CN109207969A - It is a kind of for the antimony base complex sensitized titanium dioxide composite membrane of photoproduction cathodic protection and its preparation and application - Google Patents
It is a kind of for the antimony base complex sensitized titanium dioxide composite membrane of photoproduction cathodic protection and its preparation and application Download PDFInfo
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- CN109207969A CN109207969A CN201810707961.4A CN201810707961A CN109207969A CN 109207969 A CN109207969 A CN 109207969A CN 201810707961 A CN201810707961 A CN 201810707961A CN 109207969 A CN109207969 A CN 109207969A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Abstract
The present invention relates to a kind of composite nano tube light anodes, more particularly, to a kind of antimony base complex sensitized titanium dioxide composite membrane (Sb for photoproduction cathodic protection2S3/Sb2O3/TiO2) and its prepare and apply.By one pot of hydro-thermal method by Sb2S3/Sb2O3It is carried on TiO2On nano-tube array, antimony base complex sensitized titanium dioxide composite membrane is formed, i.e., being hydrated potassium antimony tartrate using half is antimony source, Sodium Sulphate Nine Hydroxide as sulphur source, by one pot of hydro-thermal method by netted Sb2S3With rodlike Sb2O3It is carried on TiO2。Sb2S3And Sb2O3Load greatly enhance TiO2Absorption to visible light, the special structure of composite membrane and energy band distribution clearly enhance the separation rate of photo-generated carrier.Composite membrane of the invention can obviously reduce the corrosion potential of 304 stainless steels, have the characteristics that preparation method is easy, product photoelectric conversion efficiency is high, performance is stable.
Description
Technical field
The present invention relates to a kind of composite nano tube light anodes, multiple more particularly, to a kind of antimony base for photoproduction cathodic protection
Close object sensitized titanium dioxide composite membrane (Sb2S3/Sb2O3/TiO2) and its prepare and apply.
Background technique
304 stainless steels (304SS) can form protective oxide film on surface and have good corrosion resistance, therefore wide
It is general to be applied in the building of various engineerings.However, when stainless steel immersion contains Cl-Electrolyte when, oxidation film thereon can be by ring
Cl in border-It destroys and spot corrosion occurs, thus keep engineering building active time brief, in some instances it may even be possible to environment and the person and property
Safety generates threat.And it is reported that the loss as caused by corroding accounts for corresponding state including the U.S., Britain and Japan and other countries
The 1~5% of family's gross national product (GNP).Therefore, the antiseptic property for improving 304SS is a urgent ecology, economy and society
It can demand.
In recent years, photo-catelectrode protection technology causes people as a kind of environmental-friendly, energy saving novel anticorrosion technology
Extensive concern.Nineteen ninety-five, Yuan and Tsujikawa report TiO2It can be used for optical anode material, effective light implemented to copper
Raw cathodic protection.Hereafter, TiO2With the advantage of its high efficiency, low cost, hypotoxicity and good chemical stability, gradually it is applied to
Photoproduction cathodic protection field.However, TiO2Forbidden bandwidth is wide (3.2eV), low to visible light utilization efficiency, and photo-generated carrier is easily multiple
It closes, in the dark state to metal unprotect effect.These disadvantages limit TiO2Further apply.It is usually used in modified TiO2Side
Method includes metal and nonmetallic ion-doped, photosensitizer and semiconductors coupling etc..Wherein, narrow gap semiconductor it is compound not only
It can make TiO2Absorption band edge red shift, increase it to visible light utilization efficiency, and the suitable band structure of compound can effectively increase
Add the separative efficiency of carrier.
Sb2S3It is a kind of narrow band gap (1.7eV) P-type semiconductor, light absorption range almost covers all visible regions, inhales
Backscatter extinction logarithmic ratio is up to 5 × 104cm-1.Another antimony-based compounds Sb2O3It is a kind of N-type semiconductor, forbidden bandwidth (3.0eV) and TiO2
Forbidden bandwidth is similar, is widely used in fire retardant, optical device and conductive material.But at this stage, in photoproduction cathodic protection
In there are no to Sb2S3/Sb2O3/TiO2The research of light anode.
Summary of the invention
The purpose of the present invention is be directed to TiO2The light anode disadvantage low to sun light utilization efficiency and photoelectric efficiency, provides one kind
Antimony base complex sensitized titanium dioxide composite membrane (Sb for photoproduction cathodic protection2S3/Sb2O3/TiO2) and its prepare and apply.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of antimony base complex sensitized titanium dioxide composite membrane for photoproduction cathodic protection, will by one pot of hydro-thermal method
Sb2S3/Sb2O3It is carried on TiO2On nano-tube array, antimony base complex sensitized titanium dioxide composite membrane is formed.
Sb in the composite membrane2O3It is in the rodlike structural load of micron in TiO for monocline type2It is carrier transport on film
Provide direct path.Narrow band gap Sb2S3For monocline type, in tridimensional network by Sb2O3Micron bar is connected with each other, and makes TiO2It is right
The absorption band edge of visible light expands to 600~700nm.
The hydro-thermal method is that half hydration potassium antimony tartrate is dissolved in excessive ultrapure water, is stirred and evenly mixed, by nine water under stirring
It closes vulcanized sodium to be added thereto with vigorous stirring, is stirred for mixing to obtain mixed liquor, then by mixed liquor and TiO2Nanotube substrate
In hydrothermal reaction kettle, 150~200 DEG C of incubation water heatings 6~for 24 hours, composite membrane is taken out after hydro-thermal, washs, be drying to obtain Sb2S3/
Sb2O3/TiO2Composite film photo-anode.
Half hydration antimony tartrate potassium application rate is 0.3~6mmol, Sodium Sulphate Nine Hydroxide and Ban Shui in every 50mL ultrapure water
Conjunction antimony tartrate potassium application rate molar ratio is 1-2.5:1.
The hydro-thermal reaction take after film using water and ethyl alcohol alternately cleaning for several times, 50~80 DEG C of 1~6h of vacuum drying to get
Sb2S3/Sb2O3/TiO2Composite film photo-anode.
A kind of preparation method of the antimony base complex sensitized titanium dioxide composite membrane for photoproduction cathodic protection: pass through anode
Oxidizing process is simultaneously calcined in titanium plate surface modification TiO2Nano-pipe array thin film, by one pot of hydro-thermal method by Sb2S3/Sb2O3It is carried on
TiO2On nano-tube array, antimony base complex sensitized titanium dioxide composite membrane is formed.
Half hydration potassium antimony tartrate is dissolved in excessive ultrapure water, is stirred and evenly mixed, by Sodium Sulphate Nine Hydroxide in play under stirring
It is strong to be added with stirring wherein, it is stirred for mixing to obtain mixed liquor, then by mixed liquor and TiO2Nanotube substrate is in hydrothermal reaction kettle
In, 150~200 DEG C of incubation water heatings 6~for 24 hours, composite membrane is taken out after hydro-thermal, washs, be drying to obtain Sb2S3/Sb2O3/TiO2It is multiple
Close film light anode.
Half hydration antimony tartrate potassium application rate is 0.3~6mmol, Sodium Sulphate Nine Hydroxide and Ban Shui in every 50mL ultrapure water
Conjunction antimony tartrate potassium application rate molar ratio is 1-2.5:1.
The hydro-thermal reaction take after film using water and ethyl alcohol alternately cleaning for several times, 50~80 DEG C of 1~6h of vacuum drying to get
Sb2S3/Sb2O3/TiO2Composite film photo-anode.
The titanium sheet is that titanium foil content is greater than 99.9wt%, with a thickness of 0.1~0.3mm titanium foil be cut into a length of 2~
5cm, width are the titanium foil of 1~2cm.
The anodizing refers to using two electrode systems: using titanium sheet after pretreatment as working electrode, platinum electrode is made
To be placed in electrolyte to electrode, 1~2h of oxidation at voltages of 20~30V；Then 450~500 DEG C of calcinings 2 in Muffle furnace
~2.5h, and cool to room temperature with the furnace, TiO can be obtained in titanium substrate2Nano-pipe array thin film.
The pretreatment is by after 15~40min of titanium sheet EtOH Sonicate, then with 5~20min of deionized water ultrasound；It
The titanium sheet after cleaning is placed in 10~30s of polishing in polishing fluid afterwards, then is alternately cleaned for several times with deionized water and ethyl alcohol.Wherein throw
Light liquid includes 3.56wt% ammonium fluoride, 41.37vol% concentrated nitric acid (65~68wt%) and 41.37vol% hydrogen peroxide.
The electrolyte is that ammonium fluoride is dissolved in ultrapure water, and it is uniform to add ethylene glycol ultrasonic mixing.Wherein it is fluorinated
Ammonium mass fraction is 0.55wt%, and the volume ratio of ethylene glycol and ultrapure water is 10~11.
A kind of application of the antimony base complex sensitized titanium dioxide composite membrane for photoproduction cathodic protection, the composite membrane can
Optical anode material as photoproduction cathodic protection.
The Sb of photoproduction cathodic protection is used for prepared by the present invention2S3/Sb2O3/TiO2The photoproduction cathode of composite film photo-anode
Test method is protected, it is specific using the double-electrolyzer system being made of photoelectrolytic cell and corrosion electrolytic cell.Sb2S3/Sb2O3/TiO2
Composite membrane is placed in as light anode containing 0.1mol/LNa2SO3Photoelectrolytic cell.Corrode electrolytic cell and uses three-electrode system, platinum
Electrode is used as to electrode, and saturated calomel electrode is connect with light anode collectively as work as reference electrode, 304SS by conducting wire
Electrode.Photoelectrolytic cell is connect with corrosion electrolytic cell by salt bridge.Visible light source adds 420nm optical filter to provide by 300W xenon lamp,
Light anode is away from light source 10cm.Electrochemical workstation records potential change of the 304SS before and after illumination.
Basic principle of the invention: Sb2S3It is that a kind of narrow band gap (1.7eV) p-type is partly led.Its load is greatly improved
TiO2To visible absorption, and Sb2S3And TiO2Conduction band and valence band current potential relative vacuum energy level be respectively -3.7/-4.2eV and -
5.4/-7.4eV, thus staggered band structure can be formed, to be conducive to inhibit the compound of light induced electron and hole.Sb2O3It is
The N-type semiconductor that a kind of forbidden bandwidth is 3.0eV.The rodlike Sb of micron2O3, direct road is provided for the transmission of photo-generated carrier
Diameter is conducive to electron transmission to 304SS.And p-type Sb2S3With N-type Sb2O3/TiO2Interface is easily formed P-N junction built in field, more into
One step improves the separation rate of photo-generated carrier.Therefore, pass through Sb2S3And Sb2O3It is sensitized TiO altogether2TiO can be effectively improved2Film
To the photoproduction cathodic protection effect of metal.
Advantage for present invention:
1. the relatively pure TiO of composite film photo-anode of the present invention2, have excellent absorption to visible light, absorption band change expands to 600
~700nm, and photo-generated carrier separating capacity is remarkably reinforced.
2. the load of antimony base complex of the present invention uses one pot of hydro-thermal method, method is simply easily operated.
3. composite film photo-anode of the present invention is under visible light illumination, 304SS current potential can be made to be down to -750mV, current potential under dark-state
Though there is the corrosion potential for being still significantly lower than 304SS.Photoproduction cathodic protection performance is much higher than pure TiO2。
4. composite film photo-anode of the present invention still has good photoproduction cathodic protection effect, stability in the case where repeating to be opened and closed light
Well, composite membrane is bigger to the absorption of visible light and under large dosage, and photo-generated carrier separation rate improves, transient state photoelectric current
Value increases and negative move of open circuit potential becomes apparent from, and the photoproduction cathodic protection performance of composite membrane gets a promotion, it is seen that it is suitable for industry
Change.
Detailed description of the invention
Fig. 1 is the TiO that the embodiment of the present invention 1 provides2Film (a) and Sb2S3/Sb2O3/TiO2The surface shape of composite membrane (b)
Looks (SEM figure).
Fig. 2 is the TiO that the embodiment of the present invention 1 provides2Film and Sb2S3/Sb2O3/TiO2The UV, visible light of composite membrane is unrestrained anti-
Penetrate figure.
Fig. 3 be the 304SS that provides of the embodiment of the present invention 1 in 3.5%NaCl solution respectively with TiO2Film and Sb2S3/
Sb2O3/TiO2Composite film photo-anode coupling, it is seen that light irradiation front and back electrode potential changes over time curve.On indicates illumination, off
It indicates to close light source, that is, dark-state.
Fig. 4 is TiO prepared by the embodiment of the present invention 12Film and Sb2S3/Sb2O3/TiO2Composite membrane is under visible light illumination
Transient state photoelectricity flow graph.On indicates illumination, and off indicates to close light source, that is, dark-state.
Fig. 5 is the TiO that the embodiment of the present invention 2 provides2Film (a) and Sb2S3/Sb2O3/TiO2The surface shape of composite membrane (b)
Looks (SEM figure).
Fig. 6 is the TiO that the embodiment of the present invention 2 provides2Film and Sb2S3/Sb2O3/TiO2The UV, visible light of composite membrane is unrestrained anti-
Penetrate figure.
Fig. 7 be the 304SS that provides of the embodiment of the present invention 2 in 3.5%NaCl solution respectively with TiO2Film and Sb2S3/
Sb2O3/TiO2Composite film photo-anode coupling, it is seen that light irradiation front and back electrode potential changes over time curve.On indicates illumination, off
It indicates to close light source, that is, dark-state.
Fig. 8 is TiO prepared by the embodiment of the present invention 22Film and Sb2S3/Sb2O3/TiO2Composite membrane is under visible light illumination
Transient state photoelectricity flow graph.On indicates illumination, and off indicates to close light source, that is, dark-state.
Specific embodiment
The content of present invention is further illustrated below in conjunction with attached drawing.But it is noted that simply changing to what the content of present invention was done
Change also belongs within rights protection scope of the present invention.
The present invention, which passes through anodizing first and calcines, modifies TiO in titanium plate surface2Nano-pipe array thin film, Yi Banshui
Close that potassium antimony tartrate is antimony source, Sodium Sulphate Nine Hydroxide is sulphur source, by one pot of hydro-thermal method by netted Sb2S3With rodlike Sb2O3
It is carried on TiO2On nano-tube array.Sb2S3And Sb2O3Load greatly enhance TiO2Absorption to visible light, then by 304SS
Be placed in the corrosive medium of 3.5%NaCl respectively with TiO2Film and Sb2S3/Sb2O3/TiO2Composite film photo-anode lotus root connects, test
Photoproduction cathodic protection effect of the composite membrane of the present invention to 304SS.The special structure of composite membrane and energy band distribution clearly enhance light
The separation rate of raw carrier.Composite membrane of the invention can obviously reduce the corrosion potential of 304 stainless steels, have preparation method letter
Just, the feature that product photoelectric conversion efficiency is high, performance is stable.
Embodiment 1
Sb2S3/Sb2O3/TiO2The preparation method of composite membrane the following steps are included:
The pretreatment of titanium sheet: titanium foil content is greater than 99.9wt.%, is cut into 1 × 4cm with a thickness of the titanium foil of 0.3mm2's
Titanium sheet.Again by the titanium sheet sheared EtOH Sonicate 30min, deionized water ultrasound 10min, ethyl alcohol and deionized water replace later
It is dried after cleaning and is placed in sealed storage in dehydrated alcohol.It weighs 1.80g ammonium fluoride to be dissolved in 10mL deionized water, be separately added into
24mL hydrogen peroxide and 24mL concentrated nitric acid are made into polishing fluid, the titanium sheet after cleaning are put in 30s in polishing fluid, then use deionization respectively
Water, ethyl alcohol cleaning, dry stand-by.
TiO2The preparation of film: it weighs 0.33g ammonium fluoride and is dissolved in 6mL ultrapure water, add 60mL ethylene glycol, ultrasound makes
The two is uniformly mixed, and obtains anodic oxidation electrolyte.Anodic oxidation uses three-electrode system, using pretreated titanium sheet as work
Electrode, platinum electrode are to electrode, and saturated calomel electrode is reference electrode.Titanium sheet is placed in above-mentioned electrolyte, it is positive under 20V voltage
Pole aoxidizes 1h, is alternately cleaned with ethyl alcohol and deionized water later, naturally dry.Titanium sheet after drying 450 DEG C of perseverances in Muffle furnace
Temperature calcining 2h, cools to the furnace after room temperature up to TiO2Nano-tube film (referring to Fig. 1 a).
Sb2S3/Sb2O3/TiO2The preparation of composite membrane: weighing half hydration potassium antimony tartrate of 0.41g and be dissolved in 50mL ultrapure water,
0.29g Sodium Sulphate Nine Hydroxide is added in magnetic agitation 15min with vigorous stirring later, continues to obtain reaction solution after stirring 35min.
TiO will be had2The titanium substrate of film is vertically arranged in 100mL ptfe autoclave, then reaction solution is poured into the reaction kettle,
Room temperature is cooled to the furnace after 180 DEG C of heating 12h in air dry oven.The titanium substrate with composite membrane is taken out after hydro-thermal, is gone
Alternately for several times, 70 DEG C of vacuum drying 4h are to get Sb for cleaning for ionized water and ethyl alcohol2S3/Sb2O3/TiO2Composite membrane is (referring to Fig. 1 b and figure
2)。
Sb2S3/Sb2O3/TiO2The photoproduction cathodic protection of composite membrane is tested: specific using by photoelectrolytic cell and corrosion electrolytic cell
The double-electrolyzer system of composition.Sb2S3/Sb2O3/TiO2Composite membrane is placed in as light anode containing 0.1mol/L Na2SO3Light
Electrolytic cell.Corrode electrolytic cell and use three-electrode system, platinum electrode is used as to electrode, saturated calomel electrode as reference electrode,
304SS connect electrochemical workstation working electrode interface with light anode coupling by conducting wire jointly.Photoelectrolytic cell and corrosion are electrolysed
Pond is connected by salt bridge.Visible light source adds 420nm optical filter to provide by 300W xenon lamp, and light anode is away from light source 10cm.Electrochemistry
Work station records potential change of the 304SS before and after illumination (referring to Fig. 3).
Sb2S3/Sb2O3/TiO2The transient state photoelectricity current test of composite membrane: device and electrolyte solution are protected with above-mentioned photoproduction cathode
Shield test, but interface connection type is different.The specific interface of the ground wire for electrochemical workstation connects 304SS, and working electrode connects
Mouth connection Sb2S3/Sb2O3/TiO2Composite film photo-anode, reference electrode and to electrode interface be shorted with this come reduce polarization to electric current
The influence (referring to fig. 4) of density.
Fig. 1 is the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2The SEM of composite membrane schemes.Fig. 1 a can be seen that TiO2Nanotube
Regular appearance, caliber are about 80~100nm, and pipe range is about 800nm.This provides good logical for the transmission of photo-generated carrier
Road.Fig. 1 b can be seen that Sb in composite membrane2O3In micron club shaped structure, this will provide direct path, Sb for carrier transport2S3It is in
Tridimensional network is by Sb2O3Micron bar is connected with each other, but is difficult to observe by obvious TiO since the load of antimony base complex is more2
Nanotube pattern.
Fig. 2 is the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2The UV-vis DRS of composite membrane is composed.Wherein horizontal seat
It is designated as wavelength (nm), ordinate is absorption intensity.It can be seen that TiO2Film mainly absorbs ultraviolet light, and absorbing band edge is about 380nm.
Sb2S3/Sb2O3/TiO2Composite membrane is significantly increased in the absorption of visible region, absorption band edge red shift to 680nm or so.This shows
Sb2S3And Sb2O3Compound significantly increase TiO2To the absorption intensity and range of visible light.
Fig. 3 be 304SS respectively with the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2Composite membrane coupling, it is seen that before light illumination
Electrode potential versus time curve afterwards.Wherein abscissa is the time (s), and ordinate is electrode potential (mV).In visible light
Under irradiation, since light induced electron is transferred on 304SS, cathodic polarization is brought it about, is occurred so as to cause electrode potential negative rapidly
It moves.As 304SS and TiO2When film light anode couples, smaller movement occurs for electrode potential, is about down to -330mV, is lower than 304SS
Corrosion potential, play certain photoproduction cathodic protection effect.As 304SS and Sb2S3/Sb2O3/TiO2Composite film photo-anode,
Significant negative movement occurs for electrode potential, is about down to -730mV, shows that the composite membrane can play good photoproduction cathodic protection effect.
When stopping illumination, the electrode potential of 304SS is begun to ramp up, with composite film photo-anode coupling 304SS electrode potential be lower than and
Pure TiO2Stainless steel current potential when coupling.Again when illumination, the decline rapidly again of the electrode potential for the 304SS being connect with composite membrane,
Show composite membrane has good stability.
Fig. 4 is the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2The transient state photocurrent curve of composite membrane.Wherein, abscissa
For the time (s), ordinate is current density (μ A/cm2).Pure TiO2The transient state density of photocurrent maximum value of film is about 10 μ A/
cm2, as load Sb2S3And Sb2O3Afterwards, current density maxima can reach about 42 μ A/cm2.The photoelectric current dramatically increased is mainly
Since after the load of antimony base complex, TiO2To the influx and translocation of visible light, it can produce more photo-generated carriers；And matched energy
Band structure, P-N built in field and rodlike Sb2O3Electron channel all inhibits the compound of carrier, increases electrons and holes point
From and transmission efficiency.
Embodiment 2
Sb2S3/Sb2O3/TiO2The preparation method of composite membrane the following steps are included:
The pretreatment of titanium sheet: titanium foil content is greater than 99.9wt.%, is cut into 1 × 4cm with a thickness of the titanium foil of 0.3mm2's
Titanium sheet.Again by the titanium sheet sheared EtOH Sonicate 30min, deionized water ultrasound 10min, ethyl alcohol and deionized water replace later
It is dried after cleaning and is placed in sealed storage in dehydrated alcohol.It weighs 1.80g ammonium fluoride to be dissolved in 10mL deionized water, be separately added into
24mL hydrogen peroxide and 24mL concentrated nitric acid are made into polishing fluid, the titanium sheet after cleaning are put in 30s in polishing fluid, then use deionization respectively
Water, ethyl alcohol cleaning, dry stand-by.
TiO2The preparation of film: it weighs 0.33g ammonium fluoride and is dissolved in 6mL ultrapure water, add 60mL ethylene glycol, ultrasound makes
The two is uniformly mixed, and obtains anodic oxidation electrolyte.Anodic oxidation uses three-electrode system, using pretreated titanium sheet as work
Electrode, platinum electrode are to electrode, and saturated calomel electrode is reference electrode.Titanium sheet is placed in above-mentioned electrolyte, it is positive under 20V voltage
Pole aoxidizes 1h, is alternately cleaned with ethyl alcohol and deionized water later, naturally dry.Titanium sheet after drying 450 DEG C of perseverances in Muffle furnace
Temperature calcining 2h, cools to the furnace after room temperature up to TiO2Nano-tube film (referring to Fig. 5 a).
Sb2S3/Sb2O3/TiO2The preparation of composite membrane: weighing half hydration potassium antimony tartrate of 1.64g and be dissolved in 50mL ultrapure water,
1.16g Sodium Sulphate Nine Hydroxide is added in magnetic agitation 15min with vigorous stirring later, continues to obtain reaction solution after stirring 35min.
TiO will be had2The titanium substrate of film is vertically arranged in 100mL ptfe autoclave, then reaction solution is poured into the reaction kettle,
Room temperature is cooled to the furnace after 180 DEG C of heating 12h in air dry oven.The titanium substrate with composite membrane is taken out after hydro-thermal, is gone
Alternately for several times, 70 DEG C of vacuum drying 4h are to get Sb for cleaning for ionized water and ethyl alcohol2S3/Sb2O3/TiO2Composite membrane is (referring to Fig. 5 b and figure
6)。
Sb2S3/Sb2O3/TiO2The photoproduction cathodic protection of composite membrane is tested: specific using by photoelectrolytic cell and corrosion electrolytic cell
The double-electrolyzer system of composition.Sb2S3/Sb2O3/TiO2Composite membrane is placed in as light anode containing 0.1mol/L Na2SO3Light
Electrolytic cell.Corrode electrolytic cell and use three-electrode system, platinum electrode is used as to electrode, saturated calomel electrode as reference electrode,
304SS connect electrochemical workstation working electrode interface with light anode coupling by conducting wire jointly.Photoelectrolytic cell and corrosion are electrolysed
Pond is connected by salt bridge.Visible light source adds 420nm optical filter to provide by 300W xenon lamp, and light anode is away from light source 10cm.Electrochemistry
Work station records potential change of the 304SS before and after illumination (referring to Fig. 7).
Sb2S3/Sb2O3/TiO2The transient state photoelectricity current test of composite membrane: device and electrolyte solution are protected with above-mentioned photoproduction cathode
Shield test, but interface connection type is different.The specific interface of the ground wire for electrochemical workstation connects 304SS, and working electrode connects
Mouth connection Sb2S3/Sb2O3/TiO2Composite film photo-anode, reference electrode and to electrode interface be shorted with this come reduce polarization to electric current
The influence of density (referring to Fig. 8).
Fig. 5 is the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2The SEM of composite membrane schemes.Fig. 1 a can be seen that TiO2Nanotube
Pattern is neat, and caliber is about 80~100nm, and pipe range is about 800nm.This provides good logical for the transmission of photo-generated carrier
Road.Fig. 1 b can be seen that Sb in composite membrane2O3It is the micron club shaped structure of diamond shape in section, regular pattern shows that its crystallinity is good
Good, so good micron bar of crystallinity is conducive to the transmission of carrier.Sb2S3In tridimensional network by Sb2O3Micron bar phase
It connects.TiO2Nanotube pattern by but the antimony base complex of load block, wherein potassium antimony tartrate and Sodium Sulphate Nine Hydroxide are same
After the ratio amount of increasing input, Sb in product composite membrane2S3Load capacity increase, Sb2S3Club shaped structure crystallinity is more preferable.
Fig. 6 is the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2The UV-vis DRS of composite membrane is composed.Wherein horizontal seat
It is designated as wavelength (nm), ordinate is absorption intensity.It can be seen that TiO2Film mainly absorbs ultraviolet light, and absorbing band edge is about 380nm.
The load of antimony base complex significantly increases/TiO2In the absorption intensity of visible region, band edge red shift is absorbed to 680nm or so,
This is mainly due to narrow band gap Sb2S3And Sb2O3Synergistic effect.
Fig. 7 be 304SS respectively with the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2Composite membrane coupling, it is seen that before light illumination
Electrode potential versus time curve afterwards.Wherein abscissa is the time (s), and ordinate is electrode potential (mV).Due to winestone
The amount of increasing input, composite membrane are bigger to the absorption of visible light in proportion for sour antimony potassium and Sodium Sulphate Nine Hydroxide, and photo-generated carrier point
It is improved from rate, transient state photocurrent values increase and negative move of open circuit potential becomes apparent from, and the photoproduction cathodic protection performance of composite membrane is mentioned
It rises.
Under visible light illumination, since light induced electron is transferred on 304SS, cathodic polarization is brought it about, so as to cause electricity
Negative rapidly move occurs for electrode potential.As 304SS and TiO2When film light anode couples, lesser cathodic polarization occurs for electrode, about drops
To -330mV, the corrosion potential lower than 304SS plays certain photoproduction cathodic protection effect.As 304SS and Sb2S3/
Sb2O3/TiO2Composite film photo-anode, electrode potential occur significant negative movement, are about down to -770mV, show that the composite membrane can play
Good photoproduction cathodic protection effect.When stopping illumination, the electrode potential of 304SS is begun to ramp up, with composite film photo-anode coupling
304SS electrode potential even is lower than and pure TiO2Stainless steel current potential when coupling.Again when illumination, it is connect with composite membrane
The decline rapidly again of the electrode potential of 304SS, duplicate opening and closing light is the experimental results showed that composite membrane has good stability.
Fig. 8 is the TiO of preparation2Film and Sb2S3/Sb2O3/TiO2The transient state photocurrent curve of composite membrane.Wherein, abscissa
For the time (s), ordinate is current density (μ A/cm2).Pure TiO2The transient state density of photocurrent maximum value of film is about 10 μ A/
cm2, as load Sb2S3And Sb2O3Afterwards, current density maxima can reach about 50 μ A/cm2.The photoelectric current dramatically increased is mainly
Since after the load of antimony base complex, TiO2Absorption region and intensity to visible light increase, and more photo-generated carriers are generated
And it is transferred to 304SS；In addition staggered band structure and built in field and rodlike Sb2O3Electron channel is all conducive to photoproduction
The timely separation and transmission of electrons and holes, to improve TiO2Photoproduction cathodic protection effect.
Claims (10)
1. a kind of antimony base complex sensitized titanium dioxide composite membrane for photoproduction cathodic protection, it is characterised in that: pass through one pot
Hydro-thermal method is by Sb2S3/Sb2O3It is carried on TiO2On nano-tube array, antimony base complex sensitized titanium dioxide composite membrane is formed.
2. the antimony base complex sensitized titanium dioxide composite membrane according to claim 1 for photoproduction cathodic protection, feature
It is: Sb in composite membrane2O3It is in the rodlike structural load of micron in TiO for monocline type2On film, provided directly for carrier transport
Connect road.Narrow band gap Sb2S3For monocline type, in tridimensional network by Sb2O3Micron bar is connected with each other, and makes TiO2To visible light
It absorbs band edge and expands to 600~700nm.
3. the antimony base complex sensitized titanium dioxide composite membrane according to claim 1 for photoproduction cathodic protection, feature
Be: the hydro-thermal method is that half hydration potassium antimony tartrate is dissolved in excessive ultrapure water, stirs and evenly mixs, is hydrated sulphur for nine under stirring
Change sodium to be added thereto with vigorous stirring, is stirred for mixing to obtain mixed liquor, then by mixed liquor and TiO2Nanotube substrate is in water
In thermal response kettle, 150~200 DEG C of incubation water heatings 6~for 24 hours, composite membrane is taken out after hydro-thermal, washs, be drying to obtain Sb2S3/
Sb2O3/TiO2Composite film photo-anode.
4. the antimony base complex sensitized titanium dioxide composite membrane according to claim 3 for photoproduction cathodic protection, feature
It is:
Half hydration antimony tartrate potassium application rate is 0.3~6mmol, Sodium Sulphate Nine Hydroxide and half hydration wine in every 50mL ultrapure water
Stone acid antimony potassium application rate molar ratio is 1-2.5:1.
5. the antimony base complex sensitized titanium dioxide composite membrane according to claim 3 for photoproduction cathodic protection, feature
Be: the hydro-thermal reaction take after film using water and ethyl alcohol alternately cleaning for several times, 50~80 DEG C of 1~6h of vacuum drying to get
Sb2S3/Sb2O3/TiO2Composite film photo-anode.
6. a kind of preparation of the antimony base complex sensitized titanium dioxide composite membrane described in claim 1 for photoproduction cathodic protection
Method, it is characterised in that: pass through anodizing and calcine and modify TiO in titanium plate surface2Nano-pipe array thin film passes through one pot
Hydro-thermal method is by Sb2S3/Sb2O3It is carried on TiO2On nano-tube array, antimony base complex sensitized titanium dioxide composite membrane is formed.
7. the preparation side of the antimony base complex sensitized titanium dioxide composite membrane according to claim 6 for photoproduction cathodic protection
Method, it is characterised in that: half hydration potassium antimony tartrate is dissolved in excessive ultrapure water, stirs and evenly mixs, vulcanizes nine hydrations under stirring
Sodium is added thereto with vigorous stirring, is stirred for mixing to obtain mixed liquor, then by mixed liquor and TiO2Nanotube substrate is in hydro-thermal
In reaction kettle, 150~200 DEG C of incubation water heatings 6~for 24 hours, composite membrane is taken out after hydro-thermal, washs, be drying to obtain Sb2S3/Sb2O3/
TiO2Composite film photo-anode.
8. the preparation side of the antimony base complex sensitized titanium dioxide composite membrane according to claim 7 for photoproduction cathodic protection
Method, it is characterised in that: half hydration antimony tartrate potassium application rate is 0.3~6mmol, Sodium Sulphate Nine Hydroxide in every 50mL ultrapure water
It is 1-2.5:1 with half hydration antimony tartrate potassium application rate molar ratio.
9. the preparation side of the antimony base complex sensitized titanium dioxide composite membrane according to claim 8 for photoproduction cathodic protection
Method, it is characterised in that: the hydro-thermal reaction is alternately cleaned for several times after taking film using water and ethyl alcohol, 50~80 DEG C of vacuum drying 1~
6h is to get Sb2S3/Sb2O3/TiO2Composite film photo-anode.
10. a kind of antimony base complex sensitized titanium dioxide composite membrane described in claim 1 for photoproduction cathodic protection is answered
With, it is characterised in that: the composite membrane can be used as the optical anode material of photoproduction cathodic protection.
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| CN109972149A (en) * | 2019-05-06 | 2019-07-05 | 中国科学院海洋研究所 | A kind of Bi2Te3/Bi2O3/TiO2The preparation method of ternary heterojunction film |
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| CN101974743A (en) * | 2010-10-27 | 2011-02-16 | 大连三达奥克化学股份有限公司 | Ti-Mg-B surface conditioner for zinc-phosphating and preparation method thereof |
| CN103668291A (en) * | 2013-11-19 | 2014-03-26 | 青岛汇而通商贸有限公司 | Safe cleaning solution capable of avoiding damage to surface of metal |
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| CN101974743A (en) * | 2010-10-27 | 2011-02-16 | 大连三达奥克化学股份有限公司 | Ti-Mg-B surface conditioner for zinc-phosphating and preparation method thereof |
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| CN109972149A (en) * | 2019-05-06 | 2019-07-05 | 中国科学院海洋研究所 | A kind of Bi2Te3/Bi2O3/TiO2The preparation method of ternary heterojunction film |
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