CN103614759B - Nitrogen-doped titanium dioxide nano composite structure preparation method and application - Google Patents
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Abstract
The invention provides a kind of nitrogen-doped titanium dioxide nano composite structure preparation method and application, acetone, dehydrated alcohol and deionized water clean titanium sheet successively；It is made into mixed solution with dense Fluohydric acid. and concentrated hydrochloric acid；Chemical polishing titanium sheet；Using constant voltage DC anodizing, under room temperature, the titanium plate surface after chemical polishing grows film of Nano tube array of titanium dioxide, obtains the orderly Nano tube array of titanium dioxide of amorphous state；Preparation ammonia spirit；Orderly for amorphous state Nano tube array of titanium dioxide is immersed in ammonia spirit, heating, natural cooling, prepares nitrogen-doped titanium dioxide nano composite structure.This composite construction photocatalyst.Nitrogen element in ammonia spirit is doped into amorphous state Nano tube array of titanium dioxide by this preparation method, have that specific surface area is big, photocatalysis efficiency is high, good stability and repeatable high, the method can prepare cheap visible-light photocatalyst, has preferable application prospect in terms of degradation of contaminant.
Description
Technical field
The invention belongs to catalysis material technical field, relate to the preparation method of a kind of nitrogen-doped titanium dioxide nano material, particularly to the preparation method of a kind of nitrogen-doped titanium dioxide nano composite structure, i.e. N doping bigger serface titania nanometer worm/nanotube composite structure light method for preparing catalyst.
Background technology
In recent years, semiconductor nano titanium dioxide, with its advantage such as catalytic performance height, oxidability strong, good stability, non-toxic inexpensive, enjoys favor in photocatalysis field.But, titanium dioxide nano material has wider energy gap (3.0～3.2eV), light-catalyzed reaction can only occur in black light district, and solar energy utilization ratio is relatively low.Therefore people attempt compound or other material that adulterates to expand the spectral response range of titanium dioxide nano material to improve its photocatalysis efficiency.Research shows, N doping can widen the photoresponse scope of titanium dioxide nano material to visible region, greatly improves the utilization ratio of visible ray.But the material of N doping is mainly nano TiO 2 powder and titanium dioxide nano-film at present, although nano-powder has the biggest specific surface area, but is difficult to recycling；Nano thin-film is coated in substrate and is easily recycled, and but decreases the contact area with reactant, and photocatalysis efficiency is the highest.Comparatively speaking, titania nanotube has a bigger specific surface area than nanometer film, and can be fixed in substrate and carry out reclaiming thus repeatedly utilize, it is thus possible to have the biggest advantage in photocatalysis field.
Summary of the invention
It is an object of the invention to provide a kind of method simply, efficiently, stably preparing nitrogen-doped titanium dioxide nano composite structure, eliminate conventional high-temperature annealing crystallization process.
It is a further object to provide the application of a kind of nano composite structure prepared in aforementioned manners.
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 characterised in that this preparation method specifically sequentially includes the following steps:
Step 1: titanium sheet is cleaned successively in acetone, dehydrated alcohol and deionized water；
Being 1 4～8 by volume, the dense Fluohydric acid. and the concentration that take concentration >=40% respectively are the concentrated hydrochloric acid of 36%, are made into mixed solution；
Step 2: by the titanium sheet after the mixed chemical solution polished and cleaned in step 1；
Step 3: use constant voltage DC anodizing, under room temperature, the titanium plate surface after chemical polishing grows film of Nano tube array of titanium dioxide: graphite is negative electrode, and titanium sheet is anode, and the distance of two interpolars is 3～5cm；Electrolyte is containing 0.20～0.50wt.% ammonium fluoride and the ethylene glycol solution of 0.01～0.05wt.% fluohydric acid gas, oxidation voltage 40～60V, oxidization time 5～600min, and use magnetic stirrer electrolyte, after having aoxidized, being washed with deionized water clean titanium sheet, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；
By volume 1 1～10, take ammonia and deionized water that concentration is 25% respectively, be made into ammonia spirit；
Step 4: be immersed in ammonia spirit by orderly for amorphous state Nano tube array of titanium dioxide, is placed in the temperature environment of 80～100 DEG C heating 3～15 hours, natural cooling, deionized water rinsing, and nitrogen dries up, and prepares nitrogen-doped titanium dioxide nano composite structure.
Another technical solution used in the present invention is: the application of a kind of nitrogen-doped titanium dioxide nano composite structure prepared by above-mentioned preparation method, this nitrogen-doped titanium dioxide nano composite structure photocatalyst.
Prepared amorphous state Nano tube array of titanium dioxide is immersed in ammonia spirit by preparation method of the present invention, heating 3～15 hours at a certain temperature, the nitrogen element in ammonia spirit is made to be doped into amorphous state Nano tube array of titanium dioxide, form the nano titania worm/nano-tube array of N doping, it is big that this array has specific surface area, photocatalysis efficiency is high, good stability and repeatable high, shows the photocatalysis performance of excellence.Owing to this array growth is at the bottom of fixing titanio, it is simple to directly recycling, this preparation method can be used for industrialized production simultaneously, it is possible to prepares cheap visible-light photocatalyst, has preferable application prospect in terms of degradation of contaminant.
Accompanying drawing explanation
Fig. 1 is the SEM surface topography map of the nitrogen-doped titanium dioxide nano composite structure that embodiment 1 prepares.
Fig. 2 is embodiment 1 to prepare the orderly Nano tube array of titanium dioxide of amorphous state put into the XRD spectra after variable concentrations ammonia spirit soaks.
Fig. 3 is the XPS spectrum figure after being soaked in water by the orderly Nano tube array of titanium dioxide of amorphous state that embodiment 1 prepares.
Fig. 4 is the embodiment 1 prepared orderly Nano tube array of titanium dioxide of amorphous state XPS spectrum figure after ammonia soaks in the present invention.
Fig. 5 is the narrow spectrum XPS peak position that in the present invention, ammonia soaks the N peak position that titanium dioxide occurs.
Fig. 6 is the ultraviolet-visible absorption spectra figure preparing sample in embodiment 1, embodiment 2, embodiment 3 and comparative example.
Fig. 7 corresponds to the energy gap curve chart that Fig. 6 calculates.
Fig. 8 be in the present invention nitrogen-doped titanium dioxide nanometer worm/nanotube composite construction electric current of preparation with relation curve (I-V curve) figure of change in voltage.
Fig. 9 is after in embodiment 1, embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2, the nitrogen-doped titanium dioxide nanometer worm/nanotube composite construction of preparation degrades the curve chart of methyl orange solution under visible light illumination and nitrogen-doped titanium dioxide nanometer worm/nanotube composite construction of embodiment 1 being prepared makes annealing treatment again, the curve chart of methyl orange solution of degrading under visible light illumination.
Detailed description of the invention
The present invention is described in detail with detailed description of the invention below in conjunction with the accompanying drawings.
In recent years, people attempt compound or other material that adulterates to expand the spectral response range of titanium dioxide nano material to improve its photocatalysis efficiency.Research shows, N doping can widen the photoresponse scope of titanium dioxide nano material to visible region, improves the utilization ratio of visible ray greatly.But, the material of N doping is mainly nano TiO 2 powder and titanium dioxide nano-film.Although nano TiO 2 powder has the biggest specific surface area, but is difficult to recycling；Titanium dioxide nano-film is coated in substrate and is easily recycled, and but decreases the contact area with reactant, and photocatalysis efficiency is the highest.Comparatively speaking, titania nanotube has a bigger specific surface area than nanometer film, and can be fixed in substrate and carry out reclaiming thus repeatedly utilize, and therefore, has the biggest advantage in photocatalysis field.
Traditional doping process, high annealing mode to be used, need to consume relatively multiple-energy-source.Have been reported that[1][2]Claiming to soak anodised amorphous state Nano tube array of titanium dioxide in water to be allowed to crystallization and become Anatase, the method is simple to operate, can save conventional high-temperature annealing crystallization process, reduces energy loss.But use the method that amorphous state Nano tube array of titanium dioxide crystallization, the anatase titania of broadband system can only be made still can not to absorb visible ray.
To this end, we have proposed, anodised amorphous state Nano tube array of titanium dioxide is immersed in ammonia spirit, above-mentioned water environment both can be provided to make amorphous state titania nanotube crystallize, provided nitrogen source simultaneously, be doped into nitrogen element when structural remodeling.When anodised amorphous state Nano tube array of titanium dioxide is immersed in ammonia spirit, TiO unstable in amorphous state Nano tube array of titanium dioxide6 2-Octahedra by surface hydroxyl adsorbed water molecule, form the Ti (OH) of indissoluble6 2-, Ti (OH) in ammonia environment6 2-The Ti (OH) that can be formed with another the same manner6 2-Octahedral one side, simultaneously one hydrone of abjection, thereafter, other octahedra Ti (OH) is shared with a suitable angle6 2-Suitable angle can be selected to share octahedral another side with same dewatering type, in the process owing to there is substantial amounts of nitrogen in ammonia spirit, nitrogen-atoms is due to Ti (OH)6 2-The many dangling bonds in surface can be easy to be brought into the brilliant bag of this restructuring.The most just the brilliant bag of a nitrogen-doped titanium dioxide is formed.Numerous brilliant bags share crystal face and ultimately form Anatase nitrogen-doped titanium dioxide.Need not the high temperature anneal, be a kind of low energy consumption, the method for nitrogen-doped titanium dioxide nanotube array simple, efficient.
This research not only has scientific value, and has practical value, has considerable application prospect in terms of catalyzing and degrading pollutant by visible light.
Preparation method of the present invention specifically sequentially includes the following steps:
Step 1: each cleaning 10～15min in acetone, dehydrated alcohol and deionized water successively by industrial titanium sheet；
It is 1 4～8 by volume, takes the dense Fluohydric acid. of concentration >=40% respectively and concentration is the concentrated hydrochloric acid of 36%, be made into mixed solution；
Step 2: by the titanium sheet 100～180s after the mixed chemical solution polished and cleaned in step 1, then rinsing well with deionized water, nitrogen dries up；
Step 3: use constant voltage DC anodizing, under room temperature, the titanium plate surface after chemical polishing grows film of Nano tube array of titanium dioxide: graphite is negative electrode, and titanium sheet is anode, and the distance of two interpolars is 3～5cm；Electrolyte is containing 0.20～0.50wt.% ammonium fluoride (NH4The ethylene glycol solution of F) and 0.01～0.05wt.% fluohydric acid gas (HF), oxidation voltage 40～60V, oxidization time 5～600min, and use magnetic stirrer electrolyte, after having aoxidized, it is washed with deionized water clean titanium sheet, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；
By volume 1 1～10, take ammonia and deionized water that concentration is 25% respectively, be made into ammonia spirit；
Step 4: orderly for amorphous state Nano tube array of titanium dioxide is immersed in the autoclave filling ammonia spirit, this autoclave is placed in the temperature environment of 80～100 DEG C heating 3～15 hours, after natural cooling, with deionized water lavage specimens product, nitrogen dries up, and i.e. prepares Anatase nitrogen-doped titanium dioxide nanometer worm/nanotube composite construction.
Nitrogen-doped titanium dioxide nanometer worm/nano tube structure photocatalyst by preparation, being placed in the methyl orange solution that 5mL concentration is 0.5mmol/L, ice-water bath keeps 0 DEG C, stands 30min in the dark, after reaching adsorption equilibrium, move to irradiate under simulated solar radiant 0～150min.
Nitrogen-doped titanium dioxide nanometer worm/nano tube structure prepared by the inventive method has that specific surface area is big, photocatalysis efficiency is high, good stability, lower-price characteristic, shows the photocatalysis performance of excellence.And preparation method is simple, beneficially industrialized mass production, have great practical value.
List of references
[1] in water, spontaneous topographical transition and the phase transformation that anodised titania nanotube causes is processed under room temperature, kingly way love etc., " nanometer bulletin " 2011, and o. 11th, page 3649.
[2] a kind of method of simple low temperature crystallized anodic oxidation amorphous state titania nanotube, Liao Yulong etc., " ACS application material and interface ", and 2011, the 3rd phase, page 2800.
Embodiment
1
Take industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15min in acetone, dehydrated alcohol and deionized water；18 take the dense Fluohydric acid. of concentration >=40% respectively and concentration is the concentrated hydrochloric acid of 36% by volume, be made into mixed solution, by titanium sheet 180s after this mixed chemical solution polished and cleaned；Use constant voltage DC anodizing, under room temperature after a polish titanium plate surface growth film of Nano tube array of titanium dioxide: graphite is negative electrode, titanium sheet is anode, distance 3cm of two interpolars, electrolyte is the ethylene glycol solution (analytical pure) containing 0.30wt.% ammonium fluoride and 0.03wt.% Fluohydric acid., oxidation voltage 40V, oxidization time is 5min, and use magnetic stirrer electrolyte, uniform with guarantee system temperature and electrolyte, take out titanium sheet, deionized water rinsing after having aoxidized, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；By volume 11, take ammonia and deionized water that concentration is 25% respectively, be made into ammonia spirit；Orderly for this amorphous state Nano tube array of titanium dioxide is immersed in the autoclave filling this ammonia spirit, autoclave is heated 9 hours at a temperature of 90 DEG C, after natural cooling, take out sample, rinse well with deionized water, nitrogen dries up, and i.e. 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 prepares, as it is 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 length about 50nm as seen from Figure 1.Illustrate that this composite construction can be greatly improved the raising of the specific surface area of titanium dioxide, beneficially photocatalysis efficiency.
Nano titania worm/nanotube the composite construction preparing embodiment 1 carries out XRD test, its result is as shown in Figure 2, untreated anodised titania nanotube is amorphous state, after ammonia spirit immersion treatment, making it be changed into Anatase, this is effective to improving photo-catalysis capability.
Comparative example
1
Obtain the orderly Nano tube array of titanium dioxide of amorphous state as described in Example 1；By orderly for this amorphous state Nano tube array of titanium dioxide submergence in deionized water, unadulterated nano titania worm/nanotube composite construction is prepared.
Fig. 3 to Fig. 5 is that the XPS of prepared nano titania worm/nanotube composite construction characterizes.Fig. 3 is the XPS spectrum figure of nano titania worm/nanotube composite construction that comparative example 1 prepares, from figure 3, it can be seen that only occur in that the characteristic peak of Ti and O in XPS spectrum.Fig. 4 shows with ammonia spirit (by volume 11, ammonia and deionized water by concentration is 25% are made into) XPS spectrum of nano titania worm/nanotube composite construction for preparing of immersion treatment embodiment 1, found out by Fig. 4, after ammonia spirit immersion treatment, XPS spectrum goes out in addition to the characteristic peak of Ti and O, have also appeared the characteristic peak of N.Again by the narrow spectrum scanning of the XPS of N peak position in Fig. 5 it can be seen that N peak is positioned at 399.7eV, for clearance-type N doping, illustrate to use preparation method of the present invention successfully to prepare nitrogen-doped titanium dioxide nanometer worm/nanotube composite construction.
Embodiment
2
Take industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 10min in acetone, dehydrated alcohol and deionized water；14 dense Fluohydric acid. and the concentrated hydrochloric acid of concentration 36% taking concentration >=40% respectively, is made into mixed solution, by titanium sheet 120s after this mixed chemical solution polished and cleaned by volume；Use constant voltage DC anodizing, under room temperature after a polish titanium plate surface growth film of Nano tube array of titanium dioxide: graphite is negative electrode, titanium sheet is anode, distance 4cm of two interpolars, electrolyte is the ethylene glycol solution (analytical pure) containing 0.50wt.% ammonium fluoride and 0.05wt.% Fluohydric acid., oxidation voltage 60V, oxidization time 180min, and use magnetic stirrer electrolyte, uniform with guarantee system temperature and electrolyte, take out titanium sheet after having aoxidized, with deionized water rinsing, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；15 take the ammonia and deionized water that concentration is 25% respectively by volume, be made into ammonia spirit；Being immersed in this ammonia spirit by orderly for this amorphous state Nano tube array of titanium dioxide, heat 3 hours at a temperature of being placed in 100 DEG C, after natural cooling, take out sample, rinse well with deionized water, nitrogen dries up, and i.e. obtains nitrogen-doped titanium dioxide nano composite structure.
Embodiment
3
Take industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 12.5min in acetone, dehydrated alcohol and deionized water；By volume 16, take dense Fluohydric acid. and the concentrated hydrochloric acid of concentration 36% of concentration >=40% respectively, be made into mixed solution, by titanium sheet 150s after this mixed chemical solution polished and cleaned；Use titanium plate surface growth film of Nano tube array of titanium dioxide after a polish under constant voltage DC anodizing room temperature: graphite is negative electrode, titanium sheet is anode, distance 3.5cm of two interpolars, electrolyte is the ethylene glycol solution (analytical pure) containing 0.40wt.% ammonium fluoride and 0.04wt.% Fluohydric acid., oxidation voltage 50V, oxidization time 400min, and use magnetic stirrer electrolyte, uniform with guarantee system temperature and electrolyte, titanium sheet is taken out after having aoxidized, with deionized water rinsing, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；1 10 take the ammonia and deionized water that concentration is 25% respectively by volume, be made into ammonia spirit；Orderly for this amorphous state Nano tube array of titanium dioxide is immersed in the autoclave filling this ammonia spirit, autoclave is heated 15 hours at a temperature of 80 DEG C, after natural cooling, take out sample, rinse well with deionized water, nitrogen dries up, and i.e. obtains nitrogen-doped titanium dioxide nanometer worm/nano pipe light catalyst.
The sample prepared in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 is carried out ultravioletvisible absorption test respectively, obtains the curve chart shown in Fig. 6.As seen from Figure 6, along with being gradually increased of ammonia concn soaking the orderly Nano tube array of titanium dioxide of amorphous state, the light absorpting ability of the nitrogen-doped titanium dioxide nano composite structure prepared gradually strengthens, there is red shift and is extended to visible region in ABSORPTION EDGE simultaneously, the utilization rate of this visible ray to improving sample, it is achieved visible light catalytic is favourable.
The energy gap curve chart calculated corresponding to Fig. 6, such as Fig. 7, (abscissa of Fig. 7 represents photon energy, and unit is eV；The vertical coordinate of Fig. 7 be absorptance with photon energy product square, unit is (eV/cm)2).From figure 7 it can be seen that along with the increase of the ammonia spirit concentration for soaking the orderly Nano tube array of titanium dioxide of amorphous state, samples band-gap becomes narrow gradually.So, the electron excitation of titanium dioxide valence band to conduction band can also be formed electron-hole pair by the visible ray that energy is less, and electronics has strong reducing power, and hole can form hydroxyl with water or oxygen reaction.Hydroxyl has a strong oxidability, thus the stronger radical oxidation reduction of the activity that is generated of pollutant is degraded.
The nitrogen-doped titanium dioxide nano composite structure prepared in embodiment 1, embodiment 2, embodiment 3 and comparative example 1 is carried out I V test；Nano tube array of titanium dioxide orderly to amorphous state carries out I V test, the most also the orderly Nano tube array of titanium dioxide of amorphous state after processing by existing annealing process is carried out I V test, obtain curve chart as shown in Figure 8, Fig. 8 shows, the electrical conductivity of unannealed amorphous state titania nanotube is relatively low, when by embodiment 1,2, after the process of 3, electrical conductivity is remarkably reinforced, and along with the increase of ammonia spirit concentration, the electrical conductivity of sample is gradually increased.Although the electrical conductivity of the titania nanotube that employing traditional method is directly annealed increased than unannealed sample, but less than the electrical conductivity of the sample of preparation in the present invention.Electrical conductivity increases and is conducive to light induced electron transmission, thus is favourable to improving photocatalysis efficiency.
Embodiment
4
Take industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 10min in acetone, dehydrated alcohol and deionized water；It is 15 by volume, takes dense Fluohydric acid. and the concentrated hydrochloric acid of concentration 36% of concentration >=40% respectively, be made into mixed solution, by titanium sheet 100s after this mixed chemical solution polished and cleaned；Use titanium plate surface growth film of Nano tube array of titanium dioxide after a polish under constant voltage DC anodizing room temperature: graphite is negative electrode, titanium sheet is anode, the distance of two interpolars is maintained at 4.5cm, electrolyte is the ethylene glycol solution (analytical pure) containing 0.20wt.% ammonium fluoride and 0.01wt.% Fluohydric acid., oxidation voltage 45V, oxidization time 600min, and use magnetic stirrer electrolyte, uniform with guarantee system temperature and electrolyte, titanium sheet is taken out after having aoxidized, with deionized water rinsing, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；12 take the ammonia and deionized water that concentration is 25% respectively by volume, be made into ammonia spirit；Orderly for this amorphous state Nano tube array of titanium dioxide is immersed in the autoclave filling ammonia spirit, this autoclave is placed at a temperature of 85 DEG C and heats 12 hours, after natural cooling, take out sample, rinse well with deionized water, nitrogen dries up, and i.e. obtains nitrogen-doped titanium dioxide nanometer worm/nano pipe light catalyst.
Comparative example 2
Obtain the orderly Nano tube array of titanium dioxide of amorphous state as described in Example 3；Use existing annealing process Nano tube array of titanium dioxide orderly to this amorphous state to anneal, prepare crystallizing titanium dioxide nano pipe.
Comparative example 3
Prepare nitrogen-doped titanium dioxide nano composite structure as described in Example 1, then use existing annealing process that this nitrogen-doped titanium dioxide nano composite structure is made annealing treatment.
The sample Photodegradation of Methyl Orange solution under visible light illumination that will obtain in embodiment 1, embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2 and comparative example 3, obtains curve chart as shown in Figure 9.Fig. 9 vertical coordinate is the ratio of the concentration of remaining methyl orange and initial orange concentration after illumination, and vertical coordinate is closer to 1, illustrate that the methyl orange degraded is the fewest, and effect is the poorest.As seen from the figure, the degradation effect of each embodiment is substantially better than comparative example 1.In order to contrast, sample embodiment 1 prepared is again 500 DEG C of 3 hours (comparative examples 3) of annealing, the most under equal conditions test its photocatalysis performance, its photo-catalysis capability is almost suitable with embodiment 1 effect, this illustrates the most again, through ammonia immersion treatment, titania nanotube well-crystallized, it is not necessary to re-annealing processes.
From the point of view of in terms of application prospect, nitrogen-doped titanium dioxide nanometer worm/nano-tube array of the present invention, in addition to can be used for photocatalyst, has the characteristics such as characteristic of semiconductor, high electrical conductivity and big specific surface area, it may also be used for solaode due to it, super capacitor, the device such as field emmision material.Based on nitrogen-doped titanium dioxide nanometer worm/film of Nano tube array, it is expected to realize the compound of these functional devices, thus realizes the integrated of multifunction device.
Therefore, nitrogen-doped titanium dioxide nanometer worm/film of Nano tube array has the most excellent performance and more wide application prospect.
Claims (4)
1. a nitrogen-doped titanium dioxide nano composite structure preparation method, it is characterised in that this preparation method specifically sequentially includes the following steps:
Step 1: titanium sheet is cleaned successively in acetone, dehydrated alcohol and deionized water；
Being 1 4～8 by volume, the dense Fluohydric acid. and the concentration that take concentration >=40% respectively are the concentrated hydrochloric acid of 36%, are made into mixed solution；
Step 2: by the titanium sheet after the mixed chemical solution polished and cleaned in step 1；
Step 3: use constant voltage DC anodizing, under room temperature, the titanium plate surface after chemical polishing grows film of Nano tube array of titanium dioxide: graphite is negative electrode, and titanium sheet is anode, and the distance of two interpolars is 3～5cm；Electrolyte is containing 0.20～0.50wt.% ammonium fluoride and the ethylene glycol solution of 0.01～0.05wt.% fluohydric acid gas, oxidation voltage 40～60V, oxidization time 5～600min, and use magnetic stirrer electrolyte, after having aoxidized, being washed with deionized water clean titanium sheet, nitrogen dries up, and obtains the orderly Nano tube array of titanium dioxide of amorphous state；
By volume 1 1～10, take ammonia and deionized water that concentration is 25% respectively, be made into ammonia spirit；
Step 4: be immersed in ammonia spirit by orderly for amorphous state Nano tube array of titanium dioxide, is placed in the temperature environment of 80～100 DEG C heating 3～15 hours, natural cooling, deionized water rinsing, and nitrogen dries up, and prepares nitrogen-doped titanium dioxide nano composite structure.
The most according to claim 1, nitrogen-doped titanium dioxide nano composite structure preparation method, it is characterised in that in described step 1, clean 10～15min by each in acetone, dehydrated alcohol and deionized water for titanium sheet.
The most according to claim 1, nitrogen-doped titanium dioxide nano composite structure preparation method, it is characterised in that in described step 2, chemical polishing titanium sheet 100～180s, deionized water is clean, and nitrogen dries up.
4. the application of the nitrogen-doped titanium dioxide nano composite structure prepared by preparation method described in claim 1, it is characterised in that this nitrogen-doped titanium dioxide nano composite structure photocatalyst.
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| CN104399503B (en) * | 2014-10-23 | 2017-01-11 | 河海大学 | Iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst and preparation method and application thereof |
| CN109686987B (en) * | 2018-12-17 | 2020-11-24 | 中国科学院广州能源研究所 | Carbon/nitrogen-loaded titanium dioxide nanotube matrix and application thereof in microbial fuel cell |
| CN111383849A (en) * | 2018-12-28 | 2020-07-07 | 银隆新能源股份有限公司 | Preparation method of nitrogen-doped titanium dioxide nanotube loaded with molybdenum disulfide and nitrogen-doped titanium dioxide nanotube loaded with molybdenum disulfide |
| CN109821512A (en) * | 2019-01-24 | 2019-05-31 | 兰州城市学院 | Nitrogen carbon surface modifies nanometer titanium dioxide fiber head and the preparation method and application thereof |
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