CN106119858A - A kind of NiSe for photoproduction cathodic protection2/ TiO2composite nano tube array films and preparation thereof and application - Google Patents

A kind of NiSe for photoproduction cathodic protection2/ TiO2composite nano tube array films and preparation thereof and application Download PDF

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CN106119858A
CN106119858A CN201610709737.XA CN201610709737A CN106119858A CN 106119858 A CN106119858 A CN 106119858A CN 201610709737 A CN201610709737 A CN 201610709737A CN 106119858 A CN106119858 A CN 106119858A
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tio
nise
nano tube
tube array
composite nano
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CN106119858B (en
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王秀通
韦秦怡
张巧霞
李红
李鑫冉
侯保荣
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Institute of Oceanology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

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Abstract

The present invention relates to a kind of composite nano tube light anode, especially relate to a kind of NiSe for photoproduction cathodic protection2/TiO2Composite nano tube array films and preparation thereof and application.The average caliber of composite nano tube array films is 60 70 nanometers, and the thickness of pipe is 1.7 2 microns；Wherein, NiSe2Granule is modified at TiO by the method for cyclic voltammetric electro-deposition2Around the matrix nano pipe mouth of pipe.Material of the present invention and 304 rustless steel Rhizoma Nelumbinis even can obviously reduce its corrosion potential, have experimental implementation simple, and product safety is reliable, photoelectric transformation efficiency is high, the feature of stable performance.

Description

A kind of NiSe for photoproduction cathodic protection2/TiO2Composite nano tube array films and Preparation and application
Technical field
The present invention relates to a kind of composite nano tube light anode, especially relate to a kind of NiSe for photoproduction cathodic protection2/ TiO2Composite nano tube array films and preparation thereof and application.
Background technology
Corrosion of metal protected working is extremely important in actual production is lived.Metal erosion traditional from principle is prevented Handguard section has following several: protective layer, sacrificial protection, external electricity negative electrode are added in the change of metal material composition, surface Electric protection method and change corrosive environment etc..The means of change metal material composition have certain finger for the selection of initial steel Lead meaning but have little effect for the steel construction built up；The means adding protective layer in metal surface are relatively effective Also it is conventional, but coating is difficult to accomplish without leak source, tight, and it is also contemplated that the problems such as aging；Anode loss protection Method is changed anode member and often to be carried out, and does not drop to economic loss to minimum level；External electricity negative electrode electric protection method is held because of needs Continuous unidirectional current supply, is not suitable for the situation of power supply inconvenience, such as ocean platform etc..A kind of brand-new protecting hand Duan Guangsheng cathodic protection creates, and it has considered the pluses and minuses of above-mentioned whole mode, and the advantage of photoproduction cathodic protection Just be to have the strongest operability, coverlay require low, be not required to sacrificial anode part, do not consume electric energy.And through to existing The research having document we have found that TiO2Base light anode has certain photoproduction cathodic protection effect to iron and steel.But the TiO of routine2 Only ultraviolet light there is response, for promoting TiO2Photoresponse ability often use anodizing to prepare the TiO of high-sequential2Nanometer Pipe array films, to promote its electron transport ability.Adulterate with various metal and nonmetals, semiconductors coupling, conducting polymer modified Its photoelectric conversion ability is promoted etc. means.
Transient metal chalcogenide compound is made up of transition metal and chalcogen (S, Se, Te), common are NiS2, NiSe,Ni3Se2, ZnTe2, CdSe, CdTe etc..It is often used as light absorbent, high to the trans-utilization rate of solar energy. NiSe2It is the one of transition metal chalcogen compound, is also low-gap semiconductor material, have good catalytic performance and low toxicity Pollution-free.The NiSe that Zhang etc. successfully make with two one-step hydrothermals2/ RGO (redox graphene), and it is used as dyestuff Sensitization solar battery to electrode to substitute expensive Pt to electrode.There is presently no NiSe with cyclic voltammetric electro-deposition2 Modify TiO2On, and for the research of photoproduction cathodic protection.
Summary of the invention
It is an object of the invention to provide a kind of NiSe for photoproduction cathodic protection2/TiO2Composite nano tube array films and Preparation and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of NiSe for photoproduction cathodic protection2/TiO2Composite nano tube array films, putting down of composite nano tube array films All calibers are 60-70 nanometer, and the thickness of pipe is 1.7-2 micron；Wherein, NiSe2Granule is repaiied by the method for cyclic voltammetric electro-deposition Decorations are at TiO2Around the matrix nano pipe mouth of pipe.
Described composite nano tube array films is for matrix anodizing with platinized platinum for electrode with titanium foil, at working solution Middle will form the TiO of regular pattern after the oxidation of titanium foil matrix calcination processing at matrix surface2Nano-pipe array thin film, then adopts On nano-pipe array thin film, NiSe is modified by the method for cyclic voltammetric electro-deposition2, then obtain NiSe through calcination processing2/TiO2Multiple Close film of Nano tube array.
Described cyclic voltammetric electrodeposition process prepares NiSe2/TiO2Cyclic voltammetry scan scope be-0.7V 0.2V, sweep Face speed is 5mV/s 10mV/s, and scan round number of times is 10-15 time；Finally sample is dried at 60 DEG C-80 DEG C 2-4 little Time, obtain NiSe2/TiO2Complex light anode.
Described cyclic voltammetric electrolyte is pressed the volume ratio mixing of 1:4-1:6 by solution a and solution b, and wherein a solution is 0.02-0.04mol/L SeO2, 7-9%v/v salt aqueous acid, solution b is 0.05-0.07mol/L NiCl2·6H2O is water-soluble Liquid.
A kind of NiSe for photoproduction cathodic protection2/TiO2The preparation method of composite nano tube array films, described being combined is received Mitron array films is for matrix anodizing with platinized platinum for electrode with titanium foil, is aoxidized also by titanium foil matrix in working solution Form the TiO of regular pattern at matrix surface after calcination processing2Nano-pipe array thin film, then uses cyclic voltammetric electro-deposition Method modifies NiSe on nano-pipe array thin film2, then obtain NiSe through calcination processing2/TiO2Composite nano tube array films.
Particularly as follows:
1) pretreatment of Titanium base: Titanium base polishing fluid is polished, then cleans, stand-by；
2) titanium surface TiO2The preparation of film of Nano tube array: with step 1) in Titanium base make anode, platinized platinum is to electrode, In the presence of working solution through anodic oxidation and at 450-500 DEG C at calcine 1-2h, cool to room temperature afterwards with the furnace, can be at titanio Surface prepares TiO2Film of Nano tube array；
3)NiSe2/TiO2The preparation of composite film photo-anode: by step 2) TiO that obtains2Nanotube is electrolysed at cyclic voltammetric Liquid carries out electro-deposition modification.Sweep limits is-0.7V 0.2V, and surface sweeping speed is 5mV/s 10mV/s, scan round number of times It is 10 15 times, finally matrix is dried 24 hours at 60 DEG C 80 DEG C, obtains NiSe2/TiO2Complex light anode.
Described anodic oxidation be in the presence of working solution by Titanium base in 20-30V voltage anodic oxygen 1-2 hour, The most again Titanium base is placed in Muffle furnace, is raised to 450-500 DEG C and constant temperature 1-2h with the heating rate of 1-5 DEG C/min, afterwards It is cooled to room temperature.
Described cyclic voltammetric electrolyte is pressed the volume ratio mixing of 1:4-1:6 by solution a and solution b, and wherein a solution is 0.02-0.04mol/L SeO2, 7-9%v/v salt aqueous acid, solution b is 0.05-0.07mol/L NiCl2·6H2O is water-soluble Liquid.
A kind of NiSe for photoproduction cathodic protection2/TiO2The application of composite nano tube array films, described composite membrane conduct For suppressing the anti-corrosion protective film of metal erosion.When 304 rustless steels and light anode Rhizoma Nelumbinis connect, its OCP is left up to-800mV Right.
A kind of NiSe for photoproduction cathodic protection2/TiO2The application of composite nano tube array films, described composite membrane can be made For light anode.
The NiSe for photoproduction cathodic protection to above-mentioned preparation2/TiO2Composite membrane is as the photoproduction cathodic protection of light anode The test of effect, the concrete double-electrolyzer system using photoelectrolytic cell and corrosion electrolyzer composition, as shown in Figure 1.NiSe2/TiO2 Composite membrane is light anode, is placed in photoelectrolytic cell, and wherein electrolyte is 0.1mol/L Na2S solution.Corrosion electrolyzer is three electricity Polar body system, working electrode is protected metal (rustless steel), is Pt electrode to electrode, and reference electrode is saturated calomel electrode (SCE), with NaCl solution that mass concentration is 3.5% as corrosive medium.Light anode and protected metal electrode pass through wire Connecting as working electrode, photoelectrolytic cell is connected by salt bridge (containing the agar of saturated KCl) with corrosion electrolyzer.With 200W high pressure Xe lamp provides simulated solar irradiation as light source (without any optical filter), and direct irradiation is TiO in photoelectrolytic cell2Composite membrane table Face, tests electrode potential potential change before and after illumination with electrochemical workstation.
The ultimate principle of the present invention: NiSe2It is a kind of transient metal chalcogenide compound and is that a kind of Conductivity Ratio is higher Pauli paramagnetism material, is especially suitable for doing energy storage material.Its component Ni and Se is in moderate and reserves abundance.As one Kind of environmental friendliness and the narrow semiconductor photosensitive material of energy gap, can use it for TiO2The sensitization doping of light anode changes Property.Light induced electron and hole are efficiently separated, greatly reduces the recombination probability of electron hole.Last light induced electron is to electromotive force Lower stainless steel electrode transfer so that stainless steel electrode current potential is negative to be moved, thus is at by guard mode.Therefore, pass through NiSe2With TiO2Composition nano composite membrane can be effectively improved the thin film photoproduction cathodic protection effect to metal.
Advantage for present invention:
1, NiSe of the present invention2/TiO2Composite nano tube array films, has that caliber is homogeneous, regular appearance, modified coatings are uniform Feature, wider compared with pure titinium dioxide to the absorption region of light, be excellent smooth anode material.
When 2, irradiating composite membrane prepared by the present invention with simulated solar irradiation, can make in the corrosion electrolyzer being attached thereto 304 stainless steel electrode current potentials drop to below-730mV, hence it is evident that less than its corrosion potential, and significant cathodic polarization occurs.3、 With pure TiO2Nano thin-film is compared, NiSe prepared by the present invention2/TiO2Composite membrane visible ray according under to 304 stainless photoproduction Cathodic protection is better.
3, after stopping illumination, stainless steel electrode current potential has risen, but is still below stainless spontaneous potential, table Bright composite membrane the most also has good cathodic protection effect, and has good stabilizing effect.
Accompanying drawing explanation
The composite photoproduction cathodic protection measure of merit installation drawing that Fig. 1 provides for the embodiment of the present invention.
The NiSe that Fig. 2 provides for the embodiment of the present invention2/TiO2The surface topography (SEM figure) of nano thin-film.
304 rustless steels that Fig. 3 provides for the embodiment of the present invention in 3.5%NaCl solution with pure TiO2Nano thin-film and NiSe2/TiO2Even, before and after illumination, electrode potential changes over curve to nano thin-film light anode Rhizoma Nelumbinis.Wherein, abscissa is the time S (), vertical coordinate is electrode potential (V vs.SCE).On represents that illumination, off represent closedown light source i.e. dark-state.
304 rustless steels that Fig. 4 provides for the embodiment of the present invention and pure TiO2Nano thin-film and NiSe2/TiO2Nano thin-film light Transient photocurrents density curve under the different condition of anode Rhizoma Nelumbinis tie-in examination.On represents that illumination, off represent that closedown light source is the darkest State.
The NiSe that Fig. 5 provides for the embodiment of the present invention2/TiO2The surface topography (SEM figure) of nano thin-film.
304 rustless steels that Fig. 6 provides for the embodiment of the present invention in 3.5%NaCl solution with pure TiO2Nano thin-film and NiSe2/TiO2Nano thin-film light anode connects, and before and after illumination, electrode potential changes over curve.Wherein, abscissa is the time S (), vertical coordinate is electrode potential (V vs.SCE).On represents that illumination, off represent closedown light source i.e. dark-state.
304 rustless steels that Fig. 7 provides for the embodiment of the present invention and pure TiO2Nano thin-film and NiSe2/TiO2Nano thin-film light Transient photocurrents density curve under the different condition of anode Rhizoma Nelumbinis tie-in examination.On represents that illumination, off represent that closedown light source is the darkest State.
Detailed description of the invention
Embodiment 1
NiSe for photoproduction cathodic protection2/TiO2The preparation of composite nano tube array films light anode:
From the titanium foil that purity is more than 99.9% cutting specification be the titanium sheet of 20 × 15 × 0.1mm be matrix, first After in acetone, dehydrated alcohol and deionized water ultrasonic cleaning 1min successively, dry stand-by.
Polishing fluid is 0.45gNH4F is dissolved in 2.5mL H2In O, then it is separately added into 6mL H2O2With 6mL HNO3, after cleaning Titanium sheet put in polishing fluid polish 1 minute, then clean up with distilled water dry stand-by.
Weigh 0.22g NH4F, is dissolved in 4mL deionized water, adds 40mL ethylene glycol and stirs as working solution. Under room temperature, with pretreated Titanium base as anode, platinized platinum is negative electrode, and in working solution, Titanium base is in 20V voltage anodic oxygen Again 20V voltage anodic oxygenization 2 hours after after changing 2 hours, ultrasonic cleaning is dried for 1 minute.Then sample is placed on Muffle Stove, is raised to 450 DEG C and constant temperature 2h with the heating rate of 1 DEG C/min, closes power supply afterwards and cools to room temperature with the furnace, i.e. at titanium sheet table Face prepares TiO2Film of Nano tube array.
Configuration cyclic voltammetric electro-deposition electrolyte.Wherein a solution is 0.22g SeO2It is dissolved in 50mL distilled water then Add 4mL hydrochloric acid again.Solution b is 4.75g NiCl2·6H2O is dissolved in 300mL distilled water.(a and b is molten to pour a solution into b solution The volume of liquid is respectively 54ml and 300ml, directly mixes) in be made into cyclic voltammetric electrolyte.
By cyclic voltammetry by NiSe2Modify TiO2On, cyclic voltammetry scan scope is-0.7V 0.2V, surface sweeping speed For 10mV/s.Cycle-index is 10 times.Finally sample is dried 4 hours at 60 DEG C, obtains NiSe2/TiO2Complex light anode.
To the above-mentioned NiSe prepared2/TiO2Nano composite membrane carries out photoproduction cathodic protection test: with NiSe2/TiO2 Nano thin-film is light anode, is placed in containing 0.1mol/L Na2In the photoelectrolytic cell of S solution.Protected 304 rustless steels are work It is placed in corrosion electrolyzer as electrode, and with Pt electrode for electrode, saturated calomel electrode (SCE) is reference electrode, 3.5% NaCl is medium solution.The working electrode that light anode is connected electrochemical workstation with stainless steel electrode by wire is connected, photoelectricity Xie Chiyu corrosion electrolyzer is connected by salt bridge (containing the agar of saturated KCl).Using 200W Xe lamp as simulated solar irradiation during illumination Light source (without any optical filter), direct irradiation laminated film surface in photoelectrolytic cell.(seeing Fig. 2-Fig. 4)
The NiSe prepared as seen from Figure 22/TiO2The SEM figure of film of Nano tube array.It can be seen that NiSe2Particle is at TiO2 Pile up on nanotube.TiO2Nano tube structure still mays be seen indistinctly.
As seen from Figure 3 304 rustless steels in 3.5%NaCl solution respectively be in pure TiO in photoelectrolytic cell2Nano thin-film And NiSe2/TiO2Compound film electrode Rhizoma Nelumbinis connects rear electrode current potential versus time curve, and abscissa is the time (s), and vertical coordinate is Electrode potential (V).Play certain photoproduction cathodic protection effect.As rustless steel and pure TiO2When nano thin-film Rhizoma Nelumbinis connects, its electrode Current potential can be down to about-450mV.When power source, stainless electrode potential begins to ramp up to-310mV, makes rustless steel still locate In by guard mode.When connecting with composite membrane Rhizoma Nelumbinis, stainless electrode potential can fall to approximately about-730mV.When cutting off light source Time, stainless electrode potential begins to ramp up to-410mV, and 304 rustless steels are still had certain protective effect.Again Carrying out illumination, the stainless electrode potential being now connected with composite membrane is rapidly decreased to again about-710mV, shows composite membrane Have good stability.
304 rustless steels and pure TiO as seen from Figure 42Nano thin-film and NiSe2/TiO2At simulated solar irradiation when composite membrane Rhizoma Nelumbinis connects Transient photocurrents density under Zhao Sheing is respectively 50 μ A/cm2With 280 μ A/cm2Left and right, stopping density of photocurrent during illumination is 0.
Embodiment 2
NiSe for photoproduction cathodic protection2/TiO2The preparation of composite nano tube array films light anode:
From the titanium foil that purity is more than 99.9% cutting specification be the titanium sheet of 20 × 15 × 0.1mm be matrix, first After in acetone, dehydrated alcohol and deionized water ultrasonic cleaning 1min successively, dry stand-by.
Polishing fluid is 0.45g NH4F is dissolved in 2.5mL H2In O, then it is separately added into 6mL H2O2With 6mL HNO3, after cleaning Titanium sheet put in polishing fluid polish 1 minute, then clean up with distilled water dry stand-by.
Weigh 0.22g NH4F, is dissolved in 4mL deionized water, adds 40mL ethylene glycol and stirs as working solution. Under room temperature, with the Titanium base after process as anode, platinized platinum is negative electrode, and in working solution, Titanium base is in 20V voltage anodic oxygenization 2 Again 20V voltage anodic oxygenization 2 hours after after hour, ultrasonic cleaning is dried for 1 minute.Then sample is placed on Muffle furnace, with The heating rate of 1 DEG C/min is raised to 450 DEG C of also constant temperature 2 hours, closes power supply afterwards and cools to room temperature with the furnace, i.e. in Ti surface system Obtain TiO2Film of Nano tube array.
Configuration cyclic voltammetric electro-deposition electrolyte.Wherein a solution is 0.22g SeO2It is dissolved in 50mL distilled water then Add 4mL hydrochloric acid again.Solution b is 4.75g NiCl2·6H2O is dissolved in 300mL distilled water.A solution is poured into the b solution (a of 54ml Solution mixes with the b solution of 300ml) in be made into cyclic voltammetric electrolyte.
By cyclic voltammetry by NiSe2Modify TiO2On, cyclic voltammetry scan scope is-0.7V～0.2V, surface sweeping speed For 10mV/s.Cycle-index is 15 times.Finally sample is dried 4 hours at 60 DEG C, obtains NiSe2/TiO2Complex light anode.
To the above-mentioned NiSe prepared2/TiO2Nano composite membrane carries out photoproduction cathodic protection test: with NiSe2/TiO2 Nano thin-film is light anode, is placed in containing 0.1mol/L Na2In the photoelectrolytic cell of S solution.Protected 304 rustless steels are work It is placed in corrosion electrolyzer as electrode, and with Pt electrode for electrode, saturated calomel electrode (SCE) is reference electrode, 3.5% NaCl is medium solution.The working electrode that light anode is connected electrochemical workstation with stainless steel electrode by wire is connected, photoelectricity Xie Chiyu corrosion electrolyzer is connected by salt bridge (containing the agar of saturated KCl).Using 200W Xe lamp as simulated solar irradiation during illumination Light source (being not added with any optical filter)), direct irradiation laminated film surface in photoelectrolytic cell.(seeing Fig. 5-Fig. 7)
The NiSe prepared as seen from Figure 52/TiO2The SEM figure of film of Nano tube array.It can be seen that NiSe2Particle is at TiO2 Pile up on nanotube.TiO2Nano tube structure still mays be seen indistinctly.
304 rustless steels and are in NiSe in photoelectrolytic cell in 3.5%NaCl solution as seen from Figure 62/TiO2Composite membrane electricity Pole Rhizoma Nelumbinis connects rear electrode current potential versus time curve, and abscissa is time (S), and vertical coordinate is electrode potential (V).Play certain Photoproduction cathodic protection effect.When connecting with pure TiO2 nano thin-film Rhizoma Nelumbinis, stainless electrode potential can be down to about-450mV,. When power source, stainless electrode potential begins to ramp up to-310mV, makes rustless steel still in by guard mode.When stainless When steel and composite membrane Rhizoma Nelumbinis connect, its electrode potential can fall to approximately about-700mV.When cutting off light source, stainless electrode potential Begin to ramp up to-530mV, 304 rustless steels are still had certain protective effect.Again carry out illumination, now with compound The stainless electrode potential that film connects is rapidly decreased to again about-700mV, shows having good stability of composite membrane.
304 rustless steels and pure TiO as seen from Figure 72Nano thin-film and NiSe2/TiO2At simulated solar irradiation when composite membrane Rhizoma Nelumbinis connects Transient photocurrents density under Zhao Sheing is 50 μ A/cm2With 208 μ A/cm2Left and right, stopping density of photocurrent during illumination is 0.
Nano composite membrane described in the invention described above is possible not only to suppress corrosion of metal, has excellent opto-electronic conversion effect Should, as light anode, 304 rustless steels can be played good photoproduction cathodic protection effect, and it is to 304 stainless photoproduction Cathodic protection effect is than pure TiO2Nano thin-film light anode to be got well.And having good stability of composite membrane itself, also can under dark-state Maintain good photoproduction cathodic protection effect.
Other preparation method do not illustrated, can be easily carried out, the most not under the guide of above-mentioned two preparation method Redundant again.
It should be appreciated that those of ordinary skill in the art is under the enlightenment of the present invention, in the power without departing from the present invention Profit requires under the ambit protected, it is also possible to makes multiple change the such as replacement, simple combination and goes, the rights protection model of the present invention Enclose and should be as the criterion with described claim.

Claims (10)

1. the NiSe for photoproduction cathodic protection2/TiO2Composite nano tube array films, it is characterised in that: composite nano tube battle array The average caliber of row film is 60-70 nanometer, and the thickness of pipe is 1.7-2 micron；Wherein, NiSe2Granule is by cyclic voltammetric electro-deposition Method is modified at TiO2Around the matrix nano pipe mouth of pipe.
2. the NiSe for photoproduction cathodic protection as described in claim 12/TiO2Composite nano tube array films, its feature exists In: described composite nano tube array films is for matrix anodizing with platinized platinum for electrode with titanium foil, incites somebody to action in working solution Form the TiO of regular pattern at matrix surface after the oxidation of titanium foil matrix calcination processing2Nano-pipe array thin film, then uses and follows The method of ring volt-ampere electro-deposition modifies NiSe on nano-pipe array thin film2, then obtain NiSe through calcination processing2/TiO2It is combined and receives Mitron array films.
3. the NiSe for photoproduction cathodic protection as described in claim 22/TiO2Composite nano tube array films, its feature exists In: described cyclic voltammetric electrodeposition process prepares NiSe2/TiO2Cyclic voltammetry scan scope be-0.7V 0.2V, surface sweeping speed Rate is 5mV/s 10mV/s, and scan round number of times is 10-15 time；Finally sample is dried 2-4 hour at 60 DEG C-80 DEG C, To NiSe2/TiO2Complex light anode.
4. the NiSe for photoproduction cathodic protection as described in Claims 2 or 32/TiO2Composite nano tube array films, its feature It is: described cyclic voltammetric electrolyte is mixed by the volume ratio of 1:4-1:6 by solution a and solution b, and wherein a solution is 0.02-0.04mol/L SeO2, 7-9%v/v salt aqueous acid, solution b is 0.05-0.07mol/L NiCl2·6H2O is water-soluble Liquid.
5. the NiSe for photoproduction cathodic protection described in a claim 12/TiO2The preparation side of composite nano tube array films Method, it is characterised in that: described composite nano tube array films is for matrix anodizing with platinized platinum for electrode with titanium foil, Working solution will form the TiO of regular pattern at matrix surface after the oxidation of titanium foil matrix calcination processing2Nano-pipe array thin film, The method of cyclic voltammetric electro-deposition is then used to modify NiSe on nano-pipe array thin film2, then obtain NiSe through calcination processing2/ TiO2Composite nano tube array films.
6. the NiSe for photoproduction cathodic protection as described in claim 52/TiO2The preparation method of composite nano tube array films, It is characterized in that:
1) pretreatment of Titanium base: Titanium base polishing fluid is polished, then cleans, stand-by；
2) titanium surface TiO2The preparation of film of Nano tube array: with step 1) in Titanium base make anode, platinized platinum is to electrode, in work Make in the presence of liquid through anodic oxidation and at 450-500 DEG C at calcine 1-2h, cool to room temperature afterwards with the furnace, can be at titanio body surface Face prepares TiO2Film of Nano tube array；
3)NiSe2/TiO2The preparation of composite film photo-anode: by step 2) TiO that obtains2Nanotube is in cyclic voltammetric electrolyte Carry out electro-deposition modification.Sweep limits is-0.7V 0.2V, and surface sweeping speed is 5mV/s 10mV/s, and scan round number of times is 10 15 times, finally matrix is dried 24 hours at 60 DEG C 80 DEG C, obtains NiSe2/TiO2Complex light anode.
7. the NiSe for photoproduction cathodic protection as described in claim 62/TiO2The preparation method of composite nano tube array films, It is characterized in that: described anodic oxidation is for little in 20-30V voltage anodic oxygen 1-2 by Titanium base in the presence of working solution Time, the most again Titanium base is placed in Muffle furnace, is raised to 450-500 DEG C and constant temperature 1-2h with the heating rate of 1-5 DEG C/min, it After be cooled to room temperature.
8. the NiSe for photoproduction cathodic protection as described in claim 62/TiO2The preparation method of composite nano tube array films, It is characterized in that: described cyclic voltammetric electrolyte is mixed by the volume ratio of 1:4-1:6 by solution a and solution b, and wherein a is molten Liquid is 0.02-0.04mol/L SeO2, 7-9%v/v salt aqueous acid, solution b is 0.05-0.07mol/LNiCl2·6H2O Aqueous solution.
9. the NiSe for photoproduction cathodic protection described in a claim 12/TiO2The application of composite nano tube array films, its It is characterised by: described composite membrane is as the anti-corrosion protective film for suppressing metal erosion.
10. the NiSe for photoproduction cathodic protection described in a claim 12/TiO2The application of composite nano tube array films, It is characterized in that: described composite membrane can be as light anode.
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