CN104399503A - Iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst and preparation method and application thereof - Google Patents
Iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst and a preparation method and an application thereof, and belongs to the titanium dioxide photocatalyst field. The preparation method of the iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst comprises the following steps: step one, polishing a Ti sheet smoothly, immersing into a strong acid mixed solution, carrying out chemical polishing, then carrying out ultrasonic cleaning, and drying for standby application; step two, with a direct current voltage, taking the Ti sheet obtained in the step one as an anode, taking a Pt sheet as a cathode, in an electrolyte solution, carrying out anodic oxidation on the Ti sheet, and thus obtaining an amorphous titanium dioxide nanotube array; and step three, carrying out high-temperature calcination on the amorphous titanium dioxide nanotube array obtained in the step two in a nitrogen atmosphere, and carrying out crystallization molding to obtain the iron-nitrogen-fluorine co-doped titanium dioxide nanotube array photocatalyst. The method can dope three elements of iron, nitrogen and fluorine into the TiO2 nanotube array at one step simultaneously, is simple in process and convenient to operate, and cannot produce secondary pollution.
Description
Technical field
The invention belongs to titanium dioxide optical catalyst field, be specifically related to a kind of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis and its preparation method and application.
Background technology
Photocatalysis technology is the pollutant treatment technology that development in recent years is got up, and under illumination effect, produces the free radical with Strong oxdiative ability through a series of reaction, can by the organic pollution exhaustive oxidation mineralising in water body.Conductor photocatalysis degradable organic pollutant not only has that the unrivaled speed of biodegradation is fast, non-selectivity, the degraded advantage such as completely, again inexpensive, nontoxic, can obviously be better than traditional chemical oxidation method in Long-Time Service etc., thus enjoy the concern of people.In numerous conductor photocatalysis material, titanium dioxide has has inexpensive, nontoxic and stronger photochemical catalytic oxidation ability and the organic pollution process being widely used in difficult for biological degradation in water body.
In the polymorphic titanic oxide material of crowd, with the Nano tube array of titanium dioxide that Ti sheet is prepared for substrate, there is specific area large, aperture is adjustable, structurally ordered, be combined with matrix firmly, difficult drop-off, the feature of secondary pollution can not be produced, be widely used in photocatalysis degradation organic contaminant in recent years.But the energy gap of Nano tube array of titanium dioxide is wider (3.2eV), only have response to ultraviolet light, and this part ultraviolet light only accounts for the 3-4% of solar energy, very low to the utilization rate of sunshine; In addition, light induced electron and hole are produce 10
-9compound in s, causes quantum efficiency very low, limits its practical application.Therefore need to carry out modification to Nano tube array of titanium dioxide, current method of modifying both domestic and external mainly comprises metal ion mixing, nonmetallic ion-doped, semiconductors coupling, noble metal loading etc., or several method uses simultaneously.And the preparation method that more than three kinds element dopings enter Nano tube array of titanium dioxide prepared by anodizing urgently researches and develops by a step simultaneously.
Summary of the invention
the technical problem solved:the object of the invention is to overcome the deficiencies in the prior art and provide a kind of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis and its preparation method and application, this catalyst crystal formation is good, photoelectric properties are excellent.
technical scheme of the present invention:
The preparation method of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, step is as follows:
Step one: polished smooth by Ti sheet, immerses in strong acid mixed liquor, chemical polishing 10 ~ 50s, after use each ultrasonic cleaning 5 ~ 30min of acetone, absolute ethyl alcohol, deionized water successively, post-drying is for subsequent use; Wherein said strong acid mixed liquor is HF and HNO
3and H
2the mixed liquor of O, HF, HNO
3and H
2the volume ratio of O is 1 ~ 2:4 ~ 10:5 ~ 10;
Step 2: under 20-60V DC voltage, with step one gained Ti sheet for anode, with Pt sheet for negative electrode, anodic oxidation Ti sheet 2 ~ 8h, obtains unformed Nano tube array of titanium dioxide in the electrolytic solution;
Step 3: by the high-temperature calcination under nitrogen atmosphere of unformed for step 2 gained Nano tube array of titanium dioxide, calcining heat is 400-600 ° of C, calcination time is 1-4h: make its crystallization forming, obtain iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis.
The preparation method of above-described iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, in step one, HF, HNO
3and H
2the volume ratio of O is 1:4:5.
The preparation method of above-described iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, electrolyte described in step 2 comprises the following component according to mass fraction meter: deionized water is 1-10wt%, Fe(NO3)39H2O is 0.04-0.4wt%, ammonium fluoride is 0.1-2wt%, and surplus is ethylene glycol.
The preparation method of described iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, in step 2, under 40V DC voltage, with step one gained Ti sheet for anode, with Pt sheet for negative electrode, anodic oxidation Ti sheet 4h in the electrolytic solution.
The preparation method of above-mentioned iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, the calcining heat in step 3 is 450 ° of C, and calcination time is 2h.
The iron that the preparation method of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis obtains, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis.
The iron that the preparation method of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis obtains, nitrogen, the application of fluorin-doped titanium dioxide nanotube array photo catalysis agent in degradable organic pollutant.
beneficial effect
First, the present invention utilizes electrochemistry anodic oxidation, in the ethylene glycol electrolyte containing deionized water, ferric nitrate, ammonium fluoride, oxidation titanium sheet, obtained unformed Nano tube array of titanium dioxide, then in high-temperature calcination under nitrogen atmosphere, crystal formation is good, photoelectric properties are good iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis is prepared;
The second, the present invention, with nitrogen-doped titanium dioxide, makes it have narrower band gap width and stronger visible absorption ability, effectively widens its absorption region at visible ray; With iron and Fluorin doped titanium dioxide, reduce the recombination probability in its light induced electron and hole, improve the efficiency of its opto-electronic conversion, thus improve the concentration of hydroxyl radical free radical in light reaction procedure, in the research of photocatalysis degradation organic contaminant as phenol, show good visible light photocatalysis performance;
3rd, preparation method's technique of the present invention is simple, easy to operate, gained catalyst cost is low, it is convenient to reclaim, can not produce secondary pollution and can reuse, effectively improve utilization rate and the quantum efficiency of solar energy, have broad application prospects in the field such as photocatalysis degradation organic contaminant, Solar use.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of embodiment 1 gained iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis;
Fig. 2-a is the full spectrogram of X-Ray Photoelectron of embodiment 1 gained iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis;
Fig. 2-b is the x-ray photoelectron spectroscopy figure of N 1s of embodiment 1 gained iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis;
Fig. 2-c is the x-ray photoelectron spectroscopy figure of F 1s of embodiment 1 gained iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis;
Fig. 2-d is the x-ray photoelectron spectroscopy figure of Fe 2p of embodiment 1 gained iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis;
Fig. 3 is the scanning electron microscope diagram of embodiment 3 gained iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis;
Phenol surplus ratio-time history when Fig. 4 is embodiment 1 gained iron, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent degradation of phenol;
Phenol surplus ratio when Fig. 5 is embodiment 1 gained iron, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent degradation of phenol-recycling number of times graph of relation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
embodiment 1
By Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph polishing, until surface cleaning is smooth, then immerse strong acid mixed solution (HF:HNO
3: H
2o=1:4:5 volume ratio) in carry out chemical polishing 30s, use acetone soln, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min subsequently respectively.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, for subsequent use.Under 40V DC voltage, with Ti sheet for anode, Pt sheet is negative electrode, and containing 2wt% deionized water, 0.2wt% Fe(NO3)39H2O, 0.3wt% ammonium fluoride, surplus is in the electrolyte of ethylene glycol, and anodic oxidation Ti sheet 4h, prepares unformed TiO
2nano-tube array.By the TiO of gained
2nano-tube array is placed in Muffle furnace high-temperature calcination under nitrogen atmosphere, and calcining heat is 450 ° of C, and calcination time is 2h, makes its crystallization forming, iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis.
With the pattern of sem observation gained catalyst.As shown in Figure 1, the nanotube obtained in order to upper method is glittering and translucent, and the separate arrangement of every root nanotube, it can thus be appreciated that the doping of three kinds of elements does not affect the appearance structure of its nano-tube array.Its caliber is about 80nm, and wall thickness is about 12nm, and pipe range is about 11 μm.With x-ray photoelectron spectroscopy analyze iron, nitrogen, fluoro-Nano tube array of titanium dioxide chemical element composition and valence state.From Fig. 2-a to Fig. 2-d, this nanotube is made up of Ti, O, N, F, Fe, and N mainly exists with Ti-O-N, and illustrate that N mainly exists with space N form, F mainly exists with Ti-O-F, illustrates that F successfully instead of part TiO
2o in lattice, for Fe2p, shows Fe at the peak of 709.86eV
3+existence, Fe is described
3+also successfully TiO is doped into
2lattice, instead of part Ti
4+.Below all prove iron, nitrogen, fluoro-Nano tube array of titanium dioxide is successfully prepared.
embodiment 2
By Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph polishing, until surface cleaning is smooth, then immerse strong acid mixed solution (HF:HNO
3: H
2o=1:4:5 volume ratio) in carry out chemical polishing 30s, use acetone soln, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min subsequently respectively.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, for subsequent use.Under 40V DC voltage, with Ti sheet for anode, Pt sheet is negative electrode, and containing 2wt% deionized water, 0.4wt% Fe(NO3)39H2O, 0.3wt% ammonium fluoride, surplus is in the electrolyte of ethylene glycol, and anodic oxidation Ti sheet 4h, prepares unformed TiO
2nano-tube array.By the TiO of gained
2nano-tube array is placed in Muffle furnace high-temperature calcination under nitrogen atmosphere, and calcining heat is 450 ° of C, and calcination time is 2h, makes its crystallization forming, can obtain iron, nitrogen, fluoro-Nano tube array of titanium dioxide.
embodiment 3
By Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph polishing, until surface cleaning is smooth, then immerse strong acid mixed solution (HF:HNO
3: H
2o=1:4:5 volume ratio) in carry out chemical polishing 30s, use acetone soln, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min subsequently respectively.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, for subsequent use.Under 40V DC voltage, with Ti sheet for anode, Pt sheet is negative electrode, and containing 2wt% deionized water, 0.04wt% Fe(NO3)39H2O, 0.3wt% ammonium fluoride, surplus is in the electrolyte of ethylene glycol, and anodic oxidation Ti sheet 4h, prepares unformed TiO
2nano-tube array.By the TiO of gained
2nano-tube array is placed in Muffle furnace high-temperature calcination under nitrogen atmosphere, and calcining heat is 450 ° of C, and calcination time is 2h, makes its crystallization forming, can obtain iron, nitrogen, fluoro-Nano tube array of titanium dioxide.
With the pattern of sem observation iron, nitrogen, fluoro-Nano tube array of titanium dioxide.As shown in Figure 3, the caliber of obtained nanotube is about 80nm, and wall thickness is about 12nm, and pipe range is about 11 μm.Compared to Figure 1, not significantly change.
embodiment 4
By Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph polishing, until surface cleaning is smooth, then immerse strong acid mixed solution (HF:HNO
3: H
2o=1:5:5 volume ratio) in carry out chemical polishing 10s, use acetone soln, absolute ethyl alcohol, deionized water ultrasonic cleaning 5min subsequently respectively.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, for subsequent use.Under 20V DC voltage, with Ti sheet for anode, Pt sheet is negative electrode, and containing 1wt% deionized water, 0.04wt% Fe(NO3)39H2O, 0.1wt% ammonium fluoride, surplus is in the electrolyte of ethylene glycol, and anodic oxidation Ti sheet 2h, prepares unformed TiO
2nano-tube array.By the TiO of gained
2nano-tube array is placed in Muffle furnace high-temperature calcination under nitrogen atmosphere, and calcining heat is 400 ° of C, and calcination time is 4h, makes its crystallization forming, can obtain iron, nitrogen, fluoro-Nano tube array of titanium dioxide.
embodiment 5
By Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph polishing, until surface cleaning is smooth, then immerse strong acid mixed solution (HF:HNO
3: H
2o=1:6:7 volume ratio) in carry out chemical polishing 50s, use acetone soln, absolute ethyl alcohol, deionized water ultrasonic cleaning 30min subsequently respectively.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, for subsequent use.Under 60V DC voltage, with Ti sheet for anode, Pt sheet is negative electrode, and containing 10wt% deionized water, 0.04wt% Fe(NO3)39H2O, 2wt% ammonium fluoride, surplus is in the electrolyte of ethylene glycol, and anodic oxidation Ti sheet 8h, prepares unformed TiO
2nano-tube array.By the TiO of gained
2nano-tube array is placed in Muffle furnace high-temperature calcination under nitrogen atmosphere, and calcining heat is 600 ° of C, and calcination time is 1h, makes its crystallization forming, can obtain iron, nitrogen, fluoro-Nano tube array of titanium dioxide.
application examples 1the degraded of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis Pyrogentisinic Acid under visible light:
With iron, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol under visible light that embodiment 1 is obtained.Photocatalysis light source is 300w high pressure xenon lamp, and xenon lamp is by the condensed water cooling in quartzy double-jacket.Test in light-catalyzed reaction instrument, by be covered with iron, nitrogen, fluoro-Nano tube array of titanium dioxide titanium sheet vertically put into the phenol solution that 50mL mass concentration is 10mg/L.When reacting initial, first by phenol solution in the dark state magnetic agitation 30min to guarantee that reactant reaches adsorption equilibrium at catalyst surface.Then illumination 240min, gets a sample at interval of a period of time, approximately samples 0.5mL at every turn.Always with magnetic agitation in Photocatalytic Degradation Process.
The concentration of Phenol in Aqueous Solution, measure with liquid chromatograph (Agilent 1220 Infinity LC, the U.S.), mobile phase is methyl alcohol and water (v/v=7: 3, flow velocity is 1mL/min), and it is 270nm that phenol maximal ultraviolet detects absorbing wavelength.The palliating degradation degree of phenol is calculated according to concentration.The surplus ratio of phenol and the relation curve of time are as Fig. 4.As shown in Figure 4, photodegradation rate constant size order is as follows: iron, nitrogen, fluoro-titanium dioxide (
k obs=0.00531min
-1) > TiO
2(
k obs=0.00026min
-1), the degradation rate constant of iron, nitrogen, fluoro-titania nanotube is than pure TiO
2nanotube is much bigger, illustrates that the synergy of Fe, N and F greatly increases TiO
2the photocatalysis performance of the visible ray of nanotube.
application examples 2the degraded of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis Pyrogentisinic Acid under visible light:
With iron, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol under visible light that embodiment 2 is obtained.Photocatalysis light source is 300w high pressure xenon lamp, and xenon lamp is by the condensed water cooling in quartzy double-jacket.Test in light-catalyzed reaction instrument, by be covered with iron, nitrogen, fluoro-Nano tube array of titanium dioxide titanium sheet vertically put into the phenol solution that 50mL mass concentration is 10mg/L.When reacting initial, first by phenol solution in the dark state magnetic agitation 30min to guarantee that reactant reaches adsorption equilibrium at catalyst surface.Then illumination 240min, gets a sample at interval of a period of time, approximately samples 0.5mL at every turn.Always with magnetic agitation in Photocatalytic Degradation Process.
The concentration of Phenol in Aqueous Solution, measure with liquid chromatograph (Agilent 1220 Infinity LC, the U.S.), mobile phase is methyl alcohol and water (v/v=7: 3, flow velocity is 1mL/min), and it is 270nm that phenol maximal ultraviolet detects absorbing wavelength.The palliating degradation degree of phenol is calculated according to concentration.
application examples 3the degraded of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis Pyrogentisinic Acid under visible light:
With iron, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol under visible light that embodiment 3 is obtained.Photocatalysis light source is 300w high pressure xenon lamp, and xenon lamp is by the condensed water cooling in quartzy double-jacket.Test in light-catalyzed reaction instrument, by be covered with iron, nitrogen, fluoro-Nano tube array of titanium dioxide titanium sheet vertically put into the phenol solution that 50mL mass concentration is 10mg/L.When reacting initial, first by phenol solution in the dark state magnetic agitation 30min to guarantee that reactant reaches adsorption equilibrium at catalyst surface.Then illumination 240min, gets a sample at interval of a period of time, approximately samples 0.5mL at every turn.Always with magnetic agitation in Photocatalytic Degradation Process.
The concentration of Phenol in Aqueous Solution, measure with liquid chromatograph (Agilent 1220 Infinity LC, the U.S.), mobile phase is methyl alcohol and water (v/v=7: 3, flow velocity is 1mL/min), and it is 270nm that phenol maximal ultraviolet detects absorbing wavelength.The palliating degradation degree of phenol is calculated according to concentration.
application examples 4recycling iron, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent degradation of phenol:
Under visible light, iron, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol that embodiment 1 is obtained is reused.Photocatalysis light source is 300w high pressure xenon lamp, and xenon lamp is by the condensed water cooling in quartzy double-jacket.Test in light-catalyzed reaction instrument, by be covered with iron, nitrogen, fluoro-Nano tube array of titanium dioxide titanium sheet vertically put into the phenol solution that 50mL mass concentration is 10mg/L.When reacting initial, first phenol solution is stirred in the dark state 30min to guarantee that reactant reaches adsorption equilibrium at catalyst surface.Then illumination 240min, gets a sample at interval of a period of time, approximately samples 0.5mL at every turn.Always with magnetic agitation in Photocatalytic Degradation Process.The experiment condition of each recycling is identical, uses same Fe, N, F-TiO
2nano-tube array, after each illumination 240min terminates, by washed with de-ionized water 6 times, then dries 2h, to use next time under putting into baking oven 100 ° of C.
The concentration of Phenol in Aqueous Solution, measure with liquid chromatograph (Agilent 1220 Infinity LC, the U.S.), mobile phase is methyl alcohol and water (v/v=7: 3, flow velocity is 1mL/min), and it is 270nm that phenol maximal ultraviolet detects absorbing wavelength.The palliating degradation degree of phenol is calculated according to concentration.The surplus ratio of phenol and the relation curve of recycling number of times are as Fig. 5.As shown in Figure 5, when iron, nitrogen, fluoro-Nano tube array of titanium dioxide reuse 4 times, the degradation efficiency of its Pyrogentisinic Acid does not significantly reduce.And owing to being that growth is on the Ti sheet, very convenient recycling, can't produce secondary pollution, therefore known, iron, nitrogen, fluoro-Nano tube array of titanium dioxide are a kind of highly effective and visible-light photocatalysts that can reuse, and can be applicable in actual production.
Claims (7)
1. the preparation method of iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, is characterized in that, step as
Under:
Step one: polished smooth by Ti sheet, immerses in strong acid mixed liquor, chemical polishing 10 ~ 50s, after use each ultrasonic cleaning 5 ~ 30min of acetone, absolute ethyl alcohol, deionized water successively, post-drying is for subsequent use; Wherein said strong acid mixed liquor is HF and HNO
3and H
2the mixed liquor of O, HF, HNO
3and H
2the volume ratio of O is 1 ~ 2:4 ~ 10:5 ~ 10;
Step 2: under 20-60V DC voltage, with step one gained Ti sheet for anode, with Pt sheet for negative electrode, anodic oxidation Ti sheet 2 ~ 8h, obtains unformed Nano tube array of titanium dioxide in the electrolytic solution;
Step 3: by the high-temperature calcination under nitrogen atmosphere of unformed for step 2 gained Nano tube array of titanium dioxide, calcining heat is 400-600 ° of C, calcination time is 1-4h: make its crystallization forming, obtain iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis.
2. the preparation method of iron according to claim 1, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, is characterized in that, in step one, and HF, HNO
3and H
2the volume ratio of O is 1:4:5.
3. the preparation method of iron according to claim 1 and 2, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, it is characterized in that, electrolyte described in step 2 comprises the following component according to mass percent: deionized water 1-10wt%, Fe(NO3)39H2O 0.04-0.4wt%, ammonium fluoride 0.1-2wt%, surplus is ethylene glycol.
4. the preparation method of iron according to claim 1 and 2, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, is characterized in that, in step 2, under 40V DC voltage, with step one gained Ti sheet for anode, with Pt sheet for negative electrode, anodic oxidation Ti sheet 4h in the electrolytic solution.
5. the preparation method of iron according to claim 4, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis, is characterized in that, the calcining heat in step 3 is 450 ° of C, and calcination time is 2h.
6. the preparation method of iron according to claim 1, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis obtain iron, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis.
7. the preparation method of iron according to claim 1, nitrogen, the agent of fluorin-doped titanium dioxide nanotube array photo catalysis obtain iron, nitrogen, the application of fluorin-doped titanium dioxide nanotube array photo catalysis agent in degradable organic pollutant.
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