CN104399503B - 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 ferrum, nitrogen, fluorin-doped titanium dioxide nanometer
Pipe array photo catalysis agent and its preparation method and application.
Background technology
Photocatalysis technology is the Pollutant Treatment technology that development in recent years is got up, under illumination effect, through a series of
Reaction produces the free radical with Strong oxdiative ability, it is possible to by the organic pollution exhaustive oxidation mineralising in water body.Semiconductor light
Catalytic degradation organic pollution not only has that the unrivaled speed of biodegradation is fast, non-selectivity, the degraded advantage such as completely, again
Inexpensive, nontoxic, the aspect such as life-time service can be substantially better than traditional chemical oxidation method, thus enjoy the concern of people.?
In numerous conductor photocatalysis materials, titanium dioxide has has inexpensive, nontoxic and stronger photochemical catalytic oxidation ability and extensive
In water body, the organic pollution of difficult for biological degradation processes.
In many polymorphic titanic oxide materials, the Nano tube array of titanium dioxide prepared for substrate with Ti sheet, have
Specific surface area is big, and aperture is adjustable, structurally ordered, is firmly combined with matrix, difficult drop-off, will not produce the feature of secondary pollution,
It is 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 ultraviolet light is had response, and this part ultraviolet light only accounts for the 3-4% of solar energy, to the utilization rate of sunlight very
Low；Additionally, light induced electron and hole are in 10 produced-9It is combined in s, causes quantum efficiency the lowest, limit its actual application.Therefore
Needing to carry out Nano tube array of titanium dioxide modification, current method of modifying both domestic and external mainly includes that metal ion is mixed
Miscellaneous, nonmetallic ion-doped, semiconductors coupling, noble metal loading etc., or several method uses simultaneously.And a step will simultaneously
The preparation method that more than three kinds element dopings enter Nano tube array of titanium dioxide prepared by anodizing is urgently researched and developed.
Summary of the invention
Solve the technical problem that: it is an object of the invention to overcome the deficiencies in the prior art to provide a kind of ferrum, nitrogen, fluorine to be co-doped with
Miscellaneous titanium dioxide nanotube array photocatalyst and its preparation method and application, catalyst crystal formation is good, photoelectric properties are excellent for this.
Technical scheme:
Ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent, step is as follows:
Step one: polished smooth by Ti sheet, immerses in strong acid mixed liquor, chemical polishing 10 ~ 50s, after successively by acetone, nothing
Water-ethanol, deionized water each ultrasonic cleaning 5 ~ 30min, post-drying is standby；Wherein said strong acid mixed liquor is HF and HNO3And H2O
Mixed liquor, HF, HNO3And H2The volume ratio of O is 1 ~ 2:4 ~ 10:5 ~ 10；
Step 2: under 20-60V DC voltage, with step one gained Ti sheet as anode, with Pt sheet as negative electrode, in electrolysis
Liquid Anodic Oxidation Ti sheet 2 ~ 8h, obtains unformed Nano tube array of titanium dioxide；
Step 3: by unformed for step 2 gained Nano tube array of titanium dioxide high-temperature calcination under nitrogen atmosphere, calcining
Temperature is 400-600 ° of C, and calcination time is 1-4h: make its crystallization forming, obtain ferrum, nitrogen, fluorin-doped titanium dioxide nanotube
Array photo catalysis agent.
Above-described ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent, step one
In, HF, HNO3And H2The volume ratio of O is 1:4:5.
Above-described ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent, in step 2
Described electrolyte includes the following component according to mass fraction meter: deionized water is 1-10wt%, and Fe(NO3)39H2O is 0.04-
0.4wt%, ammonium fluoride is 0.1-2wt%, and surplus is ethylene glycol.
Described ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent, in step 2,
Under 40V DC voltage, with step one gained Ti sheet as anode, with Pt sheet as negative electrode, anodic oxidation Ti sheet 4h in the electrolytic solution.
Above-mentioned ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent, forging in step 3
Burning temperature is 450 ° of C, and calcination time is 2h.
Ferrum, nitrogen, fluorine that ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent prepare are co-doped with
Miscellaneous titanium dioxide nanotube array photocatalyst.
Ferrum, nitrogen, fluorine that ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent prepare are co-doped with
The application in degradable organic pollutant of the miscellaneous titanium dioxide nanotube array photocatalyst.
Beneficial effect
First, the present invention utilizes electrochemistry anodic oxidation, containing deionized water, ferric nitrate, the ethylene glycol electricity of ammonium fluoride
Solve in liquid, aoxidize titanium sheet, prepared unformed Nano tube array of titanium dioxide, then in high-temperature calcination under nitrogen atmosphere, make
Standby go out crystal formation is good, photoelectric properties are good ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent；
Second, the present invention is with nitrogen-doped titanium dioxide so that it is have narrower band gap width and higher visible absorption
Ability, widens its absorption region at visible ray effectively；With ferrum and Fluorin doped titanium dioxide, reduce its light induced electron and sky
The recombination probability in cave, improves the efficiency of its opto-electronic conversion, thus improves the concentration of hydroxyl radical free radical in light reaction procedure,
In photocatalysis degradation organic contaminant is such as the research of phenol, show good visible light photocatalysis performance；
3rd, preparation method technique of the present invention is simple and convenient to operate, and gained catalyst low cost, recovery facilitate, will not produce
Raw secondary pollution and repeatable utilization, is effectively increased utilization rate and the quantum efficiency of solar energy, organic at photocatalytic degradation
The field such as pollutant, Solar use has broad application prospects.
Accompanying drawing explanation
Fig. 1 be embodiment 1 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent scanning electron show
Micro mirror figure；
Fig. 2-a is embodiment 1 gained ferrum, nitrogen, the X-ray light of fluorin-doped titanium dioxide nanotube array photo catalysis agent
The full spectrogram of electronics；
Fig. 2-b is the X-of the N 1s of embodiment 1 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent
X-ray photoelectron spectroscopy X figure；
Fig. 2-c is the X-of the F 1s of embodiment 1 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent
X-ray photoelectron spectroscopy X figure；
Fig. 2-d is the X-of the Fe 2p of embodiment 1 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent
X-ray photoelectron spectroscopy X figure；
Fig. 3 be embodiment 3 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent scanning electron show
Micro mirror figure；
When Fig. 4 is embodiment 1 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent degradation of phenol
Phenol surplus ratio-time history；
When Fig. 5 is embodiment 1 gained ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent degradation of phenol
Phenol surplus ratio-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 example.Institute
Method of stating is conventional method if no special instructions.Described raw material the most all can obtain from open commercial sources.
Embodiment 1
Being polished by Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph, until surface cleaning is smooth, then it is mixed to immerse strong acid
Close solution (HF:HNO3: H2O=1:4:5 volume ratio) in carry out chemical polishing 30s, the most respectively with acetone soln, dehydrated alcohol,
Deionized water ultrasonic cleaning 10min.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, standby.At 40V direct current
Under voltage, with Ti sheet as anode, Pt sheet is negative electrode, containing 2wt% deionized water, 0.2wt% Fe(NO3)39H2O, 0.3wt% fluorination
Ammonium, surplus is in the electrolyte of ethylene glycol, anodic oxidation Ti sheet 4h, prepares unformed TiO2Nano-tube array.By gained
TiO2Nano-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,
Make its crystallization forming, ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent.
Pattern with sem observation gained catalyst.As shown in Figure 1, the nanotube obtained by above method
Glittering and translucent, the every separate arrangement of nanotube, it can thus be appreciated that the doping of three kinds of elements does not affect its nano-tube array
Appearance structure.Its caliber is about 80nm, and wall thickness is about 12nm, and pipe range is about 11 m.With x-ray photoelectron spectroscopy analyze ferrum,
Nitrogen, the chemical element composition of fluoro-Nano tube array of titanium dioxide and valence state thereof.From Fig. 2-a to Fig. 2-d, this nanotube by
Ti, O, N, F, Fe form, and N mainly exists with Ti-O-N, illustrate that N mainly exists with space N form, and F mainly exists with Ti-O-F,
Illustrate that F the most successfully instead of part TiO2O in lattice, for Fe2p, shows Fe at the peak of 709.86eV3+Existence,
Fe is described3+The most successfully it is doped into TiO2Lattice, instead of part Ti4+.Below ferrum, nitrogen, fluoro-titania nanotube are all proved
Array is successfully prepared.
Embodiment 2
Being polished by Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph, until surface cleaning is smooth, then it is mixed to immerse strong acid
Close solution (HF:HNO3: H2O=1:4:5 volume ratio) in carry out chemical polishing 30s, the most respectively with acetone soln, dehydrated alcohol,
Deionized water ultrasonic cleaning 10min.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, standby.At 40V direct current
Under voltage, with Ti sheet as anode, Pt sheet is negative electrode, containing 2wt% deionized water, 0.4wt% Fe(NO3)39H2O, 0.3wt% fluorination
Ammonium, surplus is in the electrolyte of ethylene glycol, anodic oxidation Ti sheet 4h, prepares unformed TiO2Nano-tube array.By gained
TiO2Nano-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,
Make its crystallization forming, i.e. can get ferrum, nitrogen, fluoro-Nano tube array of titanium dioxide.
Embodiment 3
Being polished by Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph, until surface cleaning is smooth, then it is mixed to immerse strong acid
Close solution (HF:HNO3: H2O=1:4:5 volume ratio) in carry out chemical polishing 30s, the most respectively with acetone soln, dehydrated alcohol,
Deionized water ultrasonic cleaning 10min.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, standby.At 40V direct current
Under voltage, with Ti sheet as anode, Pt sheet is negative electrode, containing 2wt% deionized water, 0.04wt% Fe(NO3)39H2O, 0.3wt% fluorine
Changing ammonium, surplus is in the electrolyte of ethylene glycol, anodic oxidation Ti sheet 4h, prepares unformed TiO2Nano-tube array.By gained
TiO2Nano-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 so that it is crystallization forming, i.e. can get ferrum, nitrogen, fluoro-Nano tube array of titanium dioxide.
With sem observation ferrum, nitrogen, the pattern of fluoro-Nano tube array of titanium dioxide.From the figure 3, it may be seen that prepare
The caliber of nanotube be about 80nm, wall thickness is about 12nm, and pipe range is about 11 m.Compared to Figure 1, do not change significantly.
Embodiment 4
Being polished by Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph, until surface cleaning is smooth, then it is mixed to immerse strong acid
Close solution (HF:HNO3: H2O=1:5:5 volume ratio) in carry out chemical polishing 10s, the most respectively with acetone soln, dehydrated alcohol,
Deionized water ultrasonic cleaning 5min.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, standby.At 20V unidirectional current
Pressure, with Ti sheet as anode, Pt sheet is negative electrode, containing 1wt% deionized water, 0.04wt% Fe(NO3)39H2O, 0.1wt% fluorination
Ammonium, surplus is in the electrolyte of ethylene glycol, anodic oxidation Ti sheet 2h, prepares unformed TiO2Nano-tube array.By gained
TiO2Nano-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,
Make its crystallization forming, i.e. can get ferrum, nitrogen, fluoro-Nano tube array of titanium dioxide.
Embodiment 5
Being polished by Ti sheet (2cm × 2cm, 99.997%) abrasive paper for metallograph, until surface cleaning is smooth, then it is mixed to immerse strong acid
Close solution (HF:HNO3: H2O=1:6:7 volume ratio) in carry out chemical polishing 50s, the most respectively with acetone soln, dehydrated alcohol,
Deionized water ultrasonic cleaning 30min.Ti sheet after process is placed in air dry oven, dries in 80 ° of C, standby.At 60V direct current
Under voltage, with Ti sheet as anode, Pt sheet is negative electrode, containing 10wt% deionized water, 0.04wt% Fe(NO3)39H2O, 2wt% fluorination
Ammonium, surplus is in the electrolyte of ethylene glycol, anodic oxidation Ti sheet 8h, prepares unformed TiO2Nano-tube array.By gained
TiO2Nano-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,
Make its crystallization forming, i.e. can get ferrum, nitrogen, fluoro-Nano tube array of titanium dioxide.
Application examples 1 ferrum, nitrogen, the fall of fluorin-doped titanium dioxide nanotube array photo catalysis agent Pyrogentisinic Acid under visible light
Solve:
With the prepared ferrum of embodiment 1, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol under visible light.Photocatalysis light
Source is 300w high pressure xenon lamp, and xenon lamp is cooled down by the condensed water in quartz double-jacket.Light-catalyzed reaction instrument is tested,
By being covered with ferrum, nitrogen, that the titanium sheet of fluoro-Nano tube array of titanium dioxide vertically puts into the phenol that 50mL mass concentration is 10mg/L is water-soluble
In liquid.When reacting initial, first by phenol solution magnetic agitation 30min in the dark state to guarantee that reactant is at catalyst surface
Reach adsorption equilibrium.Then illumination 240min, takes a sample at interval of a period of time, the most about samples 0.5mL.Photocatalysis is dropped
Always with magnetic agitation in solution preocess.
The concentration of Phenol in Aqueous Solution, measures with chromatograph of liquid (Agilent 1220 Infinity LC, the U.S.), flowing
Being methanol and water (v/v=7: 3, flow velocity is 1mL/min) mutually, phenol maximal ultraviolet detection absorbing wavelength is 270nm.According to dense
Degree calculates the palliating degradation degree of phenol.The surplus ratio of phenol and the relation curve of time such as Fig. 4.As shown in Figure 4, light degradation speed is normal
Number size orders as follows: ferrum, nitrogen, fluoro-titanium dioxide (k obs = 0.00531min-1) > TiO2 (k obs = 0.00026min-1), ferrum, nitrogen, fluoro-titania nanotube degradation rate constant than pure TiO2Nanotube is much bigger, and the association of Fe, N and F is described
Same-action greatly increases TiO2The photocatalysis performance of the visible ray of nanotube.
Application examples 2 ferrum, nitrogen, the fall of fluorin-doped titanium dioxide nanotube array photo catalysis agent Pyrogentisinic Acid under visible light
Solve:
With the prepared ferrum of embodiment 2, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol under visible light.Photocatalysis light
Source is 300w high pressure xenon lamp, and xenon lamp is cooled down by the condensed water in quartz double-jacket.Light-catalyzed reaction instrument is tested,
By being covered with ferrum, nitrogen, that the titanium sheet of fluoro-Nano tube array of titanium dioxide vertically puts into the phenol that 50mL mass concentration is 10mg/L is water-soluble
In liquid.When reacting initial, first by phenol solution magnetic agitation 30min in the dark state to guarantee that reactant is at catalyst surface
Reach adsorption equilibrium.Then illumination 240min, takes a sample at interval of a period of time, the most about samples 0.5mL.Photocatalysis is dropped
Always with magnetic agitation in solution preocess.
The concentration of Phenol in Aqueous Solution, measures with chromatograph of liquid (Agilent 1220 Infinity LC, the U.S.), flowing
Being methanol and water (v/v=7: 3, flow velocity is 1mL/min) mutually, phenol maximal ultraviolet detection absorbing wavelength is 270nm.According to dense
Degree calculates the palliating degradation degree of phenol.
Application examples 3 ferrum, nitrogen, the fall of fluorin-doped titanium dioxide nanotube array photo catalysis agent Pyrogentisinic Acid under visible light
Solve:
With the prepared ferrum of embodiment 3, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol under visible light.Photocatalysis light
Source is 300w high pressure xenon lamp, and xenon lamp is cooled down by the condensed water in quartz double-jacket.Light-catalyzed reaction instrument is tested,
By being covered with ferrum, nitrogen, that the titanium sheet of fluoro-Nano tube array of titanium dioxide vertically puts into the phenol that 50mL mass concentration is 10mg/L is water-soluble
In liquid.When reacting initial, first by phenol solution magnetic agitation 30min in the dark state to guarantee that reactant is at catalyst surface
Reach adsorption equilibrium.Then illumination 240min, takes a sample at interval of a period of time, the most about samples 0.5mL.Photocatalysis is dropped
Always with magnetic agitation in solution preocess.
The concentration of Phenol in Aqueous Solution, measures with chromatograph of liquid (Agilent 1220 Infinity LC, the U.S.), flowing
Being methanol and water (v/v=7: 3, flow velocity is 1mL/min) mutually, phenol maximal ultraviolet detection absorbing wavelength is 270nm.According to dense
Degree calculates the palliating degradation degree of phenol.
Application examples 4 reuses ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent degradation of phenol:
Under visible light, the prepared ferrum of recycling embodiment 1, nitrogen, fluoro-Nano tube array of titanium dioxide degradation of phenol.
Photocatalysis light source is 300w high pressure xenon lamp, and xenon lamp is cooled down by the condensed water in quartz double-jacket.In light-catalyzed reaction instrument
Testing, by being covered with ferrum, vertically to put into 50mL mass concentration be 10mg/L for nitrogen, the titanium sheet of fluoro-Nano tube array of titanium dioxide
Phenol solution in.When reacting initial, first phenol solution is stirred in the dark state 30min to guarantee that reactant is in catalysis
Agent surface reaches adsorption equilibrium.Then illumination 240min, takes a sample at interval of a period of time, the most about samples 0.5mL.Light
Always with magnetic agitation during catalytic degradation.The experiment condition of recycling is identical every time, uses same Fe, N, F-
TiO2Nano-tube array, after each illumination 240min terminates, cleans 6 times with deionized water, places in baking oven and dry under 100 ° of C
2h, in order to next time use.
The concentration of Phenol in Aqueous Solution, measures with chromatograph of liquid (Agilent 1220 Infinity LC, the U.S.), flowing
Being methanol and water (v/v=7: 3, flow velocity is 1mL/min) mutually, phenol maximal ultraviolet detection absorbing wavelength is 270nm.According to dense
Degree calculates the palliating degradation degree of phenol.The surplus ratio of phenol and the relation curve such as Fig. 5 reusing number of times.As shown in Figure 5, when
When ferrum, nitrogen, fluoro-Nano tube array of titanium dioxide reuse 4 times, the degradation efficiency of its Pyrogentisinic Acid the most significantly reduces.
And owing to being grown on Ti sheet, very convenient recycling, secondary pollution can't be produced, thus, it can be known that ferrum, nitrogen,
Fluoro-Nano tube array of titanium dioxide is the visible-light photocatalyst of a kind of highly effective and repeatable utilization, can be applicable to reality
During border produces.
Claims (6)
1. ferrum, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent, it is characterised in that step is such as
Under:
Step one: polished smooth by Ti sheet, immerses in strong acid mixed liquor, chemical polishing 10 ~ 50s, after successively by acetone, anhydrous second
Alcohol, deionized water each ultrasonic cleaning 5 ~ 30min, post-drying is standby；Wherein said strong acid mixed liquor is HF and HNO3And H2O's is mixed
Close liquid, HF, HNO3And H2The volume ratio of O is 1 ~ 2:4 ~ 10:5 ~ 10；
Step 2: under 20-60V DC voltage, with step one gained Ti sheet as anode, with Pt sheet as negative electrode, in the electrolytic solution
Anodic oxidation Ti sheet 2 ~ 8h, obtains unformed Nano tube array of titanium dioxide, and described electrolyte includes according to mass percent
Following component: deionized water 1-10wt%, Fe(NO3)39H2O 0.04-0.4wt%, ammonium fluoride 0.1-2wt%, surplus is ethylene glycol；
Step 3: by unformed for step 2 gained Nano tube array of titanium dioxide high-temperature calcination under nitrogen atmosphere, calcining heat
For 400-600 ° of C, calcination time is 1-4h so that it is crystallization forming, obtains ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array
Photocatalyst.
Ferrum the most according to claim 1, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent,
It is characterized in that, in step one, HF, HNO3And H2The volume ratio of O is 1:4:5.
Ferrum the most according to claim 1 and 2, nitrogen, the preparation side of fluorin-doped titanium dioxide nanotube array photo catalysis agent
Method, it is characterised in that in step 2, under 40V DC voltage, with step one gained Ti sheet as anode, with Pt sheet as negative electrode,
Electrolyte Anodic Oxidation Ti sheet 4h.
Ferrum the most according to claim 3, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent,
It is characterized in that, the calcining heat in step 3 is 450 ° of C, and calcination time is 2h.
5. ferrum described in claim 1, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent prepare
Ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent.
6. ferrum described in claim 1, nitrogen, the preparation method of fluorin-doped titanium dioxide nanotube array photo catalysis agent prepare
Ferrum, nitrogen, fluorin-doped titanium dioxide nanotube array photo catalysis agent application in degradation of phenol.
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