CN103952708A - Preparation method for Ag/SnO2/TiO2 composite membrane photoanode used for photogenerated cathodic protection - Google Patents

Preparation method for Ag/SnO2/TiO2 composite membrane photoanode used for photogenerated cathodic protection Download PDF

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CN103952708A
CN103952708A CN201410142222.7A CN201410142222A CN103952708A CN 103952708 A CN103952708 A CN 103952708A CN 201410142222 A CN201410142222 A CN 201410142222A CN 103952708 A CN103952708 A CN 103952708A
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CN103952708B (en
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李红
侯保荣
王秀通
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Institute of Oceanology of CAS
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Abstract

The invention relates to preparation methods for an Ag/SnO2/TiO2 composite membrane photoanode used for photogenerated cathodic protection, and relates to a composite membrane photoanode, and provides a preparation method for the efficient stable Ag/SnO2/TiO2 composite membrane photoanode used for photogenerated cathodic protection. The preparation method comprises: 1) preparing a titanium substrate sample, specifically taking titanium foil as a substrate, and performing ultrasonic cleaning successively in acetone, absolute ethanol and deionized water to obtain a titanium substrate sample; 2) preparing a titanium-surface TiO2 nanotube array membrane, specifically dissolving NH4 in deionized water, adding glycol, mixing uniformly, taking platinum as a counter electrode, performing anodization, calcining the titanium substrate sample, and cooling to room temperature along the furnace, so as to obtain the TiO2 nanotube array membrane on the surface of titanium; and 3) preparing the Ag/SnO2/TiO2 composite membrane, specifically preparing Ag and SnO2 nanometer particles on the surface of the TiO2 nanotube array membrane, so as to obtain the Ag/SnO2/TiO2 photoanode used for photogenerated cathodic protection.

Description

For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite membrane light anode
Technical field
The present invention relates to a kind of composite membrane light anode, especially relate to a kind of Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite membrane light anode.
Background technology
TiO 2be a kind of important multifunctional inorganic semiconductor material, have broad application prospects in fields such as gas sensor, contaminant degradation, solar hydrogen making and solar cells.In recent years, Li etc. is by the TiO under illumination 2film is connected with metal by wire; the light induced electron of its generation is transferred to metallic surface by wire; the electropotential of metal is reduced, can play to metal effect (Li H Y, the Bai X D of galvanic protection; et al.; Fabrication of titania nanotubes as cathode protection for stainless steel, Electrochemical and Solid-state Letters, 2006; 9:B28-B31), thereby TiO 2the preparation of film and its application in metallic corrosion control have caused showing great attention to of corrosion research person.But, due to TiO 2forbidden band wider (3.2eV), can only absorbing wavelength be less than the UV-light of 387nm, and can not effectively absorb visible ray, so it is lower to the utilization ratio of sunlight.In addition, light induced electron-hole is fast to recombination velocity in the time that illumination transfers dark state to, can make photoproduction galvanic protection effect be difficult to maintain.
In order to improve TiO 2to the utilization ratio of sunlight, make its absorption region expand to visible region, can take several different methods to its modification, as metal or nonmetal doping, composite semiconductor or surface sensitization etc.Wherein, Ag/TiO 2composite membrane, because Ag nano particle easily produces plasma resonance effect, can make TiO 2absorption region expand to visible region.In addition, the semi-conductor SnO that prepared by the employing sol-gel method such as Zhou 2as electron storage material and TiO 2composition composite membrane, makes it in the time that illumination transfers dark state to, also can maintain certain special role (Zhou M J, Zeng Z O, et al., Energy storage ability and anti-corrosion protection properties of TiO 2-SnO 2system, Materials and Corrosion, 2010,61:324-327).As by Ag and SnO 2synergistic application is in preparation TiO 2composite membrane likely obtains good photoelectric conversion performance, may produce good photoproduction galvanic protection effect as the composite membrane of light anode.
Stainless steel is a class important meals material, in all trades and professions, is widely used.But stainless steel is in many environment, under briny environment, corrosion phenomenon is still very serious, need to adopt certain its corrosion of measure control.Due to the difference of material and envrionment conditions, stainless corrosion control technology still needs to research and develop.
Summary of the invention
The object of the invention is to be in order to overcome the TiO of preparation in the past 2film is low to sunlight utilization ratio, photoelectric efficiency is lower and be difficult to maintain the problems such as good photoproduction galvanic protection effect under dark state, and a kind of Ag/SnO for photoproduction galvanic protection is provided 2/ TiO 2the preparation method of composite membrane light anode.
For achieving the above object, the technical solution used in the present invention is:
A kind of Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite membrane light anode,
1) titanium matrix surface TiO 2the preparation of film of Nano tube array: using platinum as to electrode, titanium matrix is anode, at NH 4in F lysate, carry out after anodic oxidation, by the calcining of titanium matrix sample, then cool to room temperature with the furnace, can make TiO at titanium matrix surface 2film of Nano tube array;
2) Ag/SnO 2/ TiO 2the preparation of composite membrane light anode: at TiO 2film of Nano tube array surface preparation Ag and SnO 2nano particle is by 15～20g SnCl 22H 2o is fully dissolved in 200mL ethanol, and 80 DEG C of heating in water bath also constantly stir and then obtain the SnO that concentration is 0.5～1mol/L 2colloidal sol, leaves standstill 1d; Will be with TiO 2the titanium matrix of film of Nano tube array is placed on SnO 2in colloidal sol, soak 20min, slowly lift out titanium matrix, through super-dry, calcining, above step 5～50 time of then circulating obtain SnO on titanium matrix surface 2/ TiO 2composite membrane; Will be with SnO 2/ TiO 2the titanium matrix of composite membrane is placed on 0.01～0.5mol/LAgNO 3in solution, use ultra violet lamp 30min, then use washed with de-ionized water, obtain the Ag/SnO for photoproduction galvanic protection 2/ TiO 2composite membrane light anode.
In described step 1), titanium matrix is for titanium foil is cleaned and obtains titanium matrix at acetone, dehydrated alcohol and deionized water for ultrasonic ripple successively, stand-by.In described titanium matrix, titanium foil content is more than 99.9%, the pure titanium foil that thickness is 0.1mm; Titanium matrix sample is rectangle, and length is 15～25mm, and width is 10～15mm.Described step 1) middle NH 4f lysate is by NH 4f is dissolved in deionized water, then adds ethylene glycol to mix, wherein NH again 4the mass ratio of F, deionized water and ethylene glycol is 2:(20～30): 400.Described step 1) condition of Anodic Oxidation is anodic oxidation 30min under 30V voltage.
Described step 2) calcining be that titanium matrix sample is placed in retort furnace and calcines 1-2h at 450-550 DEG C.
Described step 3) calcining be that sample is placed in retort furnace and calcines 1-2h at 450-550 DEG C.
Ultimate principle of the present invention: TiO 2semi-conductor SnO from different energy levels 2compound.TiO under illumination 2absorb photon and produce electron-hole pair:
TiO 2+hv→TiO 2+e -+h +
Due to SnO 2density of states(DOS) and TiO 2density of states(DOS) can overlap, both conduction band positions overlap, and can make light induced electron that both produce to SnO 2mobile:
SnO 2+xe -+xM +→M xSnO 2(M=H,Na)
Then, due to Ag/SnO 2the Schottky contacts at interface, makes the SnO of electronics from high fermi level 2forward the Ag surface of low fermi level to:
M xSnO 2+Ag+ye -+zM +→M (x+z-1)AgSnO 2+M z-y(M=H,Na)
Last electronics, to the protected metal migration connecting, increases the electronics of metallic surface, and potential drop is low to moderate far below corrosion of metal current potential, makes metal generation cathodic polarization, thereby metallic corrosion is controlled.Under dark state, be stored in SnO 2the electronics on surface continues to discharge to Ag, finally transfers to protected metallic surface, and metal is maintained to galvanic protection effect.In addition, photohole is from SnO 2valence band transfer to TiO 2valence band, effectively realize separating of electronics and hole.Therefore, pass through SnO 2, Ag and TiO 2composition nano composite membrane can effectively improve the photoproduction galvanic protection effect of film to metal.
The present invention has advantages of:
Ag/SnO prepared in accordance with the present invention 2/ TiO 2nano composite membrane, has all even complete features of coating, can be used as the light anode in photoproduction cathodic protection system.When illumination, this composite membrane can make the electropotential of the protected metal connecting significantly decline, and the more important thing is and in the time of dark state, still can maintain for a long time good galvanic protection effect.Composite membrane prepared by the inventive method is at 0.2mol/L Na 2in S+0.2mol/L NaOH solution, when radiation of visible light, can make 304 poor stainless steel electrode current potentials of the original solidity to corrosion in 3.5%NaCl solution that is attached thereto with respect to the spontaneous potential 830mV that declines, significant cathodic polarization occurs.And stopping after illumination, stainless steel electrode current potential rises less, but still lower than the about 280mV of stainless spontaneous potential, shows also have good galvanic protection effect under dark state, and have satisfactory stability effect.
The present invention first utilizes anonizing to be prepared with certain thickness TiO on titanium foil surface 2film of Nano tube array, then adopt respectively sol-gel method and photoreduction sedimentation at TiO 2film of Nano tube array surface deposition SnO 2with Ag particle.Select suitable SnO 2depositing time, cycle index, Ag +concentration with control SnO 2size and number with Ag particle.Then, there is to Ag/SnO on surface 2/ TiO 2the titanium foil of composite membrane is soaked in certain electrolyte solution as light anode, and makes it to be connected with protected metal (stainless steel) with wire, can play photoproduction galvanic protection effect to metal.
In sum, the present invention's application anonizing is first at titanium foil surface preparation TiO 2film of Nano tube array, then adopt sol-gel method and photoreduction sedimentation in film surface deposition SnO 2with Ag nano particle, to obtain Ag/SnO 2/ TiO 2composite membrane.This composite membrane demonstrates good photoproduction galvanic protection effect as light anode.
Brief description of the drawings
The TiO for preparing gained that Fig. 1 a provides for the embodiment of the present invention 2the surface topography (SEM figure) of nano thin-film.Wherein, scale is 100nm.
The Ag/SnO for preparing gained that Fig. 1 b provides for the embodiment of the present invention 2/ TiO 2the power spectrum (EDX figure) of nano thin-film.
The Ag/SnO for preparing gained that Fig. 2 provides for the embodiment of the present invention 2/ TiO 2the uv-visible absorption spectra figure of nano thin-film.Wherein, X-coordinate is wavelength (nm), and ordinate zou is absorption intensity.
The Ag/SnO for preparing gained that Fig. 3 provides for the embodiment of the present invention 2/ TiO 2the transient state photoelectricity flow graph of nano thin-film.Wherein, X-coordinate is time (s), and ordinate zou is photoelectric current (nA).
304 stainless steels that Fig. 4 provides for the embodiment of the present invention in 3.5%NaCl solution with Ag/SnO 2/ TiO 2nano thin-film light anodic bonding, electropotential temporal evolution graphic representation before and after illumination.Wherein, X-coordinate is time (h), and ordinate zou is electropotential (V vs.SCE).On represents illumination, and it is dark state that off represents to close light source.
The TiO for preparing gained that Fig. 5 a provides for the embodiment of the present invention 2the surface topography (SEM figure) of nano thin-film.Wherein, scale is 100nm.
The Ag/SnO for preparing gained that Fig. 5 b provides for the embodiment of the present invention 2/ TiO 2the power spectrum (EDX figure) of nano thin-film.
The Ag/SnO for preparing gained that Fig. 6 provides for the embodiment of the present invention 2/ TiO 2the uv-visible absorption spectra figure of nano thin-film.Wherein, X-coordinate is wavelength (nm), and ordinate zou is absorption intensity.
Fig. 7 provides the Ag/SnO of preparation for the embodiment of the present invention 2/ TiO 2the transient state photoelectricity flow graph of nano thin-film.Wherein, X-coordinate is time (s), and ordinate zou is photoelectric current (nA).
304 stainless steels that Fig. 8 provides for the embodiment of the present invention in 3.5%NaCl solution with quantum dot sensitized nano thin-film light anodic bonding, electropotential temporal evolution graphic representation before and after illumination.Wherein, X-coordinate is time (h), and ordinate zou is electropotential (V vs.SCE).On represents illumination, and off represents to close light source, i.e. dark state.
Embodiment
Embodiment 1
According to technique scheme (concrete steps), preparation TiO 2and Ag/SnO 2/ TiO 2nano thin-film, and testing film as light anode to 304 stainless galvanic protection effects.
Getting the rectangle pure titanium foil that 0.1mm is thick is sample, its long 15mm, and width is 10mm.Successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Take 0.5g NH 4f, is dissolved in 6mL deionized water, adds 100mL ethylene glycol to mix, and obtains mixed solution.Under room temperature, taking the titanium foil matrix after cleaning as anode, paillon foil is negative electrode, in above-mentioned mixed solution, with 30V voltage anodic oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, make TiO at titanium foil matrix surface 2film of Nano tube array.
By 16.74g SnCl 22H 2o is fully dissolved in 200mL ethanol, and 80 DEG C of heating in water bath constantly stirring and then evaporating solvent be until liquor capacity is 130mL, the SnO that to obtain concentration be 0.57mol/L 2colloidal sol, leaves standstill 1d; Will be with TiO 2the titanium matrix of film of Nano tube array is placed on SnO 2in colloidal sol, soak 20min, slowly lift out titanium matrix, then titanium matrix is placed in loft drier to freeze-day with constant temperature 30min at 100 DEG C.Then place it at 450 DEG C and calcine 1h, then cool to room temperature with the furnace.The above step 20 time that circulates, obtains SnO at titanium matrix surface 2/ TiO 2composite membrane; Will be with SnO 2/ TiO 2the titanium matrix of composite membrane is placed on 0.05mol/L AgNO 3in solution, use ultra violet lamp 30min, then use washed with de-ionized water, finally make the Ag/SnO for photoproduction galvanic protection 2/ TiO 2composite membrane light anode.
Ag/SnO 2/ TiO 2nano composite membrane photoproduction galvanic protection test: with Ag/SnO 2/ TiO 2nano thin-film is light anode, is placed in and contains 0.2mol/L Na 2in the photoelectrolytic cell of S+0.2mol/L NaOH solution.Protected 304 stainless steels are that working electrode is placed in corrosion electrolyzer, and taking Pt electrode as to electrode, saturated calomel electrode (SCE) is reference electrode, and 3.5%NaCl is medium solution.Light anode is connected by wire with stainless steel electrode, and photoelectrolytic cell is connected by salt bridge (containing the agar of saturated KCl) with corrosion electrolyzer.When illumination, (add uv filter, make optical source wavelength >=400nm) using 300W Xe lamp as visible light source, direct irradiation is laminated film surface in photoelectrolytic cell.
Fig. 1 a is the TiO making 2the SEM figure of film of Nano tube array.Can find out, film of Nano tube array is more even, and internal diameter is about 83nm.
Fig. 1 b is the Ag/SnO making 2/ TiO 2the EDX figure of nano composite membrane.Can find out, in composite membrane, except Ti and O element, also have Sn and Ag element.
Fig. 2 is the uv-visible absorption spectra of different nanometer film, and X-coordinate is wavelength (nm), and ordinate zou is absorption intensity.Can find out pure TiO 2the light abstraction width of nano thin-film is mainly at ultraviolet region, and its spectral absorption limit is approximately 390nm.And Ag/SnO 2/ TiO 2the visible region absorption intensity of nano composite membrane significantly increases, and spectral absorption limit moves to 600nm left and right, shows compound Ag and SnO 2particle can expand the absorption region to visible ray.
Fig. 3 is the transient state optogalvanic spectra of different nano thin-films, and X-coordinate is time (s), and ordinate zou is photoelectric current (nA).Can find out, when film is pure TiO 2when nanometer film, transient state photoelectric current maximum value is 300nA left and right, as film surface deposition Ag and SnO 2after, the transient state photoelectric current maximum value of composite membrane is 1600nA, shows to deposit Ag and SnO 2after particle, photoelectric current intensity significantly strengthens.Mainly due to Ag and SnO 2with TiO 2after compound, can reduce right compound in light induced electron-hole, expand light abstraction width, effectively improve the utilization ratio to light.
Fig. 4 be 304 stainless steels in 3.5%NaCl solution respectively with pure TiO in photoelectrolytic cell 2film and Ag/SnO 2/ TiO 2compound film electrode is coupled rear electrode current potential curve over time, and X-coordinate is time (h), and ordinate zou is electropotential (V).As the pure TiO under stainless steel and illumination 2when membrane electrode is coupled, 304 stainless current potentials from spontaneous potential approximately-be down to approximately-300mV of 120mV, have good photoproduction galvanic protection effect.In the time being connected with composite membrane, can drop to approximately-780mV of stainless electropotential under illumination, and along with ascendant trend does not appear in the prolongation electropotential of light application time, show having good stability of composite membrane.When cut off when light source stainless steel current potential than equal conditions under with pure TiO 2the low 250mV of current potential when film connects.Cut off after light source 2.5h, again carry out illumination, about the be down to rapidly again-780mV of stainless electropotential being now connected with composite membrane, and along with the carrying out of illumination, current potential is also relatively stable, still than with pure TiO 2low 480mV when film connects, has higher photoproduction galvanic protection effect.Ag/SnO is described 2/ TiO 2nano composite membrane is stable, and can play good photoproduction galvanic protection effect to 304 stainless steels.
Embodiment 2
According to technique scheme (concrete steps), preparation TiO 2and Ag/SnO 2/ TiO 2nano thin-film, and testing film as light anode to 304 stainless galvanic protection effects.
Getting the rectangle pure titanium foil that 0.1mm is thick is sample, its long 15mm, and width is 10mm.Successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Take 0.5g NH 4f, is dissolved in 6mL deionized water, adds 100mL ethylene glycol, mixes.Under room temperature, taking the titanium foil matrix after cleaning as anode, paillon foil is negative electrode, in above-mentioned mixed solution, with 30V voltage anodic oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, make TiO at titanium foil matrix surface 2film of Nano tube array.
By 16.74g SnCl 22H 2o is fully dissolved in 200mL ethanol, and 80 DEG C of heating in water bath also constantly stir until liquor capacity is 130mL, the SnO that acquisition concentration is 0.57mol/L 2colloidal sol, leaves standstill 1d; Will be with TiO 2the titanium matrix of film of Nano tube array is placed on SnO 2in colloidal sol, soak 20min, slowly lift out titanium matrix, then titanium matrix is placed in loft drier to freeze-day with constant temperature 30min at 100 DEG C.Then place it at 450 DEG C and calcine 1h, then cool to room temperature with the furnace.The above step 20 time that circulates, obtains SnO at titanium matrix surface 2/ TiO 2composite membrane; Will be with SnO 2/ TiO 2the titanium matrix of composite membrane is placed on 0.1mol/L AgNO 3in solution, use ultra violet lamp 30min, then use washed with de-ionized water, finally make the Ag/SnO for photoproduction galvanic protection 2/ TiO 2composite membrane light anode.
Ag/SnO 2/ TiO 2nano composite membrane photoproduction galvanic protection test: with Ag/SnO 2/ TiO 2nano thin-film is light anode, is placed in and contains 0.2mol/L Na 2in the photoelectrolytic cell of S+0.2mol/L NaOH solution.Protected 304 stainless steels are that working electrode is placed in corrosion electrolyzer, and taking Pt electrode as to electrode, saturated calomel electrode (SCE) is reference electrode, and 3.5%NaCl is medium solution.Light anode is connected by wire with stainless steel electrode, and photoelectrolytic cell is connected by salt bridge (containing the agar of saturated KCl) with corrosion electrolyzer.When illumination, (add uv filter, make optical source wavelength >=400nm) using 300W Xe lamp as visible light source, direct irradiation is laminated film surface in photoelectrolytic cell.
Fig. 5 a is the TiO making 2the SEM figure of film of Nano tube array.Can find out, film of Nano tube array is more even, and internal diameter is about 83nm.
Fig. 5 b is the Ag/SnO making 2/ TiO 2the EDX figure of nano composite membrane.Can find out, in composite membrane, except Ti and O element, also have Sn and Ag element.
Fig. 6 is the uv-visible absorption spectra of different nanometer film, and X-coordinate is wavelength (nm), and ordinate zou is absorption intensity.Can find out pure TiO 2the light abstraction width of nano thin-film is mainly at ultraviolet region, and its spectral absorption limit is approximately 390nm.And Ag/SnO 2/ TiO 2the visible region absorption intensity of nano composite membrane significantly increases, and spectral absorption limit moves to 600nm left and right, shows compound Ag and SnO 2particle can expand the absorption region to visible ray.
Fig. 7 is the transient state optogalvanic spectra of different nano thin-films, and X-coordinate is time (s), and ordinate zou is photoelectric current (nA).Can find out, when film is pure TiO 2when nanometer film, transient state photoelectric current maximum value is 300nA left and right, as film surface deposition Ag and SnO 2after, the transient state photoelectric current maximum value of composite membrane is 2000nA, shows to deposit Ag and SnO 2after particle, photoelectric current intensity significantly strengthens.Mainly due to Ag and SnO 2with TiO 2after compound, can reduce right compound in light induced electron-hole, expand light abstraction width, effectively improve the utilization ratio to light.
Fig. 8 be 304 stainless steels in 3.5%NaCl solution respectively with pure TiO in photoelectrolytic cell 2film and Ag/SnO 2/ TiO 2compound film electrode is coupled rear electrode current potential curve over time, and X-coordinate is time (h), and ordinate zou is electropotential (V).As the pure TiO under stainless steel and illumination 2when membrane electrode is coupled, 304 stainless current potentials from spontaneous potential approximately-be down to approximately-300mV of 120mV, play certain photoproduction galvanic protection effect.In the time being coupled with composite membrane, can drop to approximately-950mV of stainless electropotential, along with the prolongation of light application time, current potential declines gradually.When cutting off when light source, stainless electropotential starts to rise, but now 304 stainless steel electrode current potentials far below with pure TiO 2stainless steel current potential while being coupled.Again carry out illumination, be down to rapidly again-950mV of the stainless electropotential left and right being now connected with composite membrane, shows having good stability of composite membrane.
Nano composite membrane described in the invention described above not only can suppress corrosion of metal, has good opto-electronic conversion effect, can play good photoproduction galvanic protection effect as light anode to 304 stainless steels.And the having good stability of composite membrane itself, under dark state, also can maintain good photoproduction galvanic protection effect.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (7)

1. the Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that:
1) titanium matrix surface TiO 2the preparation of film of Nano tube array: using platinum as to electrode, titanium matrix is anode, at NH 4in F lysate, carry out after anodic oxidation, by the calcining of titanium matrix sample, then cool to room temperature with the furnace, can make TiO at titanium matrix surface 2film of Nano tube array;
2) Ag/SnO 2/ TiO 2the preparation of composite membrane light anode: at TiO 2film of Nano tube array surface preparation Ag and SnO 2nano particle is by 15～20g SnCl 22H 2o is fully dissolved in 200mL ethanol, and 80 DEG C of heating in water bath also constantly stir and then obtain the SnO that concentration is 0.5～1mol/L 2colloidal sol, leaves standstill 1d; Will be with TiO 2the titanium matrix of film of Nano tube array is placed on SnO 2in colloidal sol, soak 20min, slowly lift out titanium matrix, through super-dry, calcining, above step 5～50 time of then circulating obtain SnO on titanium matrix surface 2/ TiO 2composite membrane; Will be with SnO 2/ TiO 2the titanium matrix of composite membrane is placed on 0.01～0.5mol/LAgNO 3in solution, use ultra violet lamp 30min, then use washed with de-ionized water, obtain the Ag/SnO for photoproduction galvanic protection 2/ TiO 2composite membrane light anode.
2. by the Ag/SnO for photoproduction galvanic protection claimed in claim 1 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that: in described step 1), titanium matrix is for titanium foil is cleaned and obtains titanium matrix at acetone, dehydrated alcohol and deionized water for ultrasonic ripple successively, stand-by.
3. by the Ag/SnO for photoproduction galvanic protection described in claim 1 or 2 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that: in described titanium matrix titanium foil content more than 99.9%, the pure titanium foil that thickness is 0.1mm; Titanium matrix sample is rectangle, and length is 15～25mm, and width is 10～15mm.
4. by the Ag/SnO for photoproduction galvanic protection claimed in claim 1 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that: described step 1) middle NH 4f lysate is by NH 4f is dissolved in deionized water, then adds ethylene glycol to mix, wherein NH again 4the mass ratio of F, deionized water and ethylene glycol is 2:(20～30): 400.
5. by the Ag/SnO for photoproduction galvanic protection claimed in claim 1 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that: described step 1) condition of Anodic Oxidation is anodic oxidation 30min under 30V voltage.
6. by the Ag/SnO for photoproduction galvanic protection claimed in claim 1 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that: described step 2) calcining be that titanium matrix sample is placed in retort furnace and calcines 1-2h at 450-550 DEG C.
7. by the Ag/SnO for photoproduction galvanic protection claimed in claim 1 2/ TiO 2the preparation method of composite membrane light anode, is characterized in that: described step 3) calcining be that sample is placed in retort furnace and calcines 1-2h at 450-550 DEG C.
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