CN110344096A - A kind of AgSbS2It is sensitized TiO2Composite film material and its preparation and application - Google Patents
A kind of AgSbS2It is sensitized TiO2Composite film material and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of composite film photo-anodes, more particularly, to a kind of AgSbS2It is sensitized TiO2Composite film material (AgSbS2/TiO2Nano-tube array composite film material) and its prepare and apply.Structure of composite membrane of the invention is AgSbS2Nanoparticle deposition is in TiO2On nanotube.AgSbS2After nano-particles reinforcement, TiO2It is obviously improved in visible region absorption, and matched position of energy band can drive photo-generated carrier quick separating after semiconductors coupling, reduce secondary compound.AgSbS of the invention2It is sensitized TiO2Nano-tube array laminated film, when carrying out cathodic protection as optical anode material, relative to TiO2The utilization rate of visible light and the separation rate of photo-generated carrier can be improved in material, significantly reduces the electrode potential of 304 stainless steels, reduces corrosion rate.
Description
Technical field
The present invention relates to a kind of composite film photo-anodes, more particularly, to a kind of AgSbS2It is sensitized TiO2Composite film material
(AgSbS2/TiO2Nano-tube array composite film material) and its prepare and apply.
Background technique
Photoproduction cathode protection technology have it is environmental-friendly, electric current and process is protected not consume light anode material without outside supply
The characteristics of material, has the advantage for saving resource, is widely studied and applied.Photoproduction cathode protection technology is that semiconductor applies
It overlays on by protection metal surface, or is connected by conducting wire with metal as anode, to generate the skill of protective effect to metal
Art.Under illumination condition, Electron absorption photon energy in semiconductor valence band is transitted to conduction band by excitation, generates electronics-sky
Cave pair.Hole is aoxidized by electron donor, and under the action of space charge field, electronics is transferred to metal surface by conducting wire, drop
The low electrode potential of metal, plays the role of cathodic protection.
Semiconductor material, which is applied to photoproduction cathodic protection, to meet some requirements, and the conduction band current potential of semiconductor first is necessary
The corrosion potential being defeated by same solution, secondly forbidden bandwidth cannot be wide, and the electrons and holes of semiconductor are easy to again
It separates and recombination rate is low.TiO2It is a kind of common photoelectric material, there is good photocatalytic.Due to low cost and nanometer
Control is standby simple, TiO2It is widely applied in photoproduction cathode field.TiO2Band gap be 3.2eV, can only absorbing wavelength be less than
The ultraviolet light of 378nm is low to the utilization rate of visible light.Therefore, the narrow material of searching band gap is compound therewith and reduces light induced electron
It is to increase TiO with the recombination rate in hole2The important research direction of incident photon-to-electron conversion efficiency.
Summary of the invention
It is an object of that present invention to provide a kind of AgSbS2It is sensitized TiO2Composite film material (AgSbS2/TiO2Nano-tube array is multiple
Close thin-film material) and its prepare and apply.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of AgSbS2It is sensitized TiO2The preparation method of composite film material, by area load TiO2The base of film of Nano tube array
Body is impregnated into progress ion layer adsorption reaction in the solution containing Ag, S and Sb ion, so that in TiO2The surface of film of Nano tube array
Form Ag2S and Sb2S3Nano particle obtains AgSbS in matrix surface using calcining2Nano-particle modified TiO2Nanotube
Array composite film.
The area load TiO2Ion is carried out in solution of the matrix dipping containing Ag, S and Sb ion of film of Nano tube array
Layer adsorption reaction is by area load TiO2The matrix of film of Nano tube array successively carries out Ag2S deposition cycle and Sb2S3Deposition is followed
Ring makes TiO2The surface of film of Nano tube array forms Ag2S and Sb2S3Nano particle；Wherein, each circulation at least carries out primary.
The Ag2S deposition cycle is by area load TiO2The matrix of film of Nano tube array is first dipped into containing 0.05~0.1M
AgNO3Ethanol solution in impregnate 50~60s, after clean 2~3s with methanol, then immediately immersion the Na containing 0.05~0.1M2The first of S
3~4min is impregnated in alcoholic solution, cleans 2~3s with ethyl alcohol, that is, completes an Ag2S deposition cycle；According to primary depositing circulation
Mode is repeated again, that is, realizes multiple Ag2S deposition cycle, so that in TiO2Nano-tube array film surface forms Ag2S nanometers
Grain.
The Sb2S3Deposition cycle is that surface is formed Ag2The TiO of S nano particle2The matrix of film of Nano tube array is first
Immerse the SbCl containing 0.05~0.1M3Ethanol solution in impregnate 10~15s, after being cleaned with methanol, immerse immediately containing 0.05~
0.1M Na250~60s is impregnated in the methanol solution of S, is cleaned, is again dipped into after cleaning containing 0.05~0.1M SbCl with ethyl alcohol3's
50~60s is impregnated in ethanol solution, after cleaning 2~3s with methanol, immerses the Na containing 0.05~0.1M immediately2In S methanol solution,
Complete a Sb2S3Deposition cycle；It is repeated again in the way of primary depositing circulation, that is, realizes multiple Sb2S3Deposition is followed
Ring, so that i.e. in TiO2Nanotube surface forms Ag2S and Sb2S3Nano particle.
The calcining is that above-mentioned surface is formed Ag2S、Sb2S3The TiO of nano particle2The matrix of film of Nano tube array is placed in
In Muffle furnace, setting temperature is 300~350 DEG C, calcines 8~15min, i.e., obtains AgSbS in matrix surface2It is sensitized TiO2It is compound
Membrane material.
Above-mentioned record area load TiO2The matrix of film of Nano tube array is by anodic oxidation, and Titanium base surface obtains
TiO2Nano-tube array.
The anodizing is Titanium base to be cut into a certain size titanium sheet, after polished and cleaned, connects direct current
Source anode, platinum electrode connect power cathode, are placed in electrolyte together and carry out anodic oxidation.Setting supply voltage is 15~25V,
Electrolysis time is set as 1~1.5h.
The electrolyte refers to ethylene glycol, NH4F and deionized water composition anodic oxidation electrolyte, wherein ethylene glycol and
NH4The volume ratio of F solution is 10~20, NH4The mass fraction of F solution is 3~7wt.%.
It further says, the Ag2S deposition cycle refers to TiO2Film is first dipped into AgNO3In ethanol solution, dipping
50~60s after cleaning 2~3s with ethyl alcohol, immerses Na immediately2In S methanol solution, 3~4min is impregnated, finally cleans 2 with ethyl alcohol
~3s completes an Ag2S deposition cycle.
The AgNO3Ethanol solution is to weigh 0.6~1.2g AgNO3It is dissolved in 70mL ethyl alcohol, is made 0.05~0.1M's
AgNO3Ethanol solution.The Na2S methanol solution is to weigh 0.8~1.7g Na2S·9H2O is dissolved in 70mL methanol, is made 0.05
The Na of~0.1M2S methanol solution.
The Sb2S3Deposition cycle refers to TiO2Film is first dipped into SbCl3In ethanol solution, 10~15s is impregnated, is used
After ethyl alcohol cleans 2~3s, Na is immersed immediately2In S methanol solution, 50~60s is impregnated, cleans 2~3s with ethyl alcohol, after cleaning again
Immerse 0.05~0.1M SbCl3In ethanol solution, 50~60s is impregnated, after cleaning 2~3s with ethyl alcohol, immerses Na immediately2S methanol
In solution, 50~60s is impregnated, cleans 2~3s with ethyl alcohol.Complete a Sb2S3Deposition cycle.
The SbCl3Ethanol solution is to weigh 0.8~1.6g SbCl3It is dissolved in 70mL ethyl alcohol, is made 0.05~0.1M's
SbCl3Ethanol solution.The Na2S methanol solution is to weigh 0.8~1.7g Na2S·9H2O is dissolved in 70mL methanol, is made 0.05
The Na of~0.1M2S methanol solution.
A kind of AgSbS of the method preparation2It is sensitized TiO2Composite film material is prepared by the method in matrix surface
AgSbS2Nano particle is carried on TiO2Composite film material on nano-tube array.
A kind of AgSbS2It is sensitized TiO2The application of composite film material, photoproduction cathodic protection of the composite film material in metal
In application.
Application of the composite membrane as light anode, in photoproduction cathodic protection.
The composite membrane is for inhibiting metal erosion as the application in anti-corrosion protective film.
The reaction that the process mainly occurs is chemical equation are as follows:
2AgNO3+Na2S=Ag2S+2NaNO3 (1)
2SbCl3+3Na2S=Sb2S3+6NaCl (2)
Ag2S+Sb2S3=2AgSbS2 (3)
Above-mentioned AgSbS2/TiO2The photoproduction cathodic protection test method of nano-tube array composite membrane is as follows: in photoelectrolytic cell and
Corrode and tests composite membrane in the double-electrolyzer system of electrolytic cell composition to the protecting effect of 304 stainless steels.AgSbS2/TiO2Nanometer
Tube array composite film is coupled as light anode and 304 stainless steel of working electrode, and two electrodes are respectively placed in containing 0.05M Na2S and
In the photoelectrolytic cell of 0.1M NaOH mixed solution and the corrosion electrolytic cell containing 3.5wt.%NaCl solution.Saturated calomel electrode
As reference electrode, it is placed in corrosion electrolytic cell, does open circuit potential test.AgSbS2/TiO2Nano-tube array composite membrane connects work
Make electrode, 304 stainless steels ground connection is respectively placed in containing 0.05M Na2The photoelectrolytic cell of S solution and 0.1M NaOH solution and contain
Have in the corrosion electrolytic cell of 3.5wt.%NaCl solution, does transient state photoelectricity current test.Utilize xenon lamp simulated visible light, direct irradiation
In AgSbS2/TiO2Nano-tube array composite film surface.The open circuit potential figure and TiO that composite membrane and 304 stainless steels are coupled2Film
With the open circuit potential figure comparison of 304 stainless steels coupling, the difference of the two protecting effect is obtained.
Basic principle of the invention:
Semiconductor has unique band structure, and under the irradiation of incident light, electronics is excited to transit to from valence band and be led
Band.In same solution, when the conduction band current potential of semiconductor is defeated by the current potential of metal, electronics can move to potential from semiconductor more
On low metal, the cathodic protection to metal material is realized.TiO2Forbidden bandwidth is 3.2eV, and forbidden bandwidth is larger, only wavelength
It is just able to achieve less than the higher purple light of the energy of 378nm to TiO2The excitation of electronics.The wave-length coverage of visible light is about 400~
800nm, thus TiO2It is not high to the utilization rate of visible light.AgSbS2Forbidden bandwidth it is narrow, it is high to the utilization rate of light.Therefore, it compares
In TiO2, AgSbS2/TiO2Composite membrane is stronger to the response activity of visible light, can produce more light induced electrons.And it compound partly leads
The matched band structure of body inhibits carrier to recombinate, and realizes efficiently separating for light induced electron and hole, makes more polyelectron to electricity
The high metal surface migration of gesture, to reach to corrosion of metal protection effect.
Advantage for present invention:
The present invention is by AgSbS2Nano particle and TiO2Nanotube is compound, can effectively widen TiO2The wavelength of incident light is inhaled
Range is received, its utilization rate to sunlight is increased.And the matched position of energy band distribution of composite material can effectively improve electron-hole
Pair separation rate, further decrease the electrode potential of metal, improve TiO2Cathodic protection effect.Specifically:
1. light anode AgSbS of the present invention2/TiO2Nano-tube array composite membrane has uniform caliber, and since low energy gap is wide
The AgSbS of degree2Modification, TiO2Light abstraction width widen, the utilization rate of sunlight is improved.
2. by light anode AgSbS2/TiO2Nano-tube array composite membrane is placed in electrolyte solution and is coupled with 304 stainless steels
Carry out photoproduction cathodic protection test.When incident light is irradiated on the composite membrane, 304 stainless steel electrode current potentials are minimum to be dropped to-
800mV is far below its corrosion potential.Thus it is effectively protected by protection metal is available.After illumination stops, 304 are not
Rust steel electrode current potential rises to -350mV, is still below its corrosion potential, shows the AgSbS under dark-state2/TiO2Nano-tube array
Composite membrane still has certain protecting effect to 304 stainless steels.
In conclusion the AgSbS that the present invention is prepared using anodizing and continuous ionic layer absorption method2/TiO2Nanotube
It is a kind of excellent optical anode material to being there is stable anti-corrosion effect by protection metal when array composite film is as light anode.
Detailed description of the invention
Fig. 1 is TiO provided in an embodiment of the present invention2The surface topography (SEM figure) of nanotube.
Fig. 2 is sequentially completed an Ag to be provided in an embodiment of the present invention2S and Sb2S3The AgSbS of deposition cycle2/TiO2Nanometer
Tube array composite film surface topography (SEM figure), scale are 1 μm.
Fig. 3 is sequentially completed an Ag to be provided in an embodiment of the present invention2S and Sb2S3The AgSbS of deposition cycle2/TiO2Nanometer
The open circuit potential figure and TiO of tube array composite film and the coupling of 304 stainless steels2What film of Nano tube array and 304 stainless steels were coupled
Open circuit potential.Wherein, abscissa is the time (s), and ordinate is voltage (V vs.SCE).ON indicates to open light source, OFF expression pass
Black out source.
Fig. 4 is sequentially completed an Ag for what this bright embodiment provided2S and Sb2S3The AgSbS of deposition cycle2/TiO2Nanotube
Array composite film and TiO2The transient state optogalvanic spectra that nano-tube array composite membrane is coupled with 304 stainless steels respectively.Wherein, horizontal seat
It is designated as the time (s), ordinate is density of photocurrent (μ Acm-2).ON indicates to open light source, OFF expression closing light source.
Fig. 5 is sequentially completed Ag three times to be provided in an embodiment of the present invention2S and Sb2S3The AgSbS of deposition cycle2/TiO2Nanometer
The surface topography (SEM figure) of tube array composite film.
Fig. 6 is sequentially completed Ag three times to be provided in an embodiment of the present invention2S and Sb2S3The AgSbS of deposition cycle2/TiO2Nanometer
The open circuit potential figure and TiO of tube array composite film and the coupling of 304 stainless steels2The open circuit of film of Nano tube array and 304 stainless steels
Potential diagram.Wherein, abscissa is the time (s), and ordinate is voltage (V vs.SCE).ON indicates to open light source, OFF expression closing
Light source.
Fig. 7 is sequentially completed Ag three times for what this bright embodiment provided2S and Sb2S3The AgSbS of deposition cycle2/TiO2Nanotube
Array composite film and TiO2Nano-tube array composite membrane respectively with 304 stainless steels coupling after transient state optogalvanic spectra.Wherein, horizontal
Coordinate is the time (s), and ordinate is density of photocurrent (μ Acm-2).ON indicates to open light source, OFF expression closing light source.
Specific embodiment
Below with reference to embodiment and attached drawing the present invention will be further explained explanation.
Structure of composite membrane of the invention is AgSbS2Nanoparticle deposition is in TiO2On nanotube.AgSbS2Nano particle is multiple
After conjunction, TiO2It is obviously improved in visible region absorption, and matched position of energy band can drive photoproduction current-carrying after semiconductors coupling
Sub- quick separating is reduced secondary compound.AgSbS of the invention2It is sensitized TiO2Nano-tube array laminated film, as light anode material
When material carries out cathodic protection, relative to TiO2The utilization rate of visible light and the separation rate of photo-generated carrier can be improved in material, shows
The electrode potential for reducing by 304 stainless steels is write, corrosion rate is reduced.
Further, the present invention is by AgSbS2The advantages of narrow band gap and carrier are in TiO2The one-dimensional channel transfer of nanotube
Fast feature combines, and realizes TiO2The increase of active to visible absorption enhancing and carrier separation migration rate.From
And transmit more light induced electrons to by protection metal, it can be used for the photoproduction cathodic protection field of metal.
Embodiment 1
The preparation of light anode, comprising the following steps:
The pretreatment of titanium substrate: it is 1 × 4 × 0.1cm that the titanium-base that purity is 99.9%, which is cut into specification,3Titanium sheet,
Growth substrate as composite membrane.Titanium sheet is cleaned with deionized water and ethyl alcohol, is dried up spare.Weigh 7.2g NH4F is dissolved in 40mL
Deionized water in.Concentrated nitric acid and 30%H are measured in draught cupboard2O2Each 96mL and NH4F solution mixes in 500mL beaker,
Ultrasonic 5min is uniformly mixed, and is made into polishing fluid.The titanium sheet for choosing smooth no marking is put into a small amount of polishing fluid, waits 20~30s,
It is cleaned after taking out titanium sheet with deionized water.After polishing, the titanium sheet after polishing is attached in the beaker for filling deionized water, is successively used
Deionized water and EtOH Sonicate 5min alternately three times finally impregnate titanium sheet to be used in ethanol.
TiO2Nano-tube array film preparation: 0.557g NH is weighed4F is dissolved in 10mL deionized water, stirs evenly.Amount
Take 100mL ethylene glycol and NH4The mixing of F solution, stirs evenly, is made into anodic oxidation electrolyte.It is poured into about into 100mL beaker
The electrolyte of 80mL clamps titanium sheet and platinum electrode with fixture, is placed in electrolyte, is separately connected the positive and negative of DC power supply
Pole.Setting direct current power source voltage is 20V.After anodic oxidation 1h, titanium sheet is cleaned with ethyl alcohol and deionized water, is put into Muffle after drying
It is sintered in furnace, 450 DEG C of heat preservation 2h is raised to the heating rate of 5 DEG C/min, cool to room temperature with the furnace later.Titanium plate surface can be made
Obtain TiO2Nanotube (referring to Fig. 1).
AgSbS2/TiO2The preparation of nano-tube array composite membrane: 1.19g AgNO is weighed3It is dissolved in 70mL ethanol solution,
60min is stirred, 0.1M AgNO is obtained3Ethanol solution；Weigh 1.68g Na2S·9H2O is dissolved in 70mL methanol, stirs 20min, obtains
To 0.1M Na2S methanol solution.Weigh 1.60g SbCl3It is dissolved in 70mL ethyl alcohol, 20min is stirred, obtains 0.1M SbCl3Ethyl alcohol
Solution.To solution, all dissolution is with postponing, by area load TiO2The titanium sheet of film of Nano tube array immerses the AgNO of above-mentioned configuration3
Ethanol solution cleans 2~3s with ethyl alcohol at once after impregnating 60s；Then titanium sheet is immersed the Na of above-mentioned configuration2S methanol solution,
After impregnating 4min, 2~3s is cleaned with ethyl alcohol at once.Above step completes an Ag2S deposition cycle, obtains Ag2The TiO of S modification2
Film of Nano tube array.Titanium sheet Jing Guo above-mentioned processing is immersed to the SbCl of above-mentioned configuration again3Ethanol solution, after impregnating 15s, at once
2~3s is cleaned with ethyl alcohol, titanium sheet is then immersed 0.1M Na2S methanol solution, after impregnating 1min, 2 are cleaned with ethyl alcohol at once~
3s；The SbCl of above-mentioned configuration is immersed after cleaning again3Ethanol solution after impregnating 15s, cleans 2~3s with ethyl alcohol at once, immerses 0.1M
Na2S methanol solution cleans 2~3s with ethyl alcohol at once after impregnating 1min.Above step completes a Sb2S3Deposition cycle.I.e. in
Titanium-based surface obtains Ag2S and Sb2S3The TiO of modification2Film of Nano tube array.The titanium sheet handled well is leaned in sidewall of crucible, is placed in
In Muffle furnace.Muffle furnace rises to 350 DEG C with the speed of 5 DEG C/min, calcines titanium sheet 10min, obtains regular AgSbS2/
TiO2Composite membrane, obtained composite membrane are denoted as AT-1 (referring to fig. 2).
To AgSbS2/TiO2Nano-tube array composite membrane carries out photoproduction cathodic protection test: AgSbS2/TiO2Nanotube battle array
Column composite membrane is used as working electrode as light anode and the coupling of 304 stainless steels, and two electrodes are respectively placed in containing 0.05M Na2S and
In the photoelectrolytic cell of 0.1M NaOH mixed solution and the corrosion electrolytic cell containing 3.5wt.%NaCl solution, two electrolytic cells pass through
Proton exchange membrane connection, saturated calomel electrode are placed in corrosion electrolytic cell as reference electrode, do open circuit potential test.
AgSbS2/TiO2Nano-tube array composite membrane connects working electrode, and 304 stainless steels ground connection is respectively placed in containing 0.05M Na2S is molten
In the photoelectrolytic cell of liquid and 0.1M NaOH solution and the corrosion electrolytic cell containing 3.5wt.%NaCl solution, transient state photoelectric current is done
Test.Using xenon lamp simulated visible light, direct irradiation is in AgSbS2/TiO2Nano-tube array composite film surface.(referring to Fig. 3~figure
4)
Fig. 1 is TiO2The SEM of nano-tube array schemes, and scale is 1 μm, it can be seen that TiO2The internal diameter of nanotube is about 50nm,
Outer diameter is about 80nm.
Fig. 2 is that the SEM of AT-1 composite membrane schemes, and scale is 1 μm, it can be seen that AgSbS2Particle is more uniformly adhered to receive
Mitron nozzle and surrounding.
Fig. 3 is AT-1 and TiO2The open circuit potential curve that light anode acts on 304 stainless steel protections.Under illumination condition,
And TiO2304 stainless steels of light anode coupling, current potential are -420mV, and the current potential range of decrease is about 210mV；After the coupling of AT-1 composite membrane
304 stainless steels, current potential be -720mV, the current potential range of decrease is about 470mV.Therefore, TiO2Nanotube and AgSbS2/TiO2Nanotube
Array composite film has protective effect to the 304 stainless steel capital, and the protective effect of the latter is greater than the former.When closing light source, 304 stainless steels
Current potential restore initial value substantially.
Fig. 4 is AT-1 and TiO2The transient state optogalvanic spectra that light anode is coupled with 304 stainless steels respectively.Alternating is opened the light and is closed
Light, photoelectric current change in great-jump-forward.Light source is opened, photoelectric current moment rises；With the extension of light application time, under photoelectric current is rapid
It drops and the value that tends towards stability；Light source is closed, photoelectric current declines rapidly, then tends towards stability.AgSbS2/TiO2Nano-tube array is compound
The photoelectric current stationary value that film generates can reach 20 μ A/cm2, TiO2The photoelectric current stationary value that nano-tube array generates is only to 10 μ A/
cm2.What optogalvanic spectra characterized is the separating capacity of the electrons and holes in material.Relative to TiO2Nanotube, AgSbS2/TiO2
The photoelectric current that nano-tube array composite membrane generates is big, illustrates that the separating capacity of the electron hole pair in this film is strong, the probability of recombination is low,
Therefore AgSbS2/TiO2The cathodic protection effect of nano-tube array composite membrane is excellent.
Embodiment 2
The preparation of light anode, comprising the following steps:
The pretreatment of titanium substrate: it is 1 × 4 × 0.1cm that the titanium-base that purity is 99.9%, which is cut into specification,3Titanium sheet,
Growth substrate as composite membrane.Titanium sheet is cleaned with deionized water and ethyl alcohol, is dried up spare.Weigh 7.2g NH4F is dissolved in 40mL
Deionized water in.Concentrated nitric acid and 30%H are measured in draught cupboard2O2Each 96mL and NH4F solution mixes in 500mL beaker,
Ultrasonic 5min is uniformly mixed, and is made into polishing fluid.The titanium sheet for choosing smooth no marking is put into a small amount of polishing fluid, waits 20~30s,
It is cleaned after taking out titanium sheet with deionized water.After polishing, the titanium sheet after polishing is attached in the beaker for filling deionized water, is successively used
Deionized water and EtOH Sonicate 5min alternately three times finally impregnate titanium sheet to be used in ethanol.
TiO2Nano-tube array film preparation: 0.557g NH is weighed4F is dissolved in 10mL deionized water, stirs evenly.Amount
Take 100mL ethylene glycol and NH4The mixing of F solution, stirs evenly, is made into anodic oxidation electrolyte.It is poured into about into 100mL beaker
The electrolyte of 80mL clamps titanium sheet and platinum electrode with fixture, is placed in electrolyte, is separately connected the positive and negative of DC power supply
Pole.Setting direct current power source voltage is 20V.After anodic oxidation 1h, titanium sheet is cleaned with ethyl alcohol and deionized water, is put into Muffle after drying
It is sintered in furnace, 450 DEG C of heat preservation 2h is raised to the heating rate of 5 DEG C/min, cool to room temperature with the furnace later.Titanium plate surface can be made
Obtain TiO2Nanotube (referring to Fig. 1).
AgSbS2/TiO2The preparation of nano-tube array composite membrane: 1.19g AgNO is weighed3It is dissolved in 70mL ethanol solution,
60min is stirred, 0.1M AgNO is obtained3Ethanol solution；Weigh 1.68g Na2S·9H2O is dissolved in 70mL methanol, stirs 20min, obtains
To 0.1M Na2S methanol solution.Weigh 1.60g SbCl3It is dissolved in 70mL ethyl alcohol, 20min is stirred, obtains 0.1M SbCl3Ethyl alcohol
Solution.To solution, all dissolution is with postponing, by area load TiO2The titanium sheet of film of Nano tube array immerses the AgNO of above-mentioned configuration3
Ethanol solution cleans 2~3s with ethyl alcohol at once after impregnating 60s；Then titanium sheet is immersed the Na of above-mentioned configuration2S methanol solution,
After impregnating 4min, 2~3s, as an Ag are cleaned with ethyl alcohol at once2S deposition cycle.It repeats the above steps, completes Ag three times2S
Deposition cycle obtains Ag2The TiO of S modification2Film of Nano tube array.The titanium sheet Jing Guo above-mentioned processing is immersed into above-mentioned configuration again
SbCl3Ethanol solution cleans 2~3s with ethyl alcohol at once after impregnating 15s, and titanium sheet is then immersed 0.1M Na2S methanol solution, leaching
After stain 1min, 2~3s is cleaned with ethyl alcohol at once；The SbCl of above-mentioned configuration is immersed after cleaning again3Ethanol solution after impregnating 15s, is stood
Quarter cleans 2~3s with ethyl alcohol, immerses 0.1M Na2S methanol solution cleans 2~3s, as one with ethyl alcohol at once after impregnating 1min
Secondary Sb2S3Deposition cycle.Above-mentioned steps in triplicate complete Sb three times2S3Deposition cycle.Obtain Ag2S and Sb2S3Modification
TiO2Film of Nano tube array.The titanium sheet handled well is leaned in sidewall of crucible, is placed in Muffle furnace.Muffle furnace is with the speed of 5 DEG C/min
Degree rises to 350 DEG C, calcines titanium sheet 10min, obtains regular AgSbS2/TiO2Composite membrane, obtained composite membrane are denoted as AT-3
(referring to Fig. 5).
To AgSbS2/TiO2Nano-tube array composite membrane carries out photoproduction cathodic protection test: AgSbS2/TiO2Nanotube battle array
Column composite membrane is used as working electrode as light anode and the coupling of 304 stainless steels, and two electrodes are respectively placed in containing 0.05M Na2S and
In the photoelectrolytic cell of 0.1M NaOH mixed solution and the corrosion electrolytic cell containing 3.5wt.%NaCl solution, two electrolytic cells pass through
Proton exchange membrane connection, saturated calomel electrode are placed in corrosion electrolytic cell as reference electrode, do open circuit potential test.
AgSbS2/TiO2Nano-tube array composite membrane connects working electrode, and 304 stainless steels ground connection is respectively placed in containing 0.05M Na2S is molten
In the photoelectrolytic cell of liquid and 0.1M NaOH solution and the corrosion electrolytic cell containing 3.5wt.%NaCl solution, transient state photoelectric current is done
Test.Using xenon lamp simulated visible light, direct irradiation is in AgSbS2/TiO2Nano-tube array composite film surface.(referring to Fig. 6~figure
7)
Fig. 5 is that the SEM of AT-3 composite membrane pattern schemes, and scale is 1 μm.AgSbS2Particle is more uniformly adhered to nanotube
Nozzle and surrounding.Compared with Fig. 2, the nanometer nozzle of Fig. 5 blocking is more, and the nano particle of attachment is more.
Fig. 6 is AT-3 composite membrane and TiO2The open circuit potential curve that light anode acts on 304 stainless steel protections.In illumination item
Under part and TiO2304 stainless steels of light anode coupling, current potential are -410mV, and the current potential range of decrease is about 200mV；With AT-3 composite membrane
304 stainless steels after coupling, current potential are -800mV, and the current potential range of decrease is about 530mV.Therefore, AgSbS2/TiO2Nano-tube array is multiple
Close film and TiO2Nanotube has protective effect to the 304 stainless steel capital, and the protective effect of the latter is greater than the former.It is preceding when closing light source
The current potential of person restores initial value substantially, and the current potential of the latter is returned to the position for being defeated by former current potential about 70mV.
Fig. 7 is AT-3 composite membrane and TiO2The transient state optogalvanic spectra of nanotube photoelectric conversion efficiency.Alternating is opened the light and black out,
Photoelectric current changes in great-jump-forward.Light source is opened, photoelectric current moment rises；With the extension of light application time, photoelectric current declines rapidly
And the value that tends towards stability；Light source is closed, photoelectric current declines rapidly, then slightly rises and tends towards stability.AgSbS2/TiO2Nanotube battle array
The photoelectric current stationary value that column composite membrane generates is up to 30 μ A/cm2, TiO2The photoelectric current stationary value that nano-tube array generates is only to 10 μ
A/cm2.What optogalvanic spectra characterized is the separating capacity of the electrons and holes in material, relative to TiO2Nanotube, AgSbS2/
TiO2The photoelectric current that nano-tube array composite membrane generates is big, illustrates that the separating capacity of the electron hole pair in this film is more excellent, compound
Probability is obviously low, therefore AgSbS2/TiO2The protecting effect of nano-tube array composite membrane is more excellent.
Claims (9)
1. a kind of AgSbS2It is sensitized TiO2The preparation method of composite film material, it is characterised in that: by area load TiO2Nanotube battle array
The matrix of column film is impregnated into progress ion layer adsorption reaction in the solution containing Ag, S and Sb ion, so that in TiO2Nano-tube array
The surface of film forms Ag2S and Sb2S3Nano particle obtains AgSbS in matrix surface using calcining2Nano-particle modified
TiO2Nano-tube array composite membrane.
2. AgSbS according to claim 12It is sensitized TiO2The preparation method of composite film material, it is characterised in that: the surface
Load TiO2Carrying out ion layer adsorption reaction in solution of the matrix dipping containing Ag, S and Sb ion of film of Nano tube array is by table
Face loads TiO2The matrix of film of Nano tube array successively carries out Ag2S deposition cycle and Sb2S3Deposition cycle makes TiO2Nanotube battle array
The surface of column film forms Ag2S and Sb2S3Nano particle；Wherein, each circulation at least carries out primary.
3. AgSbS as described in claim 22It is sensitized TiO2The preparation method of composite film material, it is characterised in that: the Ag2S
Deposition cycle is by area load TiO2The matrix of film of Nano tube array is first dipped into containing 0.05~0.1M AgNO3Ethanol solution
50~60s of middle dipping after being cleaned with methanol, then immerses the Na containing 0.05~0.1M immediately2In the methanol solution of S dipping 3~
4min is cleaned with ethyl alcohol, that is, completes an Ag2S deposition cycle；It is repeated again in the way of primary depositing circulation, i.e., in fact
Now multiple Ag2S deposition cycle, so that in TiO2Nano-tube array film surface forms Ag2S nano particle.
4. AgSbS as described in claim 22It is sensitized TiO2The preparation method of composite film material, it is characterised in that:
The Sb2S3Deposition cycle is that surface is formed Ag2The TiO of S nano particle2The matrix of film of Nano tube array, which is first dipped into, to be contained
0.05~0.1M SbCl3Ethanol solution in impregnate 10~15s, after being cleaned with methanol, immediately immerse the Na containing 0.05~0.1M2S
Methanol solution in impregnate 50~60s, cleaned, be again dipped into after cleaning containing 0.05~0.1M SbCl with ethyl alcohol3Ethanol solution
50~60s of middle dipping after being cleaned with methanol, immerses the Na containing 0.05~0.1M immediately2In S methanol solution, that is, complete a Sb2S3
Deposition cycle；It is repeated again in the way of primary depositing circulation, that is, realizes multiple Sb2S3Deposition cycle, so that i.e. in TiO2
Nanotube surface forms Ag2S and Sb2S3Nano particle.
5. AgSbS according to claim 12It is sensitized TiO2The preparation method of composite film material, it is characterised in that: the calcining
For above-mentioned surface is formed Ag2S、Sb2S3The TiO of nano particle2The matrix of film of Nano tube array is placed in Muffle furnace, setting temperature
Degree is 300~350 DEG C, calcines 8~15min, i.e., obtains AgSbS in matrix surface2It is sensitized TiO2Composite film material.
6. a kind of AgSbS of claim 1 the method preparation2It is sensitized TiO2Composite film material, it is characterised in that: wanted by right
Method described in asking 1 prepares AgSbS in matrix surface2Nano particle is carried on TiO2Composite film material on nano-tube array.
7. a kind of AgSbS as claimed in claim 62It is sensitized TiO2The application of composite film material, it is characterised in that: the composite membrane
Application of the material in the photoproduction cathodic protection of metal.
8. AgSbS according to claim 72It is sensitized TiO2The application of composite film material, it is characterised in that: the composite membrane is made
Application for light anode, in photoproduction cathodic protection.
9. AgSbS according to claim 62It is sensitized TiO2The application of composite film material, it is characterised in that: the composite membrane exists
For inhibiting metal erosion as the application in anti-corrosion protective film.
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