode, and titanium sheet is anode, and the distance of two interpolars is 3～5cm; Electrolytic solution is for containing 0.20～0.50wt.% Neutral ammonium fluoride and the hydrofluoric ethylene glycol solution of 0.01～0.05wt.%, oxidation voltage 40～60V, oxidization time 5～600min, and use magnetic stirrer electrolytic solution, after being oxidized, with deionized water, clean titanium sheet, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state;
1 ︰ 1～10 by volume, gets respectively concentration and is 25% ammoniacal liquor and deionized water, is made into ammonia soln;
Step 4: the orderly Nano tube array of titanium dioxide of amorphous state is immersed in ammonia soln, and the temperature environment that is placed in 80～100 ℃ heats 3～15 hours, naturally cooling, deionized water rinsing, nitrogen dries up, and makes nitrogen-doped titanium dioxide nano composite structure.
2. nitrogen-doped titanium dioxide nano composite structure preparation method according to claim 1, is characterized in that, in described step 1, titanium sheet is respectively cleaned in acetone, dehydrated alcohol and deionized water to 10～15min.
3. nitrogen-doped titanium dioxide nano composite structure preparation method according to claim 1, is characterized in that, in described step 2, and chemical rightenning titanium sheet 100～180s, deionized water is cleaned, and nitrogen dries up.
4. an application for the nitrogen-doped titanium dioxide nano composite structure making by preparation method described in claim 1, is characterized in that, this nitrogen-doped titanium dioxide nano composite structure photocatalyst.
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