CN108034950A - A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof - Google Patents

A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof Download PDF

Info

Publication number
CN108034950A
CN108034950A CN201711401196.5A CN201711401196A CN108034950A CN 108034950 A CN108034950 A CN 108034950A CN 201711401196 A CN201711401196 A CN 201711401196A CN 108034950 A CN108034950 A CN 108034950A
Authority
CN
China
Prior art keywords
tio
composite membrane
sns
nano composite
cathodic protection
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711401196.5A
Other languages
Chinese (zh)
Inventor
王秀通
邵静
李鑫冉
宁晓波
雷婧
王文成
于腾
杨黎辉
黄彦良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Oceanology of CAS
Original Assignee
Institute of Oceanology of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Oceanology of CAS filed Critical Institute of Oceanology of CAS
Priority to CN201711401196.5A priority Critical patent/CN108034950A/en
Publication of CN108034950A publication Critical patent/CN108034950A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Hybrid Cells (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The present invention relates to a kind of nano composite membrane light anode, the SnS/TiO for photoproduction cathodic protection prepared more particularly, to a kind of continuous deionization sedimentation2Nano composite membrane and preparation method thereof.TiO is obtained on Titanium base surface by anodizing2Film of Nano tube array, then SnS nano particles are carried on by TiO by continuous deionization sedimentation2On film of Nano tube array, i.e., matrix surface obtains SnS/TiO2Nano composite membrane.SnS/TiO prepared by the present invention2Compound film method is simple, has excellent photoproduction cathodic protection effect, and significantly declining occurs in protected 304 stainless steel current potential under the irradiation of visible ray, can still have certain cathodic protection effect to 304 stainless steels after closing light source.

Description

A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof
Technical field
The present invention relates to a kind of nano composite membrane light anode, the use prepared more particularly, to a kind of continuous deionization sedimentation In the SnS/TiO of photoproduction cathodic protection2Nano composite membrane and preparation method thereof.
Background technology
Ocean is very strong, the very complicated environment of a corrosivity, and seawater contains a variety of salt as a kind of natural electrolytes Point, resistive retardance very little, significant corrosion effect can be caused when dissimilar metal contacts.Through investigation, China's corrosion in 2014 Cost is about 21278.2 hundred million yuan, accounts for the 3.34% of GDP then.Stainless steel is in marine environment, in itself suffered active force And under the joint effect of seawater corrosion, microorganism infringement etc., spot corrosion can still occur for stainless steel material, while can also there are gap Burn into stress corrosion cracking etc..Since the continuous development of photoelectric material and cathode protection technology, photoproduction cathodic protection are anti-in corrosion Protector for collar domain has broad application prospects.
TiO2It is a kind of relatively conventional photoelectric material, there is good photocatalytic and stability, be widely used to Photocatalysis, sensor, solar energy trans-utilization etc..But TiO2Belong to wide bandgap semiconductor compound, under normal circumstances Can only absorbing wavelength be no more than 387nm ultraviolet light, on the other hand, TiO2After being excited by illumination, electron-hole pair existence time Short, phototranstormation efficiency is relatively low.In order to improve TiO2The defects of, we are often doped modification to it, including metal Doping (such as Ag of ion+、Co2+), nonmetal doping (such as N, S), semiconductor doping (such as CeO2、CdS、V2O5) etc..
The photoelectric conversion result of SnS has been confirmed, but does not have correlation to be used for photoproduction cathodic protection at this stage SnS/TiO2The relevant report of nano composite membrane.
The content of the invention
It is an object of the invention to provide a kind of SnS/TiO2 nano composite membranes for photoproduction cathodic protection and its preparation Method.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of nano composite membrane for photoproduction cathodic protection, obtains TiO2 on Titanium base surface by anodizing and receives Mitron array films, then SnS nano particles are carried on TiO2 film of Nano tube array by continuous deionization sedimentation, i.e. matrix Surface obtains SnS/TiO2 nano composite membranes.
The anodizing is that the Titanium base after polished and cleaned is placed in electrolyte as anode, platinized platinum conduct pair Electrode, in 1~1.5h of oxidation at voltages of 20-30V, is then calcined in Muffle furnace, cools to room temperature with the furnace, you can Titanium base surface is prepared into the TiO of the higher Detitanium-ore-type of crystallinity2Film of Nano tube array.
The continuous deionization sedimentation refers to SnCl2·2H2The dilute hydrochloric acid solution of O is as cation precursor liquid, Na2S· 9H2Above-mentioned acquisition Titanium base is submerged initially in 25-35s in cation precursor liquid as anion precursor liquid by the aqueous solution of O, with super Pure water rinsing 25-35s, then 15-25s in anion precursor liquid is immersed, with ultrapure water 15-25s, this process is followed for one Ring, after multiple cyclic deposition, composite material is rinsed well, is placed in 1h in 60 DEG C of vacuum drying oven, you can obtain SnS/ TiO2Nano composite membrane.Wherein, cyclic deposition is 3-15 circulation.
The preparation method of a kind of nano composite membrane for photoproduction cathodic protection, by anodizing on Titanium base surface Obtain TiO2Film of Nano tube array, then SnS nano particles are carried on by TiO by continuous deionization sedimentation2Film of Nano tube array On, i.e., matrix surface obtains SnS/TiO2Nano composite membrane.
The anodizing is that the Titanium base after polished and cleaned is placed in electrolyte as anode, platinized platinum conduct pair Electrode, in 1~1.5h of oxidation at voltages of 20-30V, is then calcined in Muffle furnace, cools to room temperature with the furnace, you can Titanium base surface is prepared into the TiO of the higher Detitanium-ore-type of crystallinity2Film of Nano tube array.
The continuous deionization sedimentation refers to SnCl2·2H2The dilute hydrochloric acid solution of O is as cation precursor liquid, Na2S· 9H2Above-mentioned acquisition Titanium base is submerged initially in 25-35s in cation precursor liquid as anion precursor liquid by the aqueous solution of O, with super Pure water rinsing 25-35s, then 15-25s in anion precursor liquid is immersed, with ultrapure water 15-25s, this process is followed for one Ring, after multiple cyclic deposition, composite material is rinsed well, is placed in 1h in 60 DEG C of vacuum drying oven, you can obtain SnS/ TiO2Nano composite membrane.Wherein, cyclic deposition is 3-15 circulation.
The electrolyte includes NH4F, ethylene glycol and ultra-pure water, wherein the NH added4F mass is mixed solution gross mass The volume ratio of 0.40%-0.45%, ultra-pure water and ethylene glycol is 1:10-1:12.
The SnCl2·2H2The dilute hydrochloric acid solution of O, is by SnCl2·2H2O is dissolved in the dilute hydrochloric acid that pH value is 1.8~2, Obtain the SnCl that liquid concentration is 0.05~0.2mol/L2·2H2O dilute hydrochloric acid is molten；
The Na2S·9H2The aqueous solution of O is by Na2S·9H2It is 9-11 that O aqueous solutions are adjusted through pH value through HCl, obtains concentration For 0.05~0.2mol/LNa2S·9H2O obtains aqueous solution.
A kind of application of nano composite membrane for photoproduction cathodic protection, the SnS/TiO2Nano composite membrane is for light Application in raw cathodic protection.
Above-mentioned gained is used for the SnS/TiO of photoproduction cathodic protection2The photoproduction cathodic protection test method of nano composite membrane is such as Under：Using double-electrolyzer electro-chemical systems, this system is made of photoelectrolytic cell and corrosion electrolytic cell.It is put into photoelectrolytic cell The Na of 0.1mol/L2SO3Solution, by SnS/TiO2Nano composite membrane immerses Na surely as optoelectronic pole with electrode is clamping2SO3Solution In.Corrosion electrolytic cell uses three-electrode system, and 304 stainless steels are as working electrode, and saturated calomel electrode is as reference electrode, platinum Electrode is used as to electrode, three electrodes is immersed in 3.5% NaCl solution.Photoelectrolytic cell passes through salt bridging with corrosion electrolytic cell Connect, optoelectronic pole is connected with working electrode by conducting wire.Visible light source (additional ultraviolet light is used as using 100~150W high pressure Xe lamps Optical filter so that Guang Yuan Bo Chang≤400nm), shine directly into SnS/TiO in photoelectrolytic cell2Nano combined film surface, Ran Houyong Electrochemical workstation tests potential change of the metal electrode before and after illumination.
The basic principle of the present invention：
TiO2It is the n-type semiconductor that a kind of energy gap is about 3.2eV, SnS is a kind of relatively narrow p-type of energy gap Semiconductor, SnS and TiO2Contact forms hetero-junctions.Under the illumination more than ultraviolet band, light energy is not enough to excitation TiO2Produce Photoelectron, but SnS can work as sensitizer, and the electronics in SnS valence band, which is excited, transits to conduction band, and due to SnS conduction bands Potential compares TiO2It is more negative, therefore light induced electron is easy to be transferred to TiO from SnS conduction bands by heterojunction boundary2.Last photoproduction Electronics continues to be transferred to and TiO2On 304 connected stainless steels so that stainless steel current potential bears shifting, hence into cathodic protection shape State.Simultaneously as there is also difference, TiO for valence band potential2Hole in valence band can also move to SnS.In this way, composite material Photo-generate electron-hole reduces the compound of photo-generated carrier to being efficiently separated.Therefore, by preparing SnS/TiO2 Nano composite membrane can effectively improve the photoproduction cathodic protection effect to 304 stainless steels.
The present invention has the advantage that：
1. TiO prepared by the present invention2Nanotube better crystallinity degree, relatively stablizes, is easy to adhere to other semiconductor nanoparticles.
2. the present invention prepares SnS/TiO using continuous deionization sedimentation2Nano composite membrane, easy to operate, experiment condition Controllability is strong, is dried in vacuo 1h after deposition at 60 DEG C.
3. SnS/TiO prepared by the present invention2After nano composite membrane is connected with 304 stainless steels, under illumination condition, it can make The current potential of 304 stainless steels drops to -600mv~-700mv or so, and under the conditions of black out, rising situation occurs in current potential, but still low In the corrosion potential of 304 stainless steels, show the SnS/TiO2The photoproduction cathodic protection effect of nano composite membrane is obvious.
In conclusion the present invention prepares SnS/TiO using anodizing and continuous deionization sedimentation2Composite membrane, should Film shows excellent photoproduction cathodic protection effect as light anode.
Brief description of the drawings
Fig. 1 is TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano thin-film.
Fig. 2 is SnS/TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano composite membrane.
Fig. 3 is SnS/TiO provided in an embodiment of the present invention2Nano composite membrane and be placed in 3.5%NaCl solution 304 not The open circuit potential figure that rust steel couples.Wherein, abscissa is the time (s), and ordinate is current potential (V vs.SCE).On represents light According to off represents to close light source.
Fig. 4 is SnS/TiO provided in an embodiment of the present invention2Nano composite membrane and 304 stainless steels coupling after under light illumination (>= 400nm) the photocurrent-time curve of test.
Fig. 5 is SnS/TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano composite membrane.
Fig. 6 is SnS/TiO provided in an embodiment of the present invention2Nano composite membrane and be placed in 3.5%NaCl solution 304 not The open circuit potential figure that rust steel couples.Wherein, abscissa is the time (s), and ordinate is current potential (V vs.SCE).On represents light According to off represents to close light source.
Fig. 7 is SnS/TiO provided in an embodiment of the present invention2Nano composite membrane and 304 stainless steels coupling after under light illumination (>= 400nm) the photocurrent-time curve of test.
Fig. 8 is SnS/TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano composite membrane.
Fig. 9 is SnS/TiO provided in an embodiment of the present invention2Nano composite membrane and be placed in 3.5%NaCl solution 304 not The open circuit potential figure that rust steel couples.Wherein, abscissa is the time (s), and ordinate is current potential (V vs.SCE).On represents light According to off represents to close light source.
Figure 10 is SnS/TiO provided in an embodiment of the present invention2After nano composite membrane and the coupling of 304 stainless steels under light illumination (>=400nm) test photocurrent-time curve.
Embodiment
By following embodiments, the present invention is further described in detail, but the content being not intended to limit the present invention, this The simple replacement or change that field technology personnel make present invention are fallen within rights protection scope of the present invention.
The present invention is by SnS and TiO2Compound acquisition composite membrane can effectively improve the utilization rate to visible ray, reach more preferable Cathodic protection effect.
Embodiment 1：
SnS/TiO2The preparation method of nano composite membrane：
The titanium foil for taking purity to be 99.9% is sample, the Titanium base that specification is 40*10*0.1mm is cut into, successively anhydrous Ultrasound 10min, and the polishing treatment 20s in polishing fluid twice in ultrasound 30min, ultra-pure water, then clear with ultra-pure water in ethanol Wash clean, is placed in spare in absolute ethyl alcohol.Wherein polishing fluid is NH4F、H2O、HNO3And H2O2Mixed solution, H2O、HNO3With H2O2Volume ratio be 2:5:5, the NH of addition4F mass is the 2.5% of mixed solution gross mass.
Weigh 0.44gNH4F, is dissolved in 4ml ultra-pure waters, adds 80ml ethylene glycol.After ultrasonic 15min is mixed, room temperature Under, in above-mentioned electrolyte, aoxidized pretreated Titanium base as anode, platinized platinum as cathode with 20V ultors Sample, is then put into Muffle furnace at 450 DEG C and calcines 2h by 1h, then cools to room temperature with the furnace, i.e., is made on Titanium base surface TiO2Film of Nano tube array.
The SnCl of 0.05mol/L is put into A beakers2·2H2O dilute hydrochloric acid solutions, are put into B beakers isometric ultrapure Water, the Na of 0.05mol/L is put into C beakers2S·9H2O aqueous solutions, are put into isometric ultra-pure water in D beakers.It is being slowly stirred Under, Titanium base immerses to 30s in A beakers successively, 30s in B beakers, 20s in C beakers, 20s in D beakers, this process follows for one Ring, after circulating 3 times, composite material is cleaned up with ultra-pure water, is subsequently placed into 60 DEG C of vacuum drying oven dry 1h, is used In the SnS/TiO of photoproduction cathodic protection2Nano composite membrane.
The SnS/TiO prepared to the above method2Nano composite membrane photoproduction cathodic protection is tested：Using double-electrolyzer electrochemistry System, this system are made of photoelectrolytic cell and corrosion electrolytic cell.The Na of 0.1mol/L is put into photoelectrolytic cell2SO3Solution, will SnS/TiO2Nano composite membrane immerses Na surely as optoelectronic pole with electrode is clamping2SO3In solution.Corrosion electrolytic cell uses three electrodes System, 304 stainless steels are as working electrode, and saturated calomel electrode is as reference electrode, and platinum electrode is used as to electrode, by three electricity Pole is immersed in 3.5% NaCl solution.Photoelectrolytic cell is connected with corrosion electrolytic cell by salt bridge, and optoelectronic pole passes through with working electrode Conducting wire connects.Using 100~150W high pressure Xe lamps as visible light source (additional uv filter so that Guang Yuan Bo Chang≤ 400nm), SnS/TiO in photoelectrolytic cell is shone directly into2Nano combined film surface.
By Fig. 1 it can be seen that obtained TiO2The SEM figures of film of Nano tube array.As can be seen that film of Nano tube array compares Uniformly, internal diameter about 60nm.
By Fig. 2 it can be seen that obtained SnS/TiO2The SEM figures of nano composite membrane.It can be seen that SnS nano particles are main It is distributed at the inner wall and the mouth of pipe of nanotube, and distribution uniform.
As seen from Figure 3 304 stainless steels in 3.5%NaCl solution respectively with the pure TiO in photoelectrolytic cell2Film and SnS/ TiO2Electrode potential versus time curve after nano combined membrane electrode coupling, abscissa is the time (s), and ordinate is electrode Current potential (V vs.SCE).Pure TiO under stainless steel and illumination2When membrane electrode couples, the corrosion potential of 304 stainless steels is down to About -340mV, plays certain photoproduction cathodic protection effect.When being coupled with composite membrane, the electrode potential of stainless steel can drop to About -630mV, hence it is evident that the more below corrosion potential of 304 stainless steels.When cutting off light source, on the electrode potential of stainless steel starts Rise, but 304 stainless steel electrode current potentials are far below and pure TiO at this time2Stainless steel current potential during coupling.Illumination is carried out again, at this time The electrode potential for the stainless steel being connected with composite membrane is again rapid to be declined, and shows that there is composite membrane good photoproduction cathodic protection to imitate Fruit.
As seen from Figure 4 304 stainless steels respectively with the pure TiO in photoelectrolytic cell2Film and SnS/TiO2Nano combined membrane electrode After coupling, pure TiO2Film produces 8 μ A/cm in visible ray according to moment2Photoelectric current, SnS/TiO2Nano composite membrane produces under light illumination Raw photoelectric current maximum is 48 μ A/cm2.Show in TiO2Photo-current intensity significantly increases after nanotube surface composite S nS, carries The high utilization rate to visible ray.
Embodiment 2：
SnS/TiO2The preparation method of nano composite membrane：
The titanium foil for taking purity to be 99.9% is sample, the Titanium base that specification is 40*10*0.1mm is cut into, successively anhydrous Ultrasound 10min, and the polishing treatment 20s in polishing fluid twice in ultrasound 30min, ultra-pure water, then clear with ultra-pure water in ethanol Wash clean, is placed in spare in absolute ethyl alcohol.Wherein polishing fluid is NH4F、H2O、HNO3And H2O2Mixed solution, H2O、HNO3With H2O2Volume ratio be 2:5:5, the NH of addition4F mass is the 2.5% of mixed solution gross mass.
Weigh 0.44gNH4F, is dissolved in 4ml ultra-pure waters, adds 80ml ethylene glycol.After ultrasonic 15min is mixed, room temperature Under, in above-mentioned electrolyte, aoxidized pretreated Titanium base as anode, platinized platinum as cathode with 20V ultors Sample, is then put into Muffle furnace at 450 DEG C and calcines 2h by 1h, then cools to room temperature with the furnace, i.e., is made on Titanium base surface TiO2Film of Nano tube array.
The SnCl of 0.1mol/L is put into A beakers2·2H2O dilute hydrochloric acid solutions, are put into B beakers isometric ultrapure Water, the Na of 0.1mol/L is put into C beakers2S·9H2O aqueous solutions, are put into isometric ultra-pure water in D beakers.It is being slowly stirred Under, Titanium base immerses to 30s in A beakers successively, 30s in B beakers, 20s in C beakers, 20s in D beakers, this process follows for one Ring, after circulating 3 times, composite material is cleaned up with ultra-pure water, is subsequently placed into 60 DEG C of vacuum drying oven dry 1h, is used In the SnS/TiO of photoproduction cathodic protection2Nano composite membrane.
The SnS/TiO prepared to the above method2Nano composite membrane photoproduction cathodic protection is tested：Using double-electrolyzer electrochemistry System, this system are made of photoelectrolytic cell and corrosion electrolytic cell.The Na of 0.1mol/L is put into photoelectrolytic cell2SO3Solution, will SnS/TiO2Nano composite membrane immerses Na surely as optoelectronic pole with electrode is clamping2SO3In solution.Corrosion electrolytic cell uses three electrodes System, 304 stainless steels are as working electrode, and saturated calomel electrode is as reference electrode, and platinum electrode is used as to electrode, by three electricity Pole is immersed in 3.5% NaCl solution.Photoelectrolytic cell is connected with corrosion electrolytic cell by salt bridge, and optoelectronic pole passes through with working electrode Conducting wire connects.Using 100~150W high pressure Xe lamps as visible light source (additional uv filter so that Guang Yuan Bo Chang≤ 400nm), SnS/TiO in photoelectrolytic cell is shone directly into2Nano combined film surface.
By Fig. 5 it can be seen that obtained SnS/TiO2The SEM figures of nano composite membrane, it can be seen that SnS nano particles are main It is distributed at the inner wall and the mouth of pipe of nanotube, and distribution uniform.
As seen from Figure 6 304 stainless steels in 3.5%NaCl solution respectively with the pure TiO in photoelectrolytic cell2Film and SnS/ TiO2Electrode potential versus time curve after nano combined membrane electrode coupling, abscissa is the time (s), and ordinate is electrode Current potential (V vs.SCE).Pure TiO under stainless steel and illumination2When membrane electrode couples, the corrosion potential of 304 stainless steels is down to About -340mV, plays certain photoproduction cathodic protection effect.When being coupled with composite membrane, the electrode potential of stainless steel can drop to About -710mV, hence it is evident that the more below corrosion potential of 304 stainless steels.When cutting off light source, on the electrode potential of stainless steel starts Rise, but 304 stainless steel electrode current potentials are far below and pure TiO at this time2Stainless steel current potential during coupling.Illumination is carried out again, at this time The electrode potential for the stainless steel being connected with composite membrane is again rapid to be declined, and shows that there is composite membrane good photoproduction cathodic protection to imitate Fruit.
As seen from Figure 7 304 stainless steels respectively with the pure TiO in photoelectrolytic cell2Film and SnS/TiO2Nano combined membrane electrode After coupling, pure TiO2Film produces 8 μ A/cm in visible ray according to moment2Photoelectric current, SnS/TiO2Nano composite membrane produces under light illumination Raw photoelectric current maximum is 64 μ A/cm2.Show in TiO2Photo-current intensity significantly increases after nanotube surface composite S nS, carries The high utilization rate to visible ray.
Embodiment 3：
SnS/TiO2The preparation method of nano composite membrane：
The titanium foil for taking purity to be 99.9% is sample, the Titanium base that specification is 40*10*0.1mm is cut into, successively anhydrous Ultrasound 10min, and the polishing treatment 20s in polishing fluid twice in ultrasound 30min, ultra-pure water, then clear with ultra-pure water in ethanol Wash clean, is placed in spare in absolute ethyl alcohol.Wherein polishing fluid is NH4F、H2O、HNO3And H2O2Mixed solution, H2O、HNO3With H2O2Volume ratio be 2:5:5, the NH of addition4F mass is the 2.5% of mixed solution gross mass.
Weigh 0.44gNH4F, is dissolved in 4ml ultra-pure waters, adds 80ml ethylene glycol.After ultrasonic 15min is mixed, room temperature Under, in above-mentioned electrolyte, aoxidized pretreated Titanium base as anode, platinized platinum as cathode with 20V ultors Sample, is then put into Muffle furnace at 450 DEG C and calcines 2h by 1h, then cools to room temperature with the furnace, i.e., is made on Titanium base surface TiO2Film of Nano tube array.
The SnCl of 0.2mol/L is put into A beakers2·2H2O dilute hydrochloric acid solutions, are put into B beakers isometric ultrapure Water, the Na of 0.2mol/L is put into C beakers2S·9H2O aqueous solutions, are put into isometric ultra-pure water in D beakers.It is being slowly stirred Under, Titanium base immerses to 30s in A beakers successively, 30s in B beakers, 20s in C beakers, 20s in D beakers, this process follows for one Ring, after circulating 3 times, composite material is cleaned up with ultra-pure water, is subsequently placed into 60 DEG C of vacuum drying oven dry 1h, is used In the SnS/TiO of photoproduction cathodic protection2Nano composite membrane.
The SnS/TiO prepared to the above method2Nano composite membrane photoproduction cathodic protection is tested：Using double-electrolyzer electrochemistry System, this system are made of photoelectrolytic cell and corrosion electrolytic cell.The Na of 0.1mol/L is put into photoelectrolytic cell2SO3Solution, will SnS/TiO2Nano composite membrane immerses Na surely as optoelectronic pole with electrode is clamping2SO3In solution.Corrosion electrolytic cell uses three electrodes System, 304 stainless steels are as working electrode, and saturated calomel electrode is as reference electrode, and platinum electrode is used as to electrode, by three electricity Pole is immersed in 3.5% NaCl solution.Photoelectrolytic cell is connected with corrosion electrolytic cell by salt bridge, and optoelectronic pole passes through with working electrode Conducting wire connects.Using 100~150W high pressure Xe lamps as visible light source (additional uv filter so that Guang Yuan Bo Chang≤ 400nm), SnS/TiO in photoelectrolytic cell is shone directly into2Nano combined film surface.
By Fig. 8 it can be seen that obtained SnS/TiO2The SEM figures of nano composite membrane, it can be seen that SnS nano particles are main It is distributed at the inner wall and the mouth of pipe of nanotube, and distribution uniform.
As seen from Figure 9 304 stainless steels in 3.5%NaCl solution respectively with the pure TiO in photoelectrolytic cell2Film and SnS/ TiO2Electrode potential versus time curve after nano combined membrane electrode coupling, abscissa is the time (s), and ordinate is electrode Current potential (V vs.SCE).Pure TiO under stainless steel and illumination2When membrane electrode couples, the corrosion potential of 304 stainless steels is down to About -340mV, plays certain photoproduction cathodic protection effect.When being coupled with composite membrane, the electrode potential of stainless steel can drop to About -660mV, hence it is evident that the more below corrosion potential of 304 stainless steels.When cutting off light source, on the electrode potential of stainless steel starts Rise, but 304 stainless steel electrode current potentials are far below and pure TiO at this time2Stainless steel current potential during coupling.Illumination is carried out again, at this time The electrode potential for the stainless steel being connected with composite membrane is again rapid to be declined, and shows that there is composite membrane good photoproduction cathodic protection to imitate Fruit.
As seen from Figure 10 304 stainless steels respectively with the pure TiO in photoelectrolytic cell2Film and SnS/TiO2Nano composite membrane electricity After the coupling of pole, pure TiO2Film produces 8 μ A/cm in visible ray according to moment2Photoelectric current, SnS/TiO2Nano composite membrane is under light illumination The photoelectric current maximum of generation is 53 μ A/cm2.Show in TiO2Photo-current intensity significantly increases after nanotube surface composite S nS, Improve the utilization rate to visible ray.

Claims (9)

  1. A kind of 1. nano composite membrane for photoproduction cathodic protection, it is characterised in that：By anodizing on Titanium base surface Obtain TiO2Film of Nano tube array, then SnS nano particles are carried on by TiO by continuous deionization sedimentation2Film of Nano tube array On, i.e., matrix surface obtains SnS/TiO2Nano composite membrane.
  2. 2. it is used for the nano composite membrane of photoproduction cathodic protection as described in claim 1, it is characterised in that：The anodizing It is that the Titanium base after polished and cleaned is placed in electrolyte to be used as to electrode as anode, platinized platinum, the oxygen under the voltage of 20-30V Change 1~1.5h, then calcined in Muffle furnace, cool to room temperature with the furnace, you can be prepared into crystallinity on Titanium base surface The TiO of higher Detitanium-ore-type2Film of Nano tube array.
  3. 3. by the nano composite membrane for being used for photoproduction cathodic protection claim 1 or 2 described, it is characterised in that：It is described it is continuous go from Sub- sedimentation refers to SnCl2·2H2The dilute hydrochloric acid solution of O is as cation precursor liquid, Na2S·9H2The aqueous solution of O as it is cloudy from Sub- precursor liquid, 25-35s in cation precursor liquid is submerged initially in by above-mentioned acquisition Titanium base, with ultrapure water 25-35s, then is immersed 15-25s in anion precursor liquid, with ultrapure water 15-25s, this process is a circulation, will after multiple cyclic deposition Composite material is rinsed well, is placed in 1h in 60 DEG C of vacuum drying oven, you can obtain SnS/TiO2Nano composite membrane.
  4. A kind of 4. preparation method of the nano composite membrane for photoproduction cathodic protection described in claim 1, it is characterised in that：It is logical Cross anodizing and obtain TiO on Titanium base surface2Film of Nano tube array, then by continuous deionization sedimentation by SnS nanometers Particulate load is in TiO2On film of Nano tube array, i.e., matrix surface obtains SnS/TiO2Nano composite membrane.
  5. 5. it is used for the preparation method of the nano composite membrane of photoproduction cathodic protection as described in claim 4, it is characterised in that：Described Anodizing is that the Titanium base after polished and cleaned is placed in electrolyte as anode, and platinized platinum is used as to electrode, in 20-30V 1~1.5h of oxidation at voltages, then calcined in Muffle furnace, cool to room temperature with the furnace, you can in Titanium base surface system The standby TiO for obtaining the higher Detitanium-ore-type of crystallinity2Film of Nano tube array.
  6. 6. by the preparation method for the nano composite membrane for being used for photoproduction cathodic protection claim 4 or 5 described, it is characterised in that：Institute Continuous deionization sedimentation is stated to refer to SnCl2·2H2The dilute hydrochloric acid solution of O is as cation precursor liquid, Na2S·9H2O's is water-soluble Above-mentioned acquisition Titanium base is submerged initially in 25-35s in cation precursor liquid, with ultrapure water 25- by liquid as anion precursor liquid 35s, then 15-25s in anion precursor liquid is immersed, with ultrapure water 15-25s, this process is a circulation, through repeatedly circulation After deposition, composite material is rinsed well, is placed in 1h in 60 DEG C of vacuum drying oven, you can obtain SnS/TiO2Nano composite membrane.
  7. 7. it is used for the preparation method of the nano composite membrane of photoproduction cathodic protection as described in claim 5, it is characterised in that：The electricity Solution liquid includes NH4F, ethylene glycol and ultra-pure water, wherein the NH added4F mass is the 0.40%-0.45% of mixed solution gross mass, The volume ratio of ultra-pure water and ethylene glycol is 1:10-1:12.
  8. 8. it is used for the preparation method of the nano composite membrane of photoproduction cathodic protection as described in claim 6, it is characterised in that：It is described SnCl2·2H2The dilute hydrochloric acid solution of O, is by SnCl2·2H2O is dissolved in the dilute hydrochloric acid that pH value is 1.8~2, and obtaining liquid concentration is The SnCl of 0.05~0.2mol/L2·2H2O dilute hydrochloric acid is molten；
    The Na2S·9H2The aqueous solution of O is by Na2S·9H2It is 9-11 that O aqueous solutions are adjusted through pH value through HCl, and obtaining concentration is 0.05~0.2mol/LNa2S·9H2O obtains aqueous solution.
  9. A kind of 9. application of the nano composite membrane for photoproduction cathodic protection described in claim 1, it is characterised in that：It is described SnS/TiO2Application of the nano composite membrane in for photoproduction cathodic protection.
CN201711401196.5A 2017-12-22 2017-12-22 A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof Pending CN108034950A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711401196.5A CN108034950A (en) 2017-12-22 2017-12-22 A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711401196.5A CN108034950A (en) 2017-12-22 2017-12-22 A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108034950A true CN108034950A (en) 2018-05-15

Family

ID=62100222

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711401196.5A Pending CN108034950A (en) 2017-12-22 2017-12-22 A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108034950A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109680314A (en) * 2019-02-26 2019-04-26 上海大学 The preparation method of SnS nano-tube film or SnS nano-rod film
CN110016709A (en) * 2018-11-15 2019-07-16 暨南大学 Zn@P nano-deposit with photoproduction cathodic protection effect and preparation method thereof
CN112725810A (en) * 2020-12-24 2021-04-30 中国科学院海洋研究所 Ag/Ag3PO4/TiO2Nanocomposite film material and application thereof
JP7164257B1 (en) * 2022-01-18 2022-11-01 青▲島▼理工大学 Photoanode film for improving corrosion resistance of reinforcing bars for marine construction, method for producing the same, and use thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016709A (en) * 2018-11-15 2019-07-16 暨南大学 Zn@P nano-deposit with photoproduction cathodic protection effect and preparation method thereof
CN109680314A (en) * 2019-02-26 2019-04-26 上海大学 The preparation method of SnS nano-tube film or SnS nano-rod film
CN112725810A (en) * 2020-12-24 2021-04-30 中国科学院海洋研究所 Ag/Ag3PO4/TiO2Nanocomposite film material and application thereof
JP7164257B1 (en) * 2022-01-18 2022-11-01 青▲島▼理工大学 Photoanode film for improving corrosion resistance of reinforcing bars for marine construction, method for producing the same, and use thereof

Similar Documents

Publication Publication Date Title
CN108034950A (en) A kind of nano composite membrane for photoproduction cathodic protection and preparation method thereof
CN103205760B (en) For the Ag of photoproduction galvanic protection 2s/TiO 2the preparation method of composite film photo-anode
CN107723712B (en) ZnIn for photoproduction cathodic protection2S4/TiO2Preparation method of nanotube composite film photo-anode
CN106498408B (en) A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection
CN107557789B (en) A kind of optical anode material and its preparation and application
CN106894024B (en) Accumulation energy type tungstic acid/strontium titanates/nano titania composite film photo-anode preparation method
CN103952708B (en) For the Ag/SnO of photoproduction galvanic protection 2/ TiO 2the preparation method of composite film photo-anode
CN107699901B (en) Preparation method of zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection
CN104164693B (en) A preparing method of a graphene sensitized CdSe/TiO2 nanotube composite membrane
CN104357852B (en) MnSe/TiO2 composite film for photogenerated cathode protection as well as preparation and application thereof
CN104264158B (en) Preparation method of graphene/CdTe-TiO2 composite membrane photo-anode
CN108546970B (en) Bi2Se3/TiO2Nano composite film and preparation and application thereof
CN108823573A (en) A kind of hydro-thermal method preparation Ni3/S2The method of nanometer tube composite film light anode
CN104475073B (en) A kind of nano-wire array film of titanium dioxide and its preparation and application
CN105386061A (en) Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes
CN104711581A (en) MnS/TiO2 composite nanotube array film for photo-induced cathodic protection and preparation and application thereof
CN109735847B (en) AgInS for photo-generated cathodic protection2graphene/TiO2Nano composite film photo-anode and preparation and application thereof
CN105040062B (en) Cu2O nano-particles are sensitized TiO2The method of nanotube array photoelectrode
CN110042452A (en) A kind of light anode composite membrane, Its Preparation Method And Use
CN109972149B (en) Bi2Te3/Bi2O3/TiO2Preparation method of ternary heterojunction film
CN110344096B (en) AgSbS2Sensitized TiO2Composite membrane material and preparation and application thereof
CN106119858B (en) A kind of NiSe for photoproduction cathodic protection2/TiO2Composite nano tube array films and its preparation and application
CN108251849B (en) Photoelectric material for improving corrosion resistance of stainless steel and repairing method thereof
CN102543457A (en) Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film
CN114277375A (en) MnIn2S4/TiO2Nanotube bundle composite photoanode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180515

RJ01 Rejection of invention patent application after publication