CN107557789A - A kind of light anode material and its preparation and application - Google Patents

A kind of light anode material and its preparation and application Download PDF

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CN107557789A
CN107557789A CN201710804169.6A CN201710804169A CN107557789A CN 107557789 A CN107557789 A CN 107557789A CN 201710804169 A CN201710804169 A CN 201710804169A CN 107557789 A CN107557789 A CN 107557789A
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tio
bivo
anode material
light anode
film
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CN107557789B (en
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王秀通
李鑫冉
宁晓波
雷婧
王文成
李红玲
黄彦良
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Institute of Oceanology of CAS
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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.First by anodizing, using Pt as to electrode, titanium sheet substrate is working electrode, with NH4F and ethylene glycol solution are electrolyte, then titanium sheet is calcined, and TiO is prepared in titanium plate surface2Nano-pipe array thin film；Afterwards 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.The BiVO of the present invention4/TiO2Composite membrane, as the light anode of photoproduction cathodic protection, visible light utilization efficiency can be improved, hence it is evident that reduce the corrosion potential of 304 stainless steels, still there is preferable cathodic protection antiseptic effect under dark-state.

Description

A kind of light anode material and its preparation and application
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 technology
Metal erosion refers to the destruction that metal occurs under various environmental conditions and rotten.Under normal temperature, electrochemistry approach is made Into 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 may result in destruction, the pollution of product of pipeline and equipment throughout national economy every field Deng some serious accidents, heavy losses and harm are caused to economy and society.304 stainless steels (304SS) are due to its excellent power Learn, corrosion-resistant and welding performance, be used widely in numerous areas, such as Aero-Space, communications and transportation, petrochemical industry and engineering Building etc..Although stainless steel surfaces can form the generation of the passivating film prevention corrosion of densification under atmospheric environment, big in ocean Under the severe rugged environments such as gas, passivating film is easily destroyed by chlorion etc. and triggers more serious local corrosion.
Traditional electrochemical protection method needs to consume substantial amounts 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 TiO2Deng semi-conducting material as photoelectric conversion center, consumable anode is not required to；It is honest and clean using cleaning The solar energy resources of valency, does not consume electric energy；And film coverage rate requires low, operability is stronger, turns into the focus of people's research.But TiO2Energy gap is wider (3.2eV), low to visible light utilization ratio, the ultraviolet light that wavelength can only be utilized to be less than 380nm, but purple Outer light only accounts for 5% of sunshine or so, and light induced electron and hole-recombination speed make TiO soon2Can not be metal in the dark state Effectively protection is provided.Therefore it is badly in need of can solve the problem that TiO2And in the dark state photoproduction negative electrode low to sun light utilization efficiency and photoelectric efficiency The method of protective effect.
The content of the invention
It is an object of the invention to provide a kind of light anode material and its preparation and application.
To achieve the above object, the present invention use technical scheme for：
A kind of light anode material, TiO is modified to obtain through anodic oxidation, calcining to titanium plate surface successively2Nano-pipe array thin film, Then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain light anode material BiVO4/TiO2Composite membrane.
A kind of preparation method of light anode material, TiO is modified to obtain through anodic oxidation, calcining to titanium plate surface successively2Nanometer Pipe array film, then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain light anode material BiVO4/ TiO2Composite membrane.
The TiO2Nano-pipe array thin film be using the Titanium base after processing as anode, in the presence of electrolyte in 20~ 30V voltage 1~2h of anodic oxygenization, clean after oxidation, dry；And after in Muffle furnace with 1~5 DEG C/min heating rate liter To 400~500 DEG C, and 1~3h of constant temperature, near room temperature is cooled down, i.e., has 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 the 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 sealed, and contains Bi (NO) in excess3Reaction solution in, In 160~200 DEG C of 5~7h of hydro-thermal reaction, room temperature is naturally cooled to, then cleans, dry through deionized water, ethanol alternate repetition, 180~220 DEG C and 1~3h of constant temperature then are raised to 1~5 DEG C/min heating rate, 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, mol ratio Bi (NO)3:NH4VO3Mol 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 2~4mol/L HNO3Mixed liquor；Wherein, HNO3:Bi(NO)3Mol ratio is 30~50；
NH4VO3Sodium hydrate aqueous solution be NH that molar concentration is 0.05~0.1mol/L4VO3It is 2 with molar concentration ~4mol/L NaOH mixed liquor；Wherein, NaOH:NH4VO3Mol ratio is 30~50.
A kind of application of light anode material, the light anode material is in as the anti-corrosion protective film for suppressing 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 is：
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 electrodes 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 with protected metal electrode by wire is used as working electrode, photoelectrolytic cell It is connected with corrosion electrolytic cell by salt bridge (agar of the KCl containing saturation).(add ultraviolet using 300W high pressure Xe lamps as visible light source Light optical filter so that optical source wavelength >=400nm), direct irradiation TiO in photoelectrolytic cell2Composite film surface, use electrochemical operation Stand potential change of the test electrode potential before and after illumination.Schematic device is as shown in Figure 1.
The general principle of the present invention：
BiVO is mapped in illumination4/TiO2On composite membrane, due to BiVO4Energy gap is narrower, and photoresponse is wide, its valence-band electrons Excited first by incident photon and transit to conduction band, form photo-generate electron-hole pair.Again because its conduction band current potential is higher than TiO2, production Raw electrons are injected into the wider TiO of energy gap2Conduction band on, further migrate, lead to the relatively low metal surface of potential The increase of metal surface electron density is caused, electrode potential reduces, even much lower than the spontaneous corrosion potential of metal, steady into thermodynamics State area is cathode protecting state, and from environmental corrosion.And hole can be from TiO2Valence band is transferred to BiVO4Valence band, so as to realize Electron-hole efficiently separates, and makes electronics that transition can occur under the exciting of smaller luminous energy, substantially increases the profit of sunshine 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 sunshine is lifted.
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 potentials are minimum to fall to approximately -570mV, under About 500mv has been dropped, far below its corrosion potential, thus can be effectively protected；
After illumination stops, 304SS electrode potentials rise 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 summary, the present invention modifies TiO by anodizing in titanium plate surface2Nano-pipe array thin film, using water Hot method is in above-mentioned TiO2Film surface modifies BiVO4, obtained BiVO4/TiO2Composite nano tube array films are a kind of excellent light Anode material, obtained composite membrane and titanium sheet substrate is soaked in electrolyte solution as light anode, with being connected by protection metal Connect, play excellent and stable anticorrosion ability to metal using photoproduction cathodic protection effect.
Brief description of the drawings
Fig. 1 is photoproduction cathodic protection double-electrolyzer system schematic.
Fig. 2 a are TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano thin-film, scale are 2 μm, illustration Scale is 100nm.
Fig. 2 b are BiVO provided in an embodiment of the present invention4/TiO2The surface topography (SEM figures) of composite membrane, scale are 2 μm.
Fig. 3 is used TiO provided in an embodiment of the present invention2Nano-tube film and the BiVO prepared4/TiO2Composite membrane X-ray diffraction spectrogram.
Fig. 4 is used TiO provided in an embodiment of the present invention2Nano-tube film and the BiVO prepared4/TiO2Composite membrane Photogenerated current changes over time curve map before and after illumination.Wherein, abscissa is the time (s), and ordinate is density of photocurrent (μ A·cm-2).On represents illumination, and off represents that it is dark-state to close light source.
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 connects, and electrode potential changes over time curve before and after illumination.Wherein, abscissa is the time (s), ordinate is electrode potential (V vs.SCE).On represents illumination, and off represents that it is dark-state to close light source.
Fig. 6 a are TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano thin-film, scale are 2 μm, illustration Scale is 100nm.
Fig. 6 b are BiVO provided in an embodiment of the present invention4/TiO2The surface topography (SEM figures) of composite membrane, scale are 2 μm.
Fig. 7 is used TiO provided in an embodiment of the present invention2Nano-tube film and the BiVO prepared4/TiO2Composite membrane X-ray diffraction spectrogram.
Fig. 8 is used TiO provided in an embodiment of the present invention2Nano-tube film and the BiVO prepared4/TiO2Composite membrane Photogenerated current changes over time curve map before and after illumination.Wherein, wherein, abscissa is the time (s), and ordinate is that photoelectric current is close Spend (μ Acm-2).On represents illumination, and off represents that it is dark-state to close light source.
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 connects, and electrode potential changes over time curve before and after illumination.Wherein, abscissa is the time (s), ordinate is electrode potential (V vs.SCE).On represents illumination, and off represents that it is dark-state to close light source.
Embodiment
The present invention is further explained with reference to the accompanying drawings and examples.
The present invention is first by anodizing, and using Pt as to electrode, titanium sheet substrate is working electrode, with NH4F and second two Alcoholic solution is electrolyte, then titanium sheet is calcined, and TiO is prepared in titanium plate surface2Nano-pipe array thin film；Pass through hydro-thermal afterwards 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, it is placed in baking oven after incubation water heating, then BiVO is obtained through calcination processing4/TiO2Composite membrane.The BiVO of the present invention4/ TiO2Composite membrane, as the light anode of photoproduction cathodic protection, visible light utilization efficiency can be improved, hence it is evident that reduce the corruption of 304 stainless steels Current potential is lost, still there is preferable cathodic protection antiseptic effect under dark-state.
Embodiment 1
The preparation of light anode, comprises 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 more than 99.9%) As substrate, it is cleaned by ultrasonic 1min in acetone, absolute ethyl alcohol and deionized water successively, then is cleaned with ethanol, hair-dryer drying It is standby.Weigh 0.45g NH4F is dissolved in 2.5mL deionized waters, sequentially adds 6mL H2O2It is commercially available dense with 6mL 65~68% HNO3Polishing fluid is made into, the titanium sheet after cleaning is put into polishing fluid and polishes 1min, then is cleaned respectively with deionized water, ethanol, Dry up stand-by.
TiO2Nano-tube array film preparation：Weigh 0.22g NH4F, it is dissolved in 4mL deionized waters, ultrasound is completely molten to it Solution, 40mL ethylene glycol is then added, 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, in 20V voltage anodic oxygen 1h, is cleaned after oxidation through deionized water, natural Dry.Then sample is placed in Muffle furnace, 450 DEG C and constant temperature 2h is raised to 5 DEG C/min heating rate, close afterwards power supply with Stove is cooled to room temperature.TiO is made in titanium plate surface2Film of Nano tube array (referring to Fig. 2 a).
BiVO4/TiO2The preparation of composite membrane：The concentrated nitric acid of 3.8g (mass fraction 66.5%) is weighed, 20mL is dissolved in and goes In ionized water, 2mol/L HNO are obtained3Solution；1.60g NaOH are weighed, are dissolved in 20mL deionized waters, obtain 2mol/L NaOH Solution.Weigh 0.49g Bi (NO3)3·5H2O is added to the above-mentioned acquisition 2mo1/L HNO of 20mL3In solution, magnetic force stirs at room temperature 20min is mixed, obtains Bi (NO)3Aqueous solution of nitric acid；Weigh 0.12g NH4VO3It 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 add 0.09g sodium citrate, magnetic agitation 30min makes it be sufficiently mixed uniformly, Obtain reaction solution.By TiO2Nanotube is vertical or inclination is placed in 50mL autoclaves, 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, room temperature is naturally cooled to, obtained sample is spent Ionized water and absolute ethyl 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 media.Light anode and 304SS are coupled together as working electrode by wire, and Pt electrodes are to electricity Pole, saturated calomel electrode (SCE) are reference electrode.Photoelectrolytic cell passes through salt bridge (agar of the KCl containing saturation) with corrosion electrolytic cell Connection.Using 300W Xe lamps 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, its scanning electricity is tested respectively Mirror figure.By the visible obtained TiO 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 structures2The nanotube mouth of pipe, BiVO4The length of double ball particles is about 1 μm.
For TiO prepared by sign2Nano thin-film and BiVO4/TiO2The composition and structure of composite membrane, its X is tested respectively and is penetrated 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；Remove Ti and TiO2Diffraction maximum outside, in BiVO4/TiO2Monocline scheelite type BiVO is have also appeared in the XRD spectra of composite membrane4 (Monoclinic BiVO4) diffraction maximum, and do not observe other obvious diffraction maximums of impurity, illustrate modification BiVO4With pure Monoclinic system scheelite phase structure is present.
For BiVO prepared by sign4/TiO2Composite membrane electricity conversion, test 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 is about 2 μ Acm-2, when film surface modification BiVO4Afterwards, BiVO4/TiO2The transient state photoelectric current maximum 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 becomes big continuous.This is primarily due to TiO2Upper deposition BiVO4Afterwards, reduce the compound of electron-hole pair, add the absorption to visible ray, effectively increase the utilization to sunshine Rate.
For BiVO prepared by test4/TiO2304SS is placed in 3.5wt.%NaCl by composite membrane to 304SS protecting effect 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 more than pure TiO2Film.As 304SS and pure TiO2When film couples, 304SS electrode potentials are down to about -350mV, naturally rotten less than it Current potential is lost, plays certain photoproduction cathodic protection effect.When with BiVO4/TiO2When composite membrane couples, 304SS electrode potentials can drop To about -570mV, about 500mV is reduced, far below its spontaneous potential；When cutting off light source, 304SS electrode potentials start It is gradually increasing, is still below and pure TiO2Couple electrode potential during simultaneously illumination；Illumination is carried out again, and 304SS electrode potential is again - 570mV or so is rapidly decreased to, shows BiVO4/TiO2Composite membrane has good stability.
Embodiment 2
The preparation of light anode, comprises 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 more than 99.9%) As substrate, it is cleaned by ultrasonic 1min in acetone, absolute ethyl alcohol and deionized water successively, then is cleaned with ethanol, hair-dryer drying It is standby.Weigh 0.45g NH4F is dissolved in 2.5mL deionized waters, sequentially adds 6mL H2O2It is commercially available dense with 6mL 65~68% HNO3Polishing fluid is made into, the titanium sheet after cleaning is put into polishing fluid and polishes 1min, then is cleaned respectively with deionized water, ethanol, Dry up stand-by.
TiO2Nano-tube array film preparation：Weigh 0.22g NH4F, it is dissolved in 4mL deionized waters, ultrasound is completely molten to it Solution, 40mL ethylene glycol is then added, 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 oxygens 1h, naturally dry.Then Sample is placed in Muffle furnace, 450 DEG C and constant temperature 2h are raised to 5 DEG C/min heating rate, power supply is closed afterwards and cools to the furnace Room temperature.TiO is made in titanium plate surface2Film of Nano tube array.
BiVO4/TiO2The preparation of composite membrane：The concentrated nitric acid of 7.6g (mass fraction 66.5%) is weighed, 20mL is dissolved in and goes In ionized water, 4mol/L HNO is obtained3Solution；3.2g NaOH are weighed, are dissolved in 20mL deionized waters, obtain 4mol/L NaOH Solution.Weigh 0.98g Bi (NO3)3·5H2O is added to the 4mo1/L of the above-mentioned acquisitions of 20mL HNO3In solution, magnetic at room temperature Power stirs 20min, obtains Bi (NO)3Aqueous solution of nitric acid；Weigh 0.24g NH4VO3It is added to the 4mol/L of the above-mentioned acquisitions 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 add 0.18g sodium citrate, magnetic agitation 30min makes it be sufficiently mixed It is even, obtain reaction solution.By TiO2Nanotube is vertical or inclination is placed in 50mL autoclaves, and above-mentioned reaction solution is slowly poured into Reactor is until be totally submerged TiO2Nanotube, 180 DEG C, after hydro-thermal reaction 6h, room temperature is naturally cooled to, obtained sample is used Deionized water and absolute ethyl 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 media.Light anode and 304 stainless steels are coupled together as working electrode, Pt electrodes by wire is To electrode, saturated calomel electrode (SCE) is reference electrode.Photoelectrolytic cell passes through the salt bridge (fine jade of the KCl containing saturation with corrosion electrolytic cell Fat) connection.Using 300W Xe lamps as visible light source (adding uv filter so that optical source wavelength >=400nm), directly shine The BiVO penetrated in photoelectrolytic cell4/TiO2Laminated film surface.(referring to Fig. 6~Fig. 9)
To characterize prepared TiO2Nano thin-film BiVO4/TiO2Composite film surface pattern, its scanning electricity is tested respectively Mirror figure.By the visible obtained TiO 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 structure2The nanotube mouth of pipe, BiVO4The length of ellipsoid particle is about 0.5~1 μm.
For TiO prepared by sign2Nano thin-film and BiVO4/TiO2The composition and structure of composite membrane, its X is tested respectively and is penetrated 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；Remove Ti and TiO2Diffraction maximum outside, in BiVO4/TiO2Monocline scheelite type BiVO is have also appeared in the XRD spectra of composite membrane4 (Monoclinic BiVO4) diffraction maximum, and do not observe other obvious diffraction maximums of impurity, illustrate modification BiVO4With pure Monoclinic system scheelite phase structure is present.But compared with Example 1, BiVO4Diffraction maximum peak intensity substantially weaken, show the condition The BiVO of lower preparation4Crystallinity is not good enough.
For BiVO prepared by sign4/TiO2Composite membrane electricity conversion, test 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 is about 2 μ Acm-2, when film surface modification BiVO4Afterwards, BiVO4/TiO2The transient state photoelectric current maximum of composite membrane can be of about 25 μ Acm-2, exceeded well over pure TiO2Film it is temporary State photocurrent values, and as the extension of light application time, current value become big continuous.This is primarily due to TiO2Upper deposition BiVO4 Afterwards, reduce the compound of electron-hole pair, add the absorption to visible ray, effectively increase the utilization rate to sunshine.But Transient current value is more many than being reduced in embodiment 1, and this is probably because reaction reagent concentration doubles to cause BiVO4Pattern knot The difference of structure, so as to cause the difference of specific surface area, crystallinity etc., it have impact on the transmission of electric charge.
For BiVO prepared by test4/TiO2304SS is placed in by composite film photo-anode to 304SS protecting effect In 3.5wt.%NaCl corrosion electrolyte 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 more than pure TiO2Film.As 304SS and pure TiO2Film couple when, 304SS electrode potentials be down to about- 350mV, less than its spontaneous potential, play certain photoproduction cathodic protection effect.When with BiVO4/TiO2Composite membrane couples When, 304SS electrode potentials can be down to about -500mV, reduce about 300mV, far below its spontaneous potential；When cut-out light source When, 304SS electrode potentials start to gradually rise up to -350mV or so, but the 304SS being still below under this state and pure TiO2Coupling Even current potential；Illumination is carried out again, and 304SS electrode potential is rapidly decreased to -500mV or so, shows BiVO again4/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 limited by above-described embodiment System, other it is any without departing from spirit of the invention with made under principle change, modification, replacement, combine, simplification, should be Equivalent substitute mode, is included within protection scope of the present invention.

Claims (8)

  1. A kind of 1. light anode material, it is characterised in that：TiO is modified to obtain through anodic oxidation, calcining to titanium plate surface successively2Nanotube Array film, then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface modifies BiVO4Obtain light anode material BiVO4/ TiO2Composite membrane.
  2. A kind of 2. preparation method of the light anode material described in claim 1, it is characterised in that：Successively to titanium plate surface through anode TiO is modified to obtain in oxidation, calcining2Nano-pipe array thin film, then again hydrothermal treatment, calcining to above-mentioned TiO2Film surface is modified BiVO4Obtain light anode material BiVO4/TiO2Composite membrane.
  3. 3. the preparation method of the light anode material as described in claim 2, it is characterised in that：The TiO2Nano-pipe array thin film For using the Titanium base after processing as anode, in 20~30V voltage 1~2h of anodic oxygenization in the presence of electrolyte, after oxidation Clean, dry；And after being raised to 400~500 DEG C, and 1~3h of constant temperature in Muffle furnace with 1~5 DEG C/min heating rate, cool down Near room temperature, i.e., there is TiO in titanium-based piece surface modification2Film of Nano tube array.
  4. 4. the preparation method of the light anode material as described in claim 3, it is characterised in that：The electrolysis that the anodic oxidation uses Liquid is ethylene glycol and NH4The mixed liquor of the F aqueous solution；Wherein, ethylene glycol and NH4F aqueous solution volume ratios 10~20, ammonium fluoride Mass fraction is 3~7wt.%.
  5. 5. the preparation method of the light anode material as described in claim 2, it is characterised in that：It is described to be modified with TiO2Substrate is placed in Sealed in autoclave, contain Bi (NO) in excess3Reaction solution in, it is natural in 160~200 DEG C of 5~7h of hydro-thermal reaction Room temperature is cooled to, then cleans, dry through deionized water, ethanol alternate repetition, is then raised to 1~5 DEG C/min heating rate 180~220 DEG C and 1~3h of constant temperature, cool to room temperature with the furnace and obtain light anode material BiVO4/TiO2Composite membrane.
  6. 6. the preparation method of the light anode material as described in claim 5, 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, mol ratio Bi (NO)3:NH4VO3Mol ratio is 1~1.5, the final concentration of 2~5mol/ of sodium citrate L。
  7. 7. the preparation method of the light anode material as described in claim 6, it is characterised in that：
    The Bi (NO)3Aqueous solution of nitric acid be Bi (NO) that molar concentration is 0.05~0.1mol/L3With molar concentration be 2~ 4mol/L HNO3Mixed liquor；Wherein, HNO3:Bi(NO)3Mol ratio is 30~50；
    NH4VO3Sodium hydrate aqueous solution be NH that molar concentration is 0.05~0.1mol/L4VO3With molar concentration be 2~ 4mol/L NaOH mixed liquor；Wherein, NaOH:NH4VO3Mol ratio is 30~50.
  8. A kind of 8. application of the light anode material described in claim 1, it is characterised in that：The light anode material is as suppression Application in the anti-corrosion protective film of metal erosion.
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