CN107557789B - A kind of optical anode material and its preparation and application - Google Patents
A kind of optical anode material and its preparation and application Download PDFInfo
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- CN107557789B CN107557789B CN201710804169.6A CN201710804169A CN107557789B CN 107557789 B CN107557789 B CN 107557789B CN 201710804169 A CN201710804169 A CN 201710804169A CN 107557789 B CN107557789 B CN 107557789B
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Abstract
The present invention relates to nanotube array photo-anode, especially a kind of stabilization is used for the BiVO of photoproduction cathodic protection4/TiO2Nanotube array photo-anode material and its preparation and application.It is to electrode with Pt, titanium sheet substrate is working electrode, with NH first by anodizing4F and ethylene glycol solution are electrolyte, then titanium sheet is calcined, and prepare TiO in titanium plate surface2Nano-pipe array thin film；Later by hydro-thermal method, prepare respectively with Bi (NO)3And NH4VO3For the reaction solution in bismuth source and vanadium source, by TiO2Nano-pipe array thin film is totally submerged in reaction solution, is placed in baking oven after incubation water heating, then obtains BiVO through calcination processing4/TiO2Composite membrane.BiVO of the invention4/TiO2Visible light utilization efficiency can be improved as the light anode of photoproduction cathodic protection in composite membrane, hence it is evident that reduces the corrosion potential of 304 stainless steels, still has preferable cathodic protection anti-corrosion effect under dark-state.
Description
Technical field
The present invention relates to nanotube array photo-anode, especially a kind of stabilization is used for the BiVO of photoproduction cathodic protection4/TiO2
Nanotube array photo-anode material and its preparation and application.
Background technique
Metal erosion refers to the destruction that metal occurs under various environmental conditions and goes bad.Under room temperature, electrochemistry approach is made
At corrosion account for the overwhelming majority of metal erosion.By estimation, because of corrosion, irretrievable metal material accounts for total amount every year in the world
1/10th.Metal erosion spreads national economy every field, may result in the destruction of pipeline and equipment, the pollution of product
Etc. some serious accidents, heavy losses and harm are caused to economy and society.304 stainless steels (304SS) are due to its excellent power
It learns, corrosion-resistant and welding performance, is used widely in numerous areas, such as aerospace, communications and transportation, petrochemical industry and engineering
Building etc..Although stainless steel surface can form the generation that fine and close passivating film prevents corrosion under atmospheric environment, big in ocean
Under the harsh environments such as gas, passivating film is easily destroyed by chloride ion etc. and causes more serious local corrosion.
Traditional electrochemical protection method needs to consume a large amount of anode material or need to provide a large amount of electric energy.The nearly more than ten years
Come, photoproduction cathode protection technology is with TiO2Equal semiconductor materials are not required to consumable anode as photoelectric conversion center；It is honest and clean using cleaning
The solar energy resources of valence, do not consume electric energy；And the requirement of film coverage rate is low, operability is stronger, becomes the focus of people's research.However
TiO2Forbidden bandwidth is wider (3.2eV), low to visible light utilization ratio, the ultraviolet light of 380nm can only be less than using wavelength, but purple
Outer light only accounts for 5% or so of sunlight, and light induced electron and hole-recombination rate make TiO fastly2It cannot in the dark state be metal
Effective protection is provided.Therefore it is badly in need of being able to solve TiO2And in the dark state photoproduction cathode low to sun light utilization efficiency and photoelectric efficiency
The method of protective effect.
Summary of the invention
The purpose of the present invention is to provide a kind of optical anode material and its preparations and application.
To achieve the above object, the invention adopts a technical scheme as:
A kind of optical anode material successively modifies to obtain TiO through anodic oxidation, calcining to titanium plate surface2Nano-pipe array thin film,
Then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain optical anode material BiVO4/TiO2Composite membrane.
A kind of preparation method of optical anode material successively modifies to obtain TiO through anodic oxidation, calcining to titanium plate surface2Nanometer
Pipe array film, then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain optical anode material BiVO4/
TiO2Composite membrane.
The TiO2Nano-pipe array thin film be using treated Titanium base as anode, in the presence of electrolyte in 20~
30V voltage 1~2h of anodic oxygenization, cleans after oxidation, dries；Then in Muffle furnace with the heating rate liter of 1~5 DEG C/min
To 400~500 DEG C, and 1~3h of constant temperature, cooling near room temperature have TiO in titanium-based piece surface modification2Film of Nano tube array.
The electrolyte that the anodic oxidation uses is ethylene glycol and NH4The mixed liquor of F aqueous solution；Wherein, ethylene glycol and NH4F
For aqueous solution volume ratio 10~20, the mass fraction of ammonium fluoride is 3~7wt.%.
It is described to be modified with TiO2Substrate is placed in autoclave and seals, and contains Bi (NO) in excessive3Reaction solution in,
In 160~200 DEG C of 5~7h of hydro-thermal reaction, cooled to room temperature, then through the deionized water, cleaning of ethyl alcohol alternate repetition, dry,
180~220 DEG C and 1~3h of constant temperature then are raised to the heating rate of 1~5 DEG C/min, room temperature is cooled to the furnace and obtains light anode material
Expect BiVO4/TiO2Composite membrane.
It is described to contain Bi (NO)3Reaction solution be Bi (NO)3Aqueous solution of nitric acid, NH4VO3Sodium hydrate aqueous solution and
The mixed solution of sodium citrate, wherein molar ratio Bi (NO)3:NH4VO3Molar ratio 1~1.5, sodium citrate final concentration of 2~
5mol/L。
The Bi (NO)3Aqueous solution of nitric acid be Bi (NO) that molar concentration is 0.05~0.1mol/L3It is with molar concentration
The HNO of 2~4mol/L3Mixed liquor；Wherein, HNO3:Bi(NO)3Molar ratio is 30~50；
NH4VO3Sodium hydrate aqueous solution be NH that molar concentration is 0.05~0.1mol/L4VO3It is 2 with molar concentration
The mixed liquor of the NaOH of~4mol/L；Wherein, NaOH:NH4VO3Molar ratio is 30~50.
A kind of application of optical anode material, the optical anode material is in as the anti-corrosion protective film for inhibiting metal erosion
Application.
The reaction that the process mainly occurs is Bi (NO3)3Hydrolysis generates sl. sol. BiONO3, then BiONO3Again with VO3 -It is raw
Yellowly precipitate B iVO4, chemical equation are as follows:
Bi(NO3)3+H2O=2HNO3+BiONO3
BiONO3+VO3 -=BiVO4+NO3 -
By the BiVO of above-mentioned preparation4/TiO2Composite membrane carries out the photoproduction cathodic protection effect to 304SS as light anode
Test: the specific double-electrolyzer system using photoelectrolytic cell and corrosion electrolytic cell composition.BiVO4/TiO2Composite membrane is light anode,
It is placed in photoelectrolytic cell, wherein electrolyte is 0.1mol/L Na2SO3Solution.Corrosion electrolytic cell is three-electrode system, working electrode
It is Pt electrode to electrode, reference electrode is saturated calomel electrode (SCE), with 3.5wt.% for protected metal (304SS)
NaCl solution is corrosive medium.Light anode is connected to working electrode, photoelectrolytic cell by conducting wire with protected metal electrode
It is connect with corrosion electrolytic cell by salt bridge (agar of the KCl containing saturation).(add ultraviolet using 300W high pressure Xe lamp as visible light source
Light optical filter, so that optical source wavelength >=400nm), direct irradiation TiO in photoelectrolytic cell2Composite film surface uses electrochemical operation
It stands potential change of the test electrode potential before and after illumination.Schematic device is as shown in Figure 1.
Basic principle of the invention:
BiVO is mapped in illumination4/TiO2On composite membrane, due to BiVO4Forbidden bandwidth is relatively narrow, and photoresponse is wide, valence-band electrons
Conduction band is transitted to by incident photon excitation first, forms photo-generate electron-hole pair.Again since its conduction band current potential is higher than TiO2, produce
Raw electrons are injected into the wider TiO of forbidden bandwidth2Conduction band on, further migrate, lead to the lower metal surface of potential
Metal surface electron density is caused to increase, electrode potential reduces, even much lower than the spontaneous corrosion potential of metal, steady into thermodynamics
State area, that is, cathode protecting state, and from environmental corrosion.And hole can be from TiO2Valence band is transferred to BiVO4Valence band, to realize
Electron-hole efficiently separates, and makes electronics that transition can occur under the excitation of smaller luminous energy, substantially increases the benefit of sunlight
With rate.
Advantage for present invention:
1) light anode BiVO of the present invention4/TiO2Composite nano tube array films have uniform caliber and complete coating, and
Due to the BiVO of low energy gap width4Modification make TiO2The absorption region of light is widened, the utilization rate of sunlight is promoted.
2) by light anode BiVO4/TiO2Composite membrane is placed in electrolyte solution and carries out light with being connected by protection 304SS
Raw cathodic protection test, when showing the radiation of visible light composite membrane, 304SS electrode potential is minimum to fall to approximately -570mV, under
About 500mv has been dropped, its corrosion potential is far below, thus can be effectively protected；
After illumination stops, 304SS electrode potential rises to -400mv or so, but still well below its corrosion potential,
Show BiVO in the dark state4/TiO2Composite membrane still has good cathodic protection anticorrosion ability to 304SS.
In conclusion the present invention modifies TiO in titanium plate surface by anodizing2Nano-pipe array thin film, using water
Thermal method is in above-mentioned TiO2Film surface modifies BiVO4, obtained BiVO4/TiO2Composite nano tube array films are a kind of excellent light
Anode material is soaked in obtained composite membrane and titanium sheet substrate in electrolyte solution as light anode, connects with by protection metal
It connects, plays excellent and stable anticorrosion ability to metal using photoproduction cathodic protection effect.
Detailed description of the invention
Fig. 1 is photoproduction cathodic protection double-electrolyzer system schematic.
Fig. 2 a is TiO provided in an embodiment of the present invention2The surface topography (SEM figure) of nano thin-film, scale are 2 μm, illustration
Scale is 100nm.
Fig. 2 b is BiVO provided in an embodiment of the present invention4/TiO2The surface topography (SEM figure) of composite membrane, scale are 2 μm.
Fig. 3 is used TiO provided in an embodiment of the present invention2The BiVO of nano-tube film and preparation4/TiO2Composite membrane
X-ray diffraction spectrogram.
Fig. 4 is used TiO provided in an embodiment of the present invention2The BiVO of nano-tube film and preparation4/TiO2Composite membrane
Photogenerated current changes over time curve graph before and after illumination.Wherein, abscissa is the time (s), and ordinate is density of photocurrent (μ
A·cm-2).On indicates illumination, and off indicates to close light source, that is, dark-state.
Fig. 5 be 304SS provided in an embodiment of the present invention in 3.5wt.%NaCl solution respectively with TiO2Nano-tube film
And BiVO4/TiO2Composite film photo-anode connection, electrode potential changes over time curve before and after illumination.Wherein, abscissa is the time
(s), ordinate is electrode potential (V vs.SCE).On indicates illumination, and off indicates to close light source, that is, dark-state.
Fig. 6 a is TiO provided in an embodiment of the present invention2The surface topography (SEM figure) of nano thin-film, scale are 2 μm, illustration
Scale is 100nm.
Fig. 6 b is BiVO provided in an embodiment of the present invention4/TiO2The surface topography (SEM figure) of composite membrane, scale are 2 μm.
Fig. 7 is used TiO provided in an embodiment of the present invention2The BiVO of nano-tube film and preparation4/TiO2Composite membrane
X-ray diffraction spectrogram.
Fig. 8 is used TiO provided in an embodiment of the present invention2The BiVO of nano-tube film and preparation4/TiO2Composite membrane
Photogenerated current changes over time curve graph before and after illumination.Wherein, wherein abscissa is the time (s), and ordinate is that photoelectric current is close
Spend (μ Acm-2).On indicates illumination, and off indicates to close light source, that is, dark-state.
Fig. 9 be 304SS provided in an embodiment of the present invention in 3.5wt.%NaCl solution respectively with TiO2Nano-tube film
And BiVO4/TiO2Composite film photo-anode connection, electrode potential changes over time curve before and after illumination.Wherein, abscissa is the time
(s), ordinate is electrode potential (V vs.SCE).On indicates illumination, and off indicates to close light source, that is, dark-state.
Specific embodiment
Explanation that the present invention will be further explained with reference to the accompanying drawings and examples.
The present invention passes through anodizing first, is to electrode with Pt, titanium sheet substrate is working electrode, with NH4F and second two
Alcoholic solution is electrolyte, then titanium sheet is calcined, and prepares TiO in titanium plate surface2Nano-pipe array thin film；Pass through hydro-thermal later
Method is prepared respectively with Bi (NO)3And NH4VO3For the reaction solution in bismuth source and vanadium source, by TiO2Nano-pipe array thin film is totally submerged
It in reaction solution, is placed in baking oven after incubation water heating, then obtains BiVO through calcination processing4/TiO2Composite membrane.BiVO of the invention4/
TiO2Visible light utilization efficiency can be improved as the light anode of photoproduction cathodic protection in composite membrane, hence it is evident that reduces the corruption of 304 stainless steels
Current potential is lost, still there is preferable cathodic protection anti-corrosion effect under dark-state.
Embodiment 1
The preparation of light anode, comprising the following steps:
The pretreatment of titanium substrate: from the titanium sheet that cut size is 20*15mm on 0.1mm thickness titanium foil (purity is greater than 99.9%)
As substrate, 1min is successively cleaned by ultrasonic in acetone, dehydrated alcohol and deionized water, then cleaned with ethyl alcohol, hair dryer drying
It is spare.Weigh 0.45g NH4F is dissolved in 2.5mL deionized water, sequentially adds 6mL H2O2It is commercially available dense with 6mL 65~68%
HNO3It is made into polishing fluid, the titanium sheet after cleaning is put into polishing fluid and polishes 1min, then is cleaned respectively with deionized water, ethyl alcohol,
Drying is stand-by.
TiO2Nano-tube array film preparation: 0.22g NH is weighed4F is dissolved in 4mL deionized water, and ultrasound is completely molten to it
Then 40mL ethylene glycol is added in solution, then ultrasound to two-phase is completely dissolved, as working solution.At room temperature, in working solution, with place
Titanium base after reason is anode, and Pt is to clean after oxidation through deionized water to electrode in 20V voltage anodic oxygen 1h, natural
It dries.Then sample is placed in Muffle furnace, 450 DEG C and constant temperature 2h is raised to the heating rate of 5 DEG C/min, close later power supply with
Furnace is cooled to room temperature.TiO is made in titanium plate surface2Film of Nano tube array is (referring to fig. 2 a).
BiVO4/TiO2The preparation of composite membrane: weighing the concentrated nitric acid of 3.8g (mass fraction 66.5%), is dissolved in 20mL and goes
In ionized water, 2mol/L HNO is obtained3Solution；1.60g NaOH is weighed, is dissolved in 20mL deionized water, 2mol/L NaOH is obtained
Solution.Weigh the Bi (NO of 0.49g3)3·5H2O is added to the above-mentioned acquisition 2mo1/L HNO of 20mL3In solution, magnetic force is stirred at room temperature
20min is mixed, Bi (NO) is obtained3Aqueous solution of nitric acid；Weigh the NH of 0.12g4VO3It is added to 20ml 2mol/L's obtained above
In NaOH solution, magnetic agitation 20min, obtains NH at room temperature4VO3Sodium hydrate aqueous solution.By Bi (NO)3Aqueous solution of nitric acid,
NH4VO3Sodium hydrate aqueous solution mixing after the sodium citrate of 0.09g is added, magnetic agitation 30min mixes them thoroughly uniformly,
Obtain reaction solution.By TiO2Nanotube is vertical or inclination is placed in 50mL autoclave, and above-mentioned reaction solution is slowly poured into instead
Kettle is answered until being totally submerged TiO2Nanotube, 180 DEG C, after hydro-thermal reaction 6h, cooled to room temperature spends obtained sample
Ionized water and dehydrated alcohol cross washing three times, are finally placed in 200 DEG C of calcining 2h in Muffle furnace and obtain regular BiVO4/TiO2It is multiple
Close film (referring to fig. 2 b).
To BiVO4/TiO2Composite membrane carries out photoproduction cathodic protection test: with BiVO4/TiO2Composite membrane is light anode, is placed in
Contain 0.1mol/L Na2SO3In the photoelectrolytic cell of solution, protected 304SS is working electrode, is placed in containing 3.5wt.%
In the corrosion electrolytic cell of NaCl medium.Light anode and 304SS are coupled by conducting wire together as working electrode, and Pt electrode is to electricity
Pole, saturated calomel electrode (SCE) are reference electrode.Photoelectrolytic cell and corrosion electrolytic cell pass through salt bridge (agar of the KCl containing saturation)
Connection.Using 300W Xe lamp as visible light source (adding uv filter, so that optical source wavelength >=400nm), direct irradiation in
BiVO in photoelectrolytic cell4/TiO2Laminated film surface.(referring to fig. 2~Fig. 5)
To characterize prepared TiO2Nano thin-film BiVO4/TiO2Composite film surface pattern tests its scanning electricity respectively
Mirror figure.By the visible TiO obtained of Fig. 2 a2Nano thin-film array is uniform, and internal diameter is about 60~70nm.The visible BiVO of Fig. 2 b4/TiO2
TiO is more uniformly adhered to double ball peanut shape structures2Nanotube nozzle, BiVO4The length of double ball particles is about 1 μm.
To characterize prepared TiO2Nano thin-film and BiVO4/TiO2The composition and structure of composite membrane test its X respectively and penetrate
Line diffraction spectra.As seen from Figure 3, TiO2There is the diffraction maximum and anatase of Ti (Titanium) substrate in nano thin-film XRD spectra
Type TiO2(AnataseTiO2) diffraction maximum, illustrate prepared TiO2TiO in nano thin-film2Exist with anatase crystal；It removes
Ti and TiO2Diffraction maximum outside, in BiVO4/TiO2Monocline scheelite type BiVO is had also appeared in the XRD spectra of composite membrane4
(Monoclinic BiVO4) diffraction maximum, and do not observe the apparent diffraction maximum of other impurity, illustrate the BiVO of modification4With pure
Monoclinic system scheelite phase structure exists.
To characterize prepared BiVO4/TiO2Composite membrane incident photon-to-electron conversion efficiency tests pure TiO2Film and BiVO4/TiO2It is compound
The transient state optogalvanic spectra of film.From fig. 4, it can be seen that pure TiO2Film transient state photoelectric current maximum value is about 2 μ Acm-2, when film surface is modified
BiVO4Afterwards, BiVO4/TiO2The transient state photoelectric current maximum value of composite membrane can be of about 120 μ Acm-2, considerably beyond pure TiO2Film
Transient state photocurrent values, and with the extension of light application time, current value is constantly becoming larger.This is primarily due to TiO2Upper deposition
BiVO4Afterwards, reduce the compound of electron-hole pair, increase the absorption to visible light, effectively increase the utilization to sunlight
Rate.
To test prepared BiVO4/TiO2304SS is placed in 3.5wt.%NaCl to the protecting effect of 304SS by composite membrane
Corrosion electrolyte in and respectively with pure TiO2Film and BiVO4/TiO2Composite membrane coupling is light anode, and recording electrode current potential is at any time
Between change curve.As seen from Figure 5, change with the switch electrode current potential of light source in phase step type, and reduce amplitude BiVO4/TiO2It is compound
Film is greater than pure TiO2Film.As 304SS and pure TiO2When film couples, 304SS electrode potential is down to about -350mV, naturally rotten lower than it
Current potential is lost, certain photoproduction cathodic protection effect is played.When with BiVO4/TiO2When composite membrane couples, 304SS electrode potential can drop
To about -570mV, about 500mV is reduced, is far below its spontaneous potential；When cutting off light source, 304SS electrode potential starts
It is gradually increasing, is still below and pure TiO2Couple electrode potential when simultaneously illumination；Illumination is carried out again, and the electrode potential of 304SS is again
It is rapidly decreased to -570mV or so, shows BiVO4/TiO2Composite membrane has good stability.
Embodiment 2
The preparation of light anode, comprising the following steps:
The pretreatment of titanium substrate: from the titanium sheet that cut size is 20*15mm on 0.1mm thickness titanium foil (purity is greater than 99.9%)
As substrate, 1min is successively cleaned by ultrasonic in acetone, dehydrated alcohol and deionized water, then cleaned with ethyl alcohol, hair dryer drying
It is spare.Weigh 0.45g NH4F is dissolved in 2.5mL deionized water, sequentially adds 6mL H2O2It is commercially available dense with 6mL 65~68%
HNO3It is made into polishing fluid, the titanium sheet after cleaning is put into polishing fluid and polishes 1min, then is cleaned respectively with deionized water, ethyl alcohol,
Drying is stand-by.
TiO2Nano-tube array film preparation: 0.22g NH is weighed4F is dissolved in 4mL deionized water, and ultrasound is completely molten to it
Then 40mL ethylene glycol is added in solution, then ultrasound to two-phase is completely dissolved, as working solution.At room temperature, in working solution, with place
Titanium base after reason is anode, and Pt is to electrode, and deionized water is cleaned after 20V voltage anodic oxygen 1h, naturally dry.Then
Sample is placed in Muffle furnace, is raised to 450 DEG C and constant temperature 2h with the heating rate of 5 DEG C/min, power supply is closed later and cools to the furnace
Room temperature.TiO is made in titanium plate surface2Film of Nano tube array.
BiVO4/TiO2The preparation of composite membrane: weighing the concentrated nitric acid of 7.6g (mass fraction 66.5%), is dissolved in 20mL and goes
In ionized water, the HNO of 4mol/L is obtained3Solution；3.2g NaOH is weighed, is dissolved in 20mL deionized water, the NaOH of 4mol/L is obtained
Solution.Weigh the Bi (NO of 0.98g3)3·5H2O is added to the HNO of the 4mo1/L of the above-mentioned acquisition of 20mL3In solution, magnetic at room temperature
Power stirs 20min, obtains Bi (NO)3Aqueous solution of nitric acid；Weigh the NH of 0.24g4VO3It is added to the 4mol/L of the above-mentioned acquisition of 20ml
NaOH solution in, magnetic agitation 20min, obtains NH at room temperature4VO3Sodium hydrate aqueous solution.By Bi (NO)3Nitric acid it is water-soluble
Liquid, NH4VO3Sodium hydrate aqueous solution mixing after the sodium citrate of 0.18g is added, magnetic agitation 30min mixes them thoroughly
It is even, obtain reaction solution.By TiO2Nanotube is vertical or inclination is placed in 50mL autoclave, and above-mentioned reaction solution is slowly poured into
Reaction kettle is until be totally submerged TiO2Nanotube, 180 DEG C, after hydro-thermal reaction 6h, cooled to room temperature uses obtained sample
Deionized water and dehydrated alcohol cross washing three times, are finally placed in 200 DEG C of calcining 2h in Muffle furnace and obtain regular BiVO4/TiO2
Composite membrane.
To BiVO4/TiO2Composite membrane carries out photoproduction cathodic protection test: with BiVO4/TiO2Composite membrane is light anode, is placed in
Contain 0.1mol/L Na2SO3In the photoelectrolytic cell of solution, protected 304SS is working electrode, is placed in containing 3.5wt.%
In the corrosion electrolytic cell of NaCl medium.Light anode and 304 stainless steels are coupled by conducting wire together as working electrode, and Pt electrode is
To electrode, saturated calomel electrode (SCE) is reference electrode.Photoelectrolytic cell and corrosion electrolytic cell pass through the salt bridge (fine jade of the KCl containing saturation
Rouge) connection.Using 300W Xe lamp as visible light source (adding uv filter, so that optical source wavelength >=400nm), directly shine
Penetrate the BiVO in photoelectrolytic cell4/TiO2Laminated film surface.(referring to Fig. 6~Fig. 9)
To characterize prepared TiO2Nano thin-film BiVO4/TiO2Composite film surface pattern tests its scanning electricity respectively
Mirror figure.By the visible TiO obtained of Fig. 6 a2Nano thin-film array is uniform, and internal diameter is about 60~70nm.The visible BiVO of Fig. 6 b4/TiO2
TiO is more uniformly adhered to ellipsoid structure2Nanotube nozzle, BiVO4The length of ellipsoid particle is about 0.5~1 μm.
To characterize prepared TiO2Nano thin-film and BiVO4/TiO2The composition and structure of composite membrane test its X respectively and penetrate
Line diffraction spectra.As seen from Figure 7, TiO2There is the diffraction maximum and anatase of Ti (Titanium) substrate in nano thin-film XRD spectra
Type TiO2(Anatase TiO2) diffraction maximum, illustrate prepared TiO2TiO in nano thin-film2Exist with anatase crystal；It removes
Ti and TiO2Diffraction maximum outside, in BiVO4/TiO2Monocline scheelite type BiVO is had also appeared in the XRD spectra of composite membrane4
(Monoclinic BiVO4) diffraction maximum, and do not observe the apparent diffraction maximum of other impurity, illustrate the BiVO of modification4With pure
Monoclinic system scheelite phase structure exists.But compared with Example 1, BiVO4Diffraction maximum peak intensity obviously weaken, show the condition
The BiVO of lower preparation4Crystallinity is not good enough.
To characterize prepared BiVO4/TiO2Composite membrane incident photon-to-electron conversion efficiency tests pure TiO2Film and BiVO4/TiO2It is compound
The transient state optogalvanic spectra of film.As seen from Figure 8, pure TiO2Film transient state photoelectric current maximum value is about 2 μ Acm-2, when film surface is modified
BiVO4Afterwards, BiVO4/TiO2The transient state photoelectric current maximum value of composite membrane can be of about 25 μ Acm-2, far more than pure TiO2Film it is temporary
State photocurrent values, and with the extension of light application time, current value is constantly becoming larger.This is primarily due to TiO2Upper deposition BiVO4
Afterwards, reduce the compound of electron-hole pair, increase the absorption to visible light, effectively increase the utilization rate to sunlight.But
Transient current value is more many than reducing in embodiment 1, this may be because reaction reagent concentration doubles to cause BiVO4Pattern knot
The difference of structure affects the transmission of charge so as to cause the difference of specific surface area, crystallinity etc..
To test prepared BiVO4/TiO2304SS is placed in the protecting effect of 304SS by composite film photo-anode
In the corrosion electrolyte of 3.5wt.%NaCl and respectively with pure TiO2Film and BiVO4/TiO2Composite membrane coupling is light anode, record
Electrode potential changes over time curve.As seen from Figure 9, change with the switch electrode current potential of light source in phase step type, and reduce amplitude
BiVO4/TiO2Composite membrane is greater than pure TiO2Film.As 304SS and pure TiO2Film couple when, 304SS electrode potential be down to about-
350mV is lower than its spontaneous potential, plays certain photoproduction cathodic protection effect.When with BiVO4/TiO2Composite membrane coupling
When, 304SS electrode potential can be down to about -500mV, reduce about 300mV, be far below its spontaneous potential；When cutting light source
When, 304SS electrode potential starts to gradually rise up to -350mV or so, but is still below 304SS and pure TiO under this state2Coupling
Even current potential；Illumination is carried out again, and the electrode potential of 304SS is rapidly decreased to -500mV or so again, shows BiVO4/TiO2Composite membrane is steady
It is qualitative good.
Above-described embodiment is better embodiment of the present invention, but embodiments of the present invention are not by the limit of above-described embodiment
System, other are any without departing from made changes, modifications, substitutions, combinations, simplifications under spirit of the invention and principle, should be
Equivalent substitute mode, is included within the scope of the present invention.
Claims (4)
1. a kind of optical anode material, it is characterised in that: successively modify to obtain TiO through anodic oxidation, calcining to titanium plate surface2Nanotube
Array film, then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain optical anode material BiVO4/
TiO2Composite membrane；
The preparation method of the optical anode material is successively to modify to obtain TiO through anodic oxidation, calcining to titanium plate surface2Nanotube battle array
Column film, then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain optical anode material BiVO4/TiO2
Composite membrane；
The TiO2Nano-pipe array thin film is using treated titanium sheet as anode, in 20~30 V electricity in the presence of electrolyte
1~2 h of anodic oxidation is depressed, cleans, dry after oxidation；Then in being raised in Muffle furnace with the heating rate of 1~5 DEG C/min
400~500 DEG C, and 1~3 h of constant temperature, cooling near room temperature are modified with TiO in titanium plate surface2Film of Nano tube array；
The electrolyte that the anodic oxidation uses is ethylene glycol and NH4The mixed liquor of F aqueous solution；Wherein, ethylene glycol and NH4F is water-soluble
For liquid volume ratio 10~20, the mass fraction of ammonium fluoride is 3~7 wt.%；
It is modified with TiO2Titanium sheet be vertically arranged in autoclave and seal, contain Bi (NO) in excessive3Reaction solution in, In
160~200 DEG C of 5~7 h of hydro-thermal reaction, cooled to room temperature, then through deionized water, the cleaning of ethyl alcohol alternate repetition, drying, and
180~220 DEG C and 1~3 h of constant temperature are raised to the heating rate of 1~5 DEG C/min afterwards, room temperature is cooled to the furnace and obtains optical anode material
BiVO4/TiO2Composite membrane.
2. the preparation method of optical anode material according to claim 1, it is characterised in that:
It is described to contain Bi (NO)3Reaction solution be Bi (NO)3Aqueous solution of nitric acid, NH4VO3Sodium hydrate aqueous solution and citric acid
The mixed solution of sodium, wherein molar ratio Bi (NO)3: NH4VO3Molar ratio is 1~1.5, the final concentration of 2 ~ 5mol/ of sodium citrate
L。
3. the preparation method of optical anode material as described in claim 2, it is characterised in that:
The Bi (NO)3Aqueous solution of nitric acid be Bi (NO) that molar concentration is 0.05~0.1 mol/L3With molar concentration be 2~
The HNO of 4 mol/L3Mixed liquor；Wherein, HNO3: Bi(NO)3Molar ratio is 30~50；
NH4VO3Sodium hydrate aqueous solution be NH that molar concentration is 0.05~0.1 mol/L4VO3It is 2~4 with molar concentration
The mixed liquor of the NaOH of mol/L；Wherein, NaOH:NH4VO3Molar ratio is 30~50.
4. a kind of application of optical anode material described in claim 1, it is characterised in that: the optical anode material is as inhibition
Application in the anti-corrosion protective film of metal erosion.
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