CN103952708B - For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode - Google Patents

For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode Download PDF

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CN103952708B
CN103952708B CN201410142222.7A CN201410142222A CN103952708B CN 103952708 B CN103952708 B CN 103952708B CN 201410142222 A CN201410142222 A CN 201410142222A CN 103952708 B CN103952708 B CN 103952708B
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CN103952708A (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 present invention relates to the Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode, relates to a kind of composite film photo-anode.There is provided a kind of and there is high efficiency, the stable Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode.1) preparation of Titanium base sample: using titanium foil as matrix, cleans to obtain Titanium base sample in acetone, dehydrated alcohol and deionized water for ultrasonic successively; 2) titanium surface TiO 2the preparation of film of Nano tube array: by NH 4f dissolves in deionized water, adds ethylene glycol mixing, using platinum as to electrode, is calcined by sample, then cool to room temperature with the furnace after anodic oxidation, can at the obtained TiO in titanium surface 2film of Nano tube array; 3) Ag/SnO 2/ TiO 2the preparation of composite membrane: at TiO 2film of Nano tube array surface preparation Ag and SnO 2nano particle, obtains the Ag/SnO for photoproduction galvanic protection 2/ TiO 2light anode.

Description

For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode
Technical field
The present invention relates to a kind of composite film photo-anode, especially relate to a kind of Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-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. are by the TiO under illumination 2film is connected with metal by wire; its light induced electron produced transfers to metallic surface by wire; the electropotential of metal is reduced, effect (LiHY, the BaiXD of galvanic protection can be played metal; etal.; Fabricationoftitaniananotubesascathodeprotectionforstain lesssteel, ElectrochemicalandSolid-stateLetters, 2006; 9:B28-B31), thus TiO 2the preparation of film and its application in metallic corrosion controls cause showing great attention to of corrosion research person.But, due to TiO 2forbidden band wider (3.2eV), absorbing wavelength can only be less than the UV-light of 387nm, and effectively can not absorb visible ray, so it is lower to the utilization ratio of sunlight.In addition, photo-generate electron-hole is fast to the recombination velocity when illumination transfers dark-state to, and photoproduction galvanic protection effect can be made to be difficult to maintain.
In order to improve TiO 2to the utilization ratio of sunlight, make its absorption region expand to visible region, multiple method can be taked its modification, as metal or nonmetal doping, composite semiconductor or surface sensitization etc.Wherein, Ag/TiO 2composite membrane easily produces plasma resonance effect due to Ag nano particle, can make TiO 2absorption region expand to visible region.In addition, Zhou etc. adopt semi-conductor SnO prepared by sol-gel method 2as electron storage material and TiO 2composition composite membrane, makes it also can maintain certain special role (ZhouMJ, ZengZO, etal., Energystorageabilityandanti-corrosionprotectionpropertie sofTiO when illumination transfers dark-state to 2-SnO 2system, MaterialsandCorrosion, 2010,61:324-327).As by Ag and SnO 2synergistic application is in preparation TiO 2composite membrane likely obtains good photoelectric conversion performance, and the composite membrane as light anode may produce excellent photoproduction galvanic protection effect.
Stainless steel is a class important meals material, is widely used in all trades and professions.But in many circumstances, as under briny environment, corrosion phenomenon is still very serious for stainless steel, needs to adopt its corrosion of certain controlling measurement.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 to overcome the TiO prepared in the past 2film is low to sunlight utilization ratio, photoelectric efficiency is lower and be difficult in the dark state maintain the problems such as good photoproduction galvanic protection effect, provides a kind of Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-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 film photo-anode,
1) Titanium base surface TiO 2the preparation of film of Nano tube array: using platinum as to electrode, Titanium base is anode, at NH 4after carrying out anodic oxidation in F lysate, Titanium base sample is calcined, then cools to room temperature with the furnace, can at the obtained TiO in Titanium base surface 2film of Nano tube array;
2) Ag/SnO 2/ TiO 2the preparation of composite film photo-anode: at TiO 2film of Nano tube array surface preparation Ag and SnO 2nano particle is by 15 ~ 20gSnCl 22H 2o is fully dissolved in 200mL ethanol, and 80 DEG C of heating in water bath also constantly stir and then obtain concentration is the SnO of 0.5 ~ 1mol/L 2colloidal sol, leaves standstill 1d; Will with TiO 2the Titanium base of film of Nano tube array is placed on SnO 2soak 20min in colloidal sol, slowly lift out Titanium base, through super-dry, calcining, above step 5 ~ 50 time of then circulating, namely obtain SnO on the surface at Titanium base 2/ TiO 2composite membrane; Will with SnO 2/ TiO 2the Titanium base 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 film photo-anode.
In described step 1), Titanium base is for obtaining Titanium base in the cleaning of acetone, dehydrated alcohol and deionized water for ultrasonic ripple successively by titanium foil, stand-by.In described Titanium base, titanium foil content is more than 99.9%, and thickness is the pure titanium foil of 0.1mm; Titanium base sample is rectangle, and length is 15 ~ 25mm, and width is 10 ~ 15mm.Described step 1) middle NH 4f lysate is by NH 4f dissolves in deionized water, then adds ethylene glycol mixing again, wherein NH 4the mass ratio of F, deionized water and ethylene glycol is 2:(20 ~ 30): 400.Described step 1) condition of Anodic Oxidation is in 30V voltage anodic oxygen 30min.
Described step 2) calcining be Titanium base sample is placed in retort furnace at 450-550 DEG C, calcine 1-2h.
Described step 3) calcining be sample is placed in retort furnace at 450-550 DEG C, calcine 1-2h.
Ultimate principle of the present invention: TiO 2from the semi-conductor SnO of different energy level 2compound.TiO under illumination 2absorb photons produces 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, can make both produce light induced electron to SnO 2mobile:
SnO 2+xe -+xM +→M xSnO 2(M=H,Na)
Then, due to Ag/SnO 2the Schottky contacts at interface, makes electronics from the SnO of 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 is to the protected metal migration connected, and the electronics of metallic surface is increased, and potential drop is low to moderate far below corrosion of metal current potential, makes metal generation cathodic polarization, thus metallic corrosion is controlled.Under dark-state, be stored in SnO 2the electronics on surface continues release to Ag, finally transfers to protected metallic surface, maintains galvanic protection effect to metal.In addition, photohole is from SnO 2valence band transfer to TiO 2valence band, effectively realize being separated of electronics and hole.Therefore, SnO is passed through 2, Ag and TiO 2composition nano composite membrane effectively can improve the photoproduction galvanic protection effect of film to metal.
The advantage that the present invention has:
Ag/SnO prepared in accordance with the present invention 2/ TiO 2nano composite membrane, has coating uniform and complete feature, can be used as the light anode in photoproduction cathodic protection system.During illumination, this composite membrane can make the electropotential of the protected metal of connection significantly decline, and the more important thing is still to maintain excellent galvanic protection effect for a long time when dark-state.Composite membrane prepared by the inventive method is at 0.2mol/LNa 2in S+0.2mol/LNaOH solution, during radiation of visible light, the 304 poor stainless steel electrode current potentials of original solidity to corrosion in 3.5%NaCl solution that are in that can make to be attached thereto to decline 830mV relative to spontaneous potential, and significant cathodic polarization occurs.And after stopping illumination, stainless steel electrode current potential rises less, but still is about 280mV lower than stainless spontaneous potential, shows also have good galvanic protection effect in the dark state, and has satisfactory stability effect.
The present invention first utilizes anonizing to have certain thickness TiO in the preparation of titanium foil surface 2film of Nano tube array, then adopt sol-gel method and photoreduction sedimentation at TiO respectively 2film of Nano tube array surface deposition SnO 2with Ag particle.Select suitable SnO 2depositing time, cycle index, Ag +concentration with control SnO 2with the size and number of Ag particle.Then, surface there is Ag/SnO 2/ TiO 2the titanium foil of composite membrane is soaked in as light anode in certain electrolyte solution, 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 excellent photoproduction galvanic protection effect as light anode.
Accompanying drawing explanation
The TiO 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 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 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 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 the 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 anode connects, electropotential change curve in time before and after illumination.Wherein, X-coordinate is the time (h), and ordinate zou is electropotential (Vvs.SCE).On represents illumination, and off represents closedown light source and dark-state.
The TiO 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 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 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 the time (s), and ordinate zou is photoelectric current (nA).
304 stainless steels that Fig. 8 provides for the embodiment of the present invention are connected with quantum dot sensitized nano thin-film light anode in 3.5%NaCl solution, electropotential change curve in time before and after illumination.Wherein, X-coordinate is the time (h), and ordinate zou is electropotential (Vvs.SCE).On represents illumination, and off represents closedown 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 thick rectangle pure titanium foil of 0.1mm is sample, its long 15mm, and width is 10mm.Successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Take 0.5gNH 4f, is dissolved in 6mL deionized water, adds the mixing of 100mL ethylene glycol, obtains mixed solution.Under room temperature, with the titanium foil matrix after clean for anode, paillon foil is negative electrode, in above-mentioned mixed solution, with 30V ultor oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, namely obtain TiO at titanium foil matrix surface 2film of Nano tube array.
By 16.74gSnCl 22H 2o is fully dissolved in 200mL ethanol, and also constantly stirring and then evaporating solvent are until liquor capacity is 130mL to 80 DEG C of heating in water bath, and obtaining concentration is the SnO of 0.57mol/L 2colloidal sol, leaves standstill 1d; Will with TiO 2the Titanium base of film of Nano tube array is placed on SnO 2soak 20min in colloidal sol, slowly lift out Titanium base, then Titanium base to be placed in loft drier freeze-day with constant temperature 30min at 100 DEG C.Then calcine 1h at placing it in 450 DEG C, then cool to room temperature with the furnace.Circulate above step 20 time, namely obtains SnO on Titanium base surface 2/ TiO 2composite membrane; Will with SnO 2/ TiO 2the Titanium base of composite membrane is placed on 0.05mol/LAgNO 3in solution, use ultra violet lamp 30min, then use washed with de-ionized water, finally obtain the Ag/SnO for photoproduction galvanic protection 2/ TiO 2composite film photo-anode.
Ag/SnO 2/ TiO 2nano composite membrane photoproduction galvanic protection is tested: with Ag/SnO 2/ TiO 2nano thin-film is light anode, is placed in containing 0.2mol/LNa 2in the photoelectrolytic cell of S+0.2mol/LNaOH solution.Protected 304 stainless steels are that working electrode is placed in corrosion electrolyzer, and are to electrode with Pt electrode, and 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 (agar containing saturated KCl) with corrosion electrolyzer.Using 300WXe lamp as visible light source (add uv filter, make optical source wavelength >=400nm) during illumination, direct irradiation is laminated film surface in photoelectrolytic cell.
Fig. 1 a is obtained TiO 2the SEM figure of film of Nano tube array.Can find out, film of Nano tube array is relatively more even, and internal diameter is about 83nm.
Fig. 1 b is obtained Ag/SnO 2/ TiO 2the EDX figure of nano composite membrane.Can find out, in composite membrane except Ti and O element, also to there is 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.Pure TiO can be found out 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 about 600nm, 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-film, and X-coordinate is the time (s), and ordinate zou is photoelectric current (nA).Can find out, when film is pure TiO 2during nanometer film, transient state photoelectric current maximum value is about 300nA, 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, photo-current intensity significantly strengthens.Mainly due to Ag and SnO 2with TiO 2after compound, the compound that photo-generate electron-hole is right can be reduced, expand light abstraction width, effectively improve the utilization ratio to light.
Fig. 4 be 304 stainless steels in 3.5%NaCl solution respectively be in pure TiO in photoelectrolytic cell 2film and Ag/SnO 2/ TiO 2the coupling rear electrode current potential of compound film electrode curve over time, X-coordinate is the time (h), and ordinate zou is electropotential (V).As the pure TiO under stainless steel and illumination 2when membrane electrode is coupling, 304 stainless current potentials are down to about-300mV from spontaneous potential about-120mV, have good photoproduction galvanic protection effect.When being connected with composite membrane, under illumination, stainless electropotential can drop to about-780mV, and does not occur ascendant trend along with the prolongation electropotential of light application time, shows having good stability of composite membrane.When cutting off light source stainless steel current potential than equal conditions under with pure TiO 2the low 250mV of current potential when film connects.After cutting off light source 2.5h, again carry out illumination, the stainless electropotential be now connected with composite membrane is down to about-780mV rapidly again, 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 thick rectangle pure titanium foil of 0.1mm is sample, its long 15mm, and width is 10mm.Successively ultrasonic cleaning 10min successively in acetone, dehydrated alcohol and deionized water.
Take 0.5gNH 4f, is dissolved in 6mL deionized water, adds 100mL ethylene glycol, mixing.Under room temperature, with the titanium foil matrix after clean for anode, paillon foil is negative electrode, in above-mentioned mixed solution, with 30V ultor oxidation 30min.Then sample is placed in retort furnace and calcines 2h at 450 DEG C, then cool to room temperature with the furnace, namely obtain TiO at titanium foil matrix surface 2film of Nano tube array.
By 16.74gSnCl 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, and obtaining concentration is the SnO of 0.57mol/L 2colloidal sol, leaves standstill 1d; Will with TiO 2the Titanium base of film of Nano tube array is placed on SnO 2soak 20min in colloidal sol, slowly lift out Titanium base, then Titanium base to be placed in loft drier freeze-day with constant temperature 30min at 100 DEG C.Then calcine 1h at placing it in 450 DEG C, then cool to room temperature with the furnace.Circulate above step 20 time, namely obtains SnO on Titanium base surface 2/ TiO 2composite membrane; Will with SnO 2/ TiO 2the Titanium base of composite membrane is placed on 0.1mol/LAgNO 3in solution, use ultra violet lamp 30min, then use washed with de-ionized water, finally obtain the Ag/SnO for photoproduction galvanic protection 2/ TiO 2composite film photo-anode.
Ag/SnO 2/ TiO 2nano composite membrane photoproduction galvanic protection is tested: with Ag/SnO 2/ TiO 2nano thin-film is light anode, is placed in containing 0.2mol/LNa 2in the photoelectrolytic cell of S+0.2mol/LNaOH solution.Protected 304 stainless steels are that working electrode is placed in corrosion electrolyzer, and are to electrode with Pt electrode, and 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 (agar containing saturated KCl) with corrosion electrolyzer.Using 300WXe lamp as visible light source (add uv filter, make optical source wavelength >=400nm) during illumination, direct irradiation is laminated film surface in photoelectrolytic cell.
Fig. 5 a is obtained TiO 2the SEM figure of film of Nano tube array.Can find out, film of Nano tube array is relatively more even, and internal diameter is about 83nm.
Fig. 5 b is obtained Ag/SnO 2/ TiO 2the EDX figure of nano composite membrane.Can find out, in composite membrane except Ti and O element, also to there is 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.Pure TiO can be found out 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 about 600nm, 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-film, and X-coordinate is the time (s), and ordinate zou is photoelectric current (nA).Can find out, when film is pure TiO 2during nanometer film, transient state photoelectric current maximum value is about 300nA, 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, photo-current intensity significantly strengthens.Mainly due to Ag and SnO 2with TiO 2after compound, the compound that photo-generate electron-hole is right can be reduced, expand light abstraction width, effectively improve the utilization ratio to light.
Fig. 8 be 304 stainless steels in 3.5%NaCl solution respectively be in pure TiO in photoelectrolytic cell 2film and Ag/SnO 2/ TiO 2the coupling rear electrode current potential of compound film electrode curve over time, X-coordinate is the time (h), and ordinate zou is electropotential (V).As the pure TiO under stainless steel and illumination 2when membrane electrode is coupling, 304 stainless current potentials are down to about-300mV from spontaneous potential about-120mV, play certain photoproduction galvanic protection effect.When coupling with composite membrane, stainless electropotential can drop to about-950mV, and along with the prolongation of light application time, current potential declines gradually.When cut off light source time, stainless electropotential start rise, but now 304 stainless steel electrode current potentials far below with pure TiO 2stainless steel current potential time coupling.Again carry out illumination, the stainless electropotential be now connected with composite membrane is down to about-950mV rapidly again, shows having good stability of composite membrane.
Nano composite membrane described in the invention described above not only can suppress corrosion of metal, has excellent 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, also can maintain good photoproduction galvanic protection effect under dark-state.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (6)

1. the Ag/SnO for photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode, is characterized in that:
1) Titanium base surface TiO 2the preparation of film of Nano tube array: using platinum as to electrode, Titanium base is anode, at NH 4after carrying out anodic oxidation in F lysate, Titanium base sample is calcined, then cools to room temperature with the furnace, can at the obtained TiO in Titanium base surface 2film of Nano tube array;
2) Ag/SnO 2/ TiO 2the preparation of composite film photo-anode: at TiO 2film of Nano tube array surface preparation Ag and SnO 2nano particle is by 15 ~ 20gSnCl 22H 2o is fully dissolved in 200mL ethanol, and 80 DEG C of heating in water bath also constantly stir and then obtain concentration is the SnO of 0.5 ~ 1mol/L 2colloidal sol, leaves standstill 1d; Will with TiO 2the Titanium base of film of Nano tube array is placed on SnO 2soak 20min in colloidal sol, slowly lift out Titanium base, through super-dry, calcining, above step 5 ~ 50 time of then circulating, namely obtain SnO on the surface at Titanium base 2/ TiO 2composite membrane; Will with SnO 2/ TiO 2the Titanium base 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 film photo-anode;
In described Titanium base, titanium foil content is more than 99.9%, and thickness is the pure titanium foil of 0.1mm; Titanium base sample is rectangle, and length is 15 ~ 25mm, and width is 10 ~ 15mm.
2. by the Ag/SnO for photoproduction galvanic protection according to claim 1 2/ TiO 2the preparation method of composite film photo-anode, is characterized in that: described step 1) middle Titanium base is for obtaining Titanium base in the cleaning of acetone, dehydrated alcohol and deionized water for ultrasonic ripple successively by titanium foil, stand-by.
3. by the Ag/SnO for photoproduction galvanic protection according to claim 1 2/ TiO 2the preparation method of composite film photo-anode, is characterized in that: described step 1) middle NH 4f lysate is by NH 4f dissolves in deionized water, then adds ethylene glycol mixing again, wherein NH 4the mass ratio of F, deionized water and ethylene glycol is 2:(20 ~ 30): 400.
4. by the Ag/SnO for photoproduction galvanic protection according to claim 1 2/ TiO 2the preparation method of composite film photo-anode, is characterized in that: described step 1) condition of Anodic Oxidation is in 30V voltage anodic oxygen 30min.
5. by the Ag/SnO for photoproduction galvanic protection according to claim 1 2/ TiO 2the preparation method of composite film photo-anode, is characterized in that: described step 2) calcining be Titanium base sample is placed in retort furnace at 450-550 DEG C, calcine 1-2h.
6. by the Ag/SnO for photoproduction galvanic protection according to claim 1 2/ TiO 2the preparation method of composite film photo-anode, is characterized in that: described step 2) calcining be sample is placed in retort furnace at 450-550 DEG C, calcine 1-2h.
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