CN106498408A - A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection - Google Patents
A kind of preparation of the nano composite membrane light anode for photoproduction cathodic protection Download PDFInfo
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- CN106498408A CN106498408A CN201611143229.6A CN201611143229A CN106498408A CN 106498408 A CN106498408 A CN 106498408A CN 201611143229 A CN201611143229 A CN 201611143229A CN 106498408 A CN106498408 A CN 106498408A
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- 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
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- 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
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Abstract
The present invention relates to a kind of nano composite membrane light anode, more particularly, to a kind of ZnFe for photoproduction cathodic protection2O4/TiO2The preparation of nano composite membrane light anode.TiO is obtained by anodizing first2Film of Nano tube array, then passes through hydro-thermal method again by ZnFe2O4Nano-particle is carried on TiO2On film of Nano tube array.ZnFe prepared by the present invention2O4/TiO2Composite membrane; the characteristics of having coating complete and uniform, can utilize visible ray as light anode, being had by protection electrode potential for connection is significantly declined in illumination; and when closing light source switchs to dark-state, certain cathodic protection effect still can be produced to metal.
Description
Technical field
The present invention relates to a kind of nano composite membrane light anode, more particularly, to a kind of for photoproduction cathodic protection
ZnFe2O4/TiO2The preparation of nano composite membrane light anode.
Background technology
Nano-TiO2Material becomes domestic and international with its good photoelectric characteristic, chemical stability and the advantages of not consuming electric energy
The focus of research.Wherein, protect metal material to cause corrosion from the corrosion i.e. photoproduction cathodic protection effect of media environment to grind
The great interest of the person of studying carefully.Light induced electron causes metal surface electron density to increase, macroscopic view to the relatively low metal surface migration of potential
Electrode potential reduction, even much lower than the spontaneous corrosion potential of metal is shown as, so that metal enters thermodynamics steady-state zone
That is cathode protecting state.Now, TiO2It is the anode as non-sacrificial, it is not necessary to consume electric energy, reusable, this is
TiO2An important advantage.However, the photo-generate electron-hole that photon excitation is produced causes the effect of light quantum to being easy to compound
Rate is not high, can not play effective photoproduction cathodic protection effect under no light condition.In order to solve the above problems, multiple sides can be taken
Method is modified to which, such as metal or nonmetal doping, composite semiconductor or surface sensitization etc..In order to keep TiO during dark-state2
The photoelectrochemical property of film of Nano tube array, as electron stored energy material and is made up of using the quasiconductor of different energy levels researcher
Composite membrane so as to can also maintain certain special role when illumination switchs to dark-state.
Improve TiO2One of maximally effective method of photoresponse is：Couple with the quasiconductor (such as CdS, CdSe etc.) of low energy gap,
Wherein there is the ZnFe of spinel structure2O4Have to visible ray sensitivity, the characteristics such as chemistry or photochemical corrosion, and it does not occur
Energy gap is 1.9eV, when with TiO2During coupling, improve can photoelectric transformation efficiency, as a kind of nano composite material light sun
Pole can obtain better photoelectric conversion performance, can produce more excellent photoproduction cathodic protection effect.
Rustless steel as a kind of important metal, with good corrosion resistance, thermostability, low temperature intensity and mechanical property,
All have been widely used in every profession and trade, but, in many environments, stainless corrosion phenomenon is still very serious, needs to adopt
With controlling measurement, which corrodes.Due to the difference of environment, stainless corrosion control technology remains a need for being researched and developed.
Content of the invention
It is an object of the invention to overcome being difficult to the problems such as maintaining photoproduction cathodic protection effect under no light condition, there is provided one
Plant the ZnFe for photoproduction cathodic protection2O4/TiO2The preparation method of nano composite membrane.
For achieving the above object, the technical solution used in the present invention is：
A kind of preparation method of the nano composite membrane for photoproduction cathodic protection, obtains TiO by anodizing first2
Film of Nano tube array, then passes through hydro-thermal method again by ZnFe2O4Nano-particle is carried on TiO2On film of Nano tube array.
The anodizing refers to be to electrode, by pretreated Titanium base in 20～30V with platinized platinum in the electrolytic solution
0.5～1h of anodic oxidation is carried out under voltage, is cooled to room temperature, you can be obtained on titanium surface after then calcining at 400～450 DEG C
TiO2Film of Nano tube array.
The electrolyte is containing 0.5～0.6wt%NH4The ethylene glycol solution of F, 1～1.3vol% ultra-pure water；
The pretreatment of the Titanium base is：By Titanium base successively in methanol, acetone, isopropanol, polishing fluid, in deionized water
Titanium base is cleaned by ultrasonic.Wherein, the proportioning of polishing fluid is HF:HNO3:H2O=1:4:5～1:5:6 (vol ratios).
Specifically, the titanium foil adopts purity for more than 99.9%, and thickness is 0.1～0.2mm, and length is 15～35mm,
Width is the pure titanium foil of 10～25mm；Each ultrasonic cleaning time is 2～4min.
The hydro-thermal method refers to Zn (NO3)2With Fe (NO3)3Press 1:2～1:3 molar concentration rate mixing, then adjusts mixing
Liquid ph values are 9～11, by mixed liquor and the TiO2Film of Nano tube array is placed in reactor, heat treatment at 100～180 DEG C
10～12h, after cooling, is rinsed repeatedly with dehydrated alcohol and deionized water, dries 3～4h, that is, obtain at 60～80 DEG C
ZnFe2O4/TiO2Nano composite membrane.
The regulation mixed liquor ph values use the NaOH solution of 3～5M.
The acquisition ZnFe2O4/TiO2Nano composite membrane can be used as the application in photoproduction cathodic protection composite membrane.
Above-mentioned gained is used for the ZnFe of photoproduction cathodic protection2O4/TiO2The photoproduction cathodic protection method of testing of nano composite membrane
As follows：Using double-electrolyzer electro-chemical systems, this system is made up of photoelectrolytic cell and corrosion electrolyzer, as shown in figure 1, photoelectrolysis
With ZnFe in pond2O4/TiO2Nano composite membrane is contained in 0.1～0.2mol/L Na as optoelectronic pole2In S solution, corrosion electrolysis
In pond with by protection metal (rustless steel) as working electrode, saturated calomel electrode (SCE) as reference electrode, Pt electrodes be to electricity
The highest is placed in 3.5～4.0% NaCl solution, by optoelectronic pole be connected with wire by protection metal, photoelectrolytic cell and corrosion
Electrolyzer is connected by salt bridge (agar containing saturation KCl), using 100～150W high pressure Xe lamps as visible light source (additional purple
Outer smooth optical filter so that optical source wavelength 400nm), shine directly into ZnFe in photoelectrolytic cell2O4/TiO2Nano composite membrane table
Face, then, tests potential change of the metal electrode before and after illumination with electrochemical workstation.
The ultimate principle of the present invention：ZnFe2O4It is a kind of soft magnetic materials of function admirable, is that there is very highlight catalytic active
And the semiconductor catalyst sensitive to visible ray, its energy gap is narrower, when photon energy can excite ZnFe2O4Can not excite
TiO2When, due to TiO2Conduction band is less than ZnFe2O4, be conducive to electronics from ZnFe2O4Migrate to TiO2, separation efficiency is improve, greatly
The recombination probability of electron hole is reduced greatly, and last light induced electron produces photoproduction electricity to the stainless steel surfaces migration being attached thereto
Stream, makes that stainless steel electrode current potential is negative to be moved so as in by guard mode from corrosion.Therefore, by preparing ZnFe2O4/TiO2
Nano composite membrane, is allowed to be connected with stainless steel metal, can effectively improve the Corrosion Protection of metal.
Advantage for present invention：
(1) ZnFe that will there is very highlight catalytic active2O4Material and more ripe photoelectric material TiO2Compound, can have
The raising protective capabilities of the TiO2 to metal of effect, improves its photoproduction cathodic protection performance.
(2) by hydro-thermal method in the TiO for having prepared2ZnFe is loaded on film of Nano tube array2O4Nano-particle, method letter
Easily, and preparation condition is controllable, only need to be by the TiO for preparing2Film of Nano tube array and ZnFe2O4Mixed liquor is put into reaction together
Kettle heat treatment, then drying and processing；So cause ZnFe2O4/TiO2Composite membrane, with uniform diameter, regular appearance,
And Load Balanced is the characteristics of arrange.Improve pure TiO2Light abstraction width, can as photoproduction cathodic protection composite film material should
In the middle of aseptic technic.
(3) ZnFe prepared by the present invention2O4/TiO2When composite membrane is with being connected by protection metal, in radiation of visible light
Under, 304 stainless steel electrode current potentials in the middle of corrosion electrolyzer drop to -780mV or so, have dropped than corrosion potential
, there is significant cathodic polarization phenomenon, show that the photoproduction cathodic protection effect of composite membrane is notable in 500mV or so.Visible when stopping
Light irradiation, though stainless steel electrode current potential rises, is still below stainless corrosion potential, shows also have in the dark state well
Cathodic protection effect, with good stabilizing effect.
In sum, the present invention prepares ZnFe using anodizing and hydro-thermal method2O4/TiO2Composite membrane, the thin film conduct
Light anode shows excellent photoproduction cathodic protection effect.
Description of the drawings
Fig. 1 is composite membrane photoproduction cathodic protection test device provided in an embodiment of the present invention, and left side is corrosion electrolyzer, contains
Dress 3.5%NaCl solution, is that calomel electrode is reference electrode to electrode with platinized platinum respectively, and 304 rustless steels that polish are work
Electrode.Right side is photoelectrolytic cell, contains 0.1mol/L Na2S (hole trapping agents) solution, with ZnFe2O4/TiO2Nano composite membrane
As light anode, it is connected with 304 rustless steels with wire.When there is illumination, light induced electron is from ZnFe2O4Conduction band transitions arrive
TiO2, be most attached thereto backward 304 stainless steel surfaces migration, produce photogenerated current, make 304 rustless steels occur cathodic polarization,
So as to play a protective role to 304 rustless steels.
Fig. 2 a are TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano thin-film, scale is 100nm.
Fig. 2 b are ZnFe provided in an embodiment of the present invention2O4/TiO2The surface topography (SEM figures) of nano composite membrane, scale is
100nm.
Fig. 3 is ZnFe provided in an embodiment of the present invention2O4/TiO2The solid diffuse-reflectance ultraviolet-visible light of nano composite membrane
Spectrum, wherein, abscissa is wavelength (nm), and vertical coordinate is absorption intensity.
Fig. 4 is ZnFe provided in an embodiment of the present invention2O4/TiO2Nano composite membrane be placed in 3.5%NaCl solution
The OCP figure that the coupling of 304 rustless steels is obtained.Wherein, abscissa is the time (s), and vertical coordinate is current potential (V vs.SCE).on
Represent that illumination, off represent closing light source i.e. dark-state.
Fig. 5 a are TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano thin-film, scale is 100nm.
Fig. 5 b are ZnFe provided in an embodiment of the present invention2O4/TiO2The surface topography (SEM figures) of nano composite membrane, scale is
100nm.
Fig. 6 is ZnFe provided in an embodiment of the present invention2O4/TiO2The solid diffuse-reflectance ultraviolet-visible light of nano composite membrane
Spectrum, wherein, abscissa is wavelength (nm), and vertical coordinate is absorption intensity.
Fig. 7 is ZnFe provided in an embodiment of the present invention2O4/TiO2Nano composite membrane be placed in 3.5%NaCl solution
The OCP figure that the coupling of 304 rustless steels is obtained.Wherein, abscissa is the time (s), and vertical coordinate is current potential (V vs.SCE).on
Represent that illumination, off represent closing light source i.e. dark-state.
Fig. 8 a are TiO provided in an embodiment of the present invention2The surface topography (SEM figures) of nano thin-film, scale is 100nm.
Fig. 8 b are ZnFe provided in an embodiment of the present invention2O4/TiO2The surface topography (SEM figures) of nano composite membrane, scale is
100nm.
Fig. 9 is ZnFe provided in an embodiment of the present invention2O4/TiO2The solid diffuse-reflectance ultraviolet-visible light of nano composite membrane
Spectrum, wherein, abscissa is wavelength (nm), and vertical coordinate is absorption intensity.
Figure 10 is ZnFe provided in an embodiment of the present invention2O4/TiO2Nano composite membrane be placed in 3.5%NaCl solution
The OCP figure that the coupling of 304 rustless steels is obtained.Wherein, abscissa is the time (s), and vertical coordinate is current potential (V vs.SCE).on
Represent that illumination, off represent closing light source i.e. dark-state.
Specific embodiment
Following instance is used for the present invention to be described, but is not limited to the scope of the present invention.
The present invention prepares TiO by anodizing2Film of Nano tube array, then nano-particle is loaded by hydro-thermal method.This
Method is simple to operate, and stable reaction can control, and through once heat treatment, first drying after preparation solution, just can load quasiconductor
Material, and can preferably improve the Corrosion Protection of metal.ZnFe prepared by the present invention2O4/TiO2Composite membrane, with coating
Complete and uniform the characteristics of, visible ray can be utilized as light anode, connection is made in illumination is had by protection electrode potential
Significantly decline, and when closing light source switchs to dark-state, certain cathodic protection effect still can be produced to metal.
Embodiment 1：
ZnFe2O4/TiO2The preparation method of nano composite membrane：
It is sample to take the thick rectangle pure titanium foils of 0.1mm, titanium foil of the cutting specification for 15 × 10mm, successively methanol, third
Each ultrasonic cleaning 2 minutes in ketone, isopropanol, polishing fluid, deionized water.The proportioning of its polishing fluid is HF:HNO3:H2O=1:4:
5 (vol ratios).
Weigh 0.55gNH4F, is dissolved in 1.3ml ultra-pure waters, adds 100ml ethylene glycol.Mix, under room temperature, to locate in advance
Titanium foil after reason is anode, and platinized platinum is negative electrode, in above-mentioned electrolyte, aoxidizes 1h with 20V ultors, is then put into sample
2h is calcined in Muffle furnace at 450 DEG C, then cools to room temperature with the furnace, i.e., TiO is obtained on Ti surfaces2Film of Nano tube array.
Configuration ZnFe2O4Solution, weighs the Zn (NO of 5mM3)2Fe (NO with 10mM3)3Mixing, places on magnetic stirring apparatuss
Stirring 30min, while the NaOH from 3M adjusts ZnFe2O4Solution ph to 11, then by mixed liquor and TiO2Nano-tube array
Film is put in reactor together, is then placed in baking oven heat treatment 10h at 100 DEG C, after cooling, with dehydrated alcohol and deionization
Water is rinsed repeatedly, then drying and processing 4h at 60 DEG C in an oven, obtains the ZnFe for photoproduction cathodic protection2O4/TiO2Nanometer
Composite membrane.
ZnFe prepared by said method2O4/TiO2Nano composite membrane photoproduction cathodic protection is tested：Using double-electrolyzer electricity
Chemical system, as shown in figure 1, this system is made up of photoelectrolytic cell and corrosion electrolyzer, with ZnFe in photoelectrolytic cell2O4/TiO2Receive
Nano composite material is contained in 0.1mol/L Na as optoelectronic pole2In S solution, in corrosion electrolyzer, to be protected metal, (304 are not
Rust steel) as working electrode, saturated calomel electrode (SCE) be reference electrode, Pt electrodes be electrode is contained in 3.5% NaCl
In solution, optoelectronic pole is connected with wire with metal is protected, photoelectrolytic cell and corrosion electrolyzer pass through salt bridge (KCl containing saturation
Agar) connection, using 100W high pressure Xe lamps as visible light source (additional uv filter so that optical source wavelength
400nm), the ZnFe in photoelectrolytic cell is shone directly into2O4/TiO2Nano composite membrane surface.
Obtained TiO can be seen by Fig. 2 a2The SEM figures of film of Nano tube array.As can be seen that film of Nano tube array compares
Uniformly, the equal 100nm of internal diameter, Fig. 2 b can see obtained ZnFe2O4/TiO2The SEM figures of nano composite membrane, it can be seen that
ZnFe2O4Nano-particle is mainly distributed at the inwall and the mouth of pipe of nanotube, and distribution uniform.
The solid diffuse-reflectance ultraviolet-visible spectrum of different nanometer film as seen from Figure 3, abscissa is wavelength (nm), vertical coordinate
For absorption intensity.It can be seen that pure TiO2The light abstraction width of nano thin-film mainly in ultraviolet region, as compound ZnFe2O4Nanometer
After granule, the visible region absorption intensity of nanometer film is dramatically increased, and shows ZnFe2O4Granule can expand the absorption model to visible ray
Enclose.
As seen from Figure 4 304 rustless steels in 3.5%NaCl solution respectively with pure TiO in the photoelectrolytic cell2Film and
ZnFe2O4/TiO2Nano combined membrane electrode couples rear electrode current potential versus time curve, and abscissa is the time (s), indulges and sits
It is designated as electrode potential (V vs.SCE).Pure TiO under rustless steel with illumination2When membrane electrode is coupled, 304 stainless corrosion electricity
Potential drop plays certain photoproduction cathodic protection effect to about -250mV.When coupling with composite membrane, stainless electrode potential can
- 770mV is fallen to approximately, with the prolongation of light application time, current potential is gradually reduced.When light source is cut off, stainless electrode potential
Begin to ramp up, but now 304 stainless steel electrode current potentials are far below and pure TiO2Rustless steel current potential during coupling.Light is carried out again
According to the stainless electrode potential being now connected with composite membrane is rapidly decreased to -770mV or so, shows the stability of composite membrane again
Well.
Embodiment 2：
ZnFe2O4/TiO2The preparation method of nano composite membrane：
It is sample to take the thick rectangle pure titanium foils of 0.1mm, titanium foil of the cutting specification for 15 × 10mm, successively methanol, third
Each ultrasonic cleaning 2 minutes in ketone, isopropanol, polishing fluid, deionized water.The proportioning of its polishing fluid is HF:HNO3:H2O=1:4:
5 (vol ratios).
Weigh 0.55gNH4F, is dissolved in 1.3ml ultra-pure waters, adds 100ml ethylene glycol.Mix, under room temperature, to locate in advance
Titanium foil after reason is anode, and platinized platinum is negative electrode, in above-mentioned electrolyte, aoxidizes 1h with 20V ultors, is then put into sample
2h is calcined in Muffle furnace at 450 DEG C, then cools to room temperature with the furnace, i.e., TiO is obtained on Ti surfaces2Film of Nano tube array.
Configuration ZnFe2O4Solution, weighs the Zn (NO of 25mM3)2Fe (NO with 50mM3)3Mixing, places on magnetic stirring apparatuss
Stirring 30min, while the NaOH from 3M adjusts ZnFe2O4Solution ph to 11, then by mixed liquor and TiO2Nano-tube array
Film is put in reactor together, is then placed in baking oven heat treatment 10h at 100 DEG C, after cooling, with dehydrated alcohol and deionization
Water is rinsed repeatedly, then drying and processing 4h at 60 DEG C in an oven, obtains the ZnFe for photoproduction cathodic protection2O4/TiO2Nanometer
Composite membrane.
ZnFe prepared by said method2O4/TiO2Nano composite membrane photoproduction cathodic protection is tested：Using double-electrolyzer electricity
Chemical system, as shown in figure 1, this system is made up of photoelectrolytic cell and corrosion electrolyzer, with ZnFe in photoelectrolytic cell2O4/TiO2Receive
Nano composite material is contained in 0.1mol/L Na as optoelectronic pole2In S solution, in corrosion electrolyzer, to be protected metal, (304 are not
Rust steel) as working electrode, saturated calomel electrode (SCE) be reference electrode, Pt electrodes be electrode is contained in 3.5% NaCl
In solution, optoelectronic pole is connected with wire with metal is protected, photoelectrolytic cell and corrosion electrolyzer pass through salt bridge (KCl containing saturation
Agar) connection, using 100W high pressure Xe lamps as visible light source (additional uv filter so that optical source wavelength
400nm), the ZnFe in photoelectrolytic cell is shone directly into2O4/TiO2Nano composite membrane surface.
Obtained TiO can be seen by Fig. 5 a2The SEM figures of film of Nano tube array.As can be seen that film of Nano tube array compares
Uniformly, internal diameter is 100nm, and Fig. 5 b can see obtained ZnFe2O4/TiO2The SEM figures of nano composite membrane, it can be seen that
ZnFe2O4Nano-particle is mainly distributed at the inwall and the mouth of pipe of nanotube, and distribution uniform.
The solid diffuse-reflectance ultraviolet-visible spectrum of different nanometer film as seen from Figure 6, abscissa is wavelength (nm), vertical coordinate
For absorption intensity.It can be seen that pure TiO2The light abstraction width of nano thin-film mainly in ultraviolet region, as compound ZnFe2O4Nanometer
After granule, the visible region absorption intensity of nanometer film is dramatically increased, and shows ZnFe2O4Granule can expand the absorption model to visible ray
Enclose.
As seen from Figure 7 304 rustless steels in 3.5%NaCl solution respectively with pure TiO in the photoelectrolytic cell2Film and
ZnFe2O4/TiO2Nano combined membrane electrode couples rear electrode current potential versus time curve, and abscissa is the time (s), indulges and sits
It is designated as electrode potential (V vs.SCE).Pure TiO under rustless steel with illumination2When membrane electrode is coupled, 304 stainless corrosion electricity
Potential drop plays certain photoproduction cathodic protection effect to about -250mV.When coupling with composite membrane, stainless electrode potential can
- 660mV is fallen to approximately, with the prolongation of light application time, current potential is gradually reduced.When light source is cut off, stainless electrode potential
Begin to ramp up, but now 304 stainless steel electrode current potentials are far below and pure TiO2Rustless steel current potential during coupling.Light is carried out again
According to the stainless electrode potential being now connected with composite membrane is rapidly decreased to -660mV or so, shows the stability of composite membrane again
Well.
Embodiment 3：
ZnFe2O4/TiO2The preparation method of nano composite membrane：
It is sample to take the thick rectangle pure titanium foils of 0.1mm, titanium foil of the cutting specification for 15 × 10mm, successively methanol, third
Each ultrasonic cleaning 2 minutes in ketone, isopropanol, polishing fluid, deionized water.The proportioning of its polishing fluid is HF:HNO3:H2O=1:4:
5 (vol ratios).
Weigh 0.55gNH4F, is dissolved in 1.3ml ultra-pure waters, adds 100ml ethylene glycol.Mix, under room temperature, to locate in advance
Titanium foil after reason is anode, and platinized platinum is negative electrode, in above-mentioned electrolyte, aoxidizes 1h with 20V ultors, is then put into sample
2h is calcined in Muffle furnace at 450 DEG C, then cools to room temperature with the furnace, i.e., TiO is obtained on Ti surfaces2Film of Nano tube array.
Configuration ZnFe2O4Solution, weighs the Zn (NO of 50mM3)2Fe (NO with 100mM3)3Mixing, places magnetic stirring apparatuss
Upper stirring 30min, while the NaOH from 3M adjusts ZnFe2O4Solution ph to 11, then by mixed liquor and TiO2Nanotube battle array
Row film is put in reactor together, is then placed in baking oven heat treatment 10h at 100 DEG C, after cooling, with dehydrated alcohol and go from
Sub- water is rinsed repeatedly, then drying and processing 4h at 60 DEG C in an oven, obtains the ZnFe for photoproduction cathodic protection2O4/TiO2Receive
Rice composite membrane.
ZnFe prepared by said method2O4/TiO2Nano composite membrane photoproduction cathodic protection is tested：Using double-electrolyzer electricity
Chemical system, as shown in figure 1, this system is made up of photoelectrolytic cell and corrosion electrolyzer, with ZnFe in photoelectrolytic cell2O4/TiO2Receive
Nano composite material is contained in 0.1mol/L Na as optoelectronic pole2In S solution, in corrosion electrolyzer, to be protected metal, (304 are not
Rust steel) as working electrode, saturated calomel electrode (SCE) be reference electrode, Pt electrodes be electrode is contained in 3.5% NaCl
In solution, optoelectronic pole is connected with wire with metal is protected, photoelectrolytic cell and corrosion electrolyzer pass through salt bridge (KCl containing saturation
Agar) connection, using 100W high pressure Xe lamps as visible light source (additional uv filter so that optical source wavelength
400nm), the ZnFe in photoelectrolytic cell is shone directly into2O4/TiO2Nano composite membrane surface.
Obtained TiO can be seen by Fig. 8 a2The SEM figures of film of Nano tube array.As can be seen that film of Nano tube array compares
Uniformly, internal diameter is 100nm, and Fig. 8 b can see obtained ZnFe2O4/TiO2The SEM figures of nano composite membrane, it can be seen that
ZnFe2O4Nano-particle is mainly distributed at the inwall and the mouth of pipe of nanotube, and distribution uniform.
The solid diffuse-reflectance ultraviolet-visible spectrum of different nanometer film as seen from Figure 9, abscissa is wavelength (nm), vertical coordinate
For absorption intensity.It can be seen that pure TiO2The light abstraction width of nano thin-film mainly in ultraviolet region, as compound ZnFe2O4Nanometer
After granule, the visible region absorption intensity of nanometer film is dramatically increased, and shows ZnFe2O4Granule can expand the absorption model to visible ray
Enclose.
As seen from Figure 10 304 rustless steels in 3.5%NaCl solution respectively with pure TiO in the photoelectrolytic cell2Film and
ZnFe2O4/TiO2Nano combined membrane electrode couples rear electrode current potential versus time curve, and abscissa is the time (s), indulges and sits
It is designated as electrode potential (V vs.SCE).Pure TiO under rustless steel with illumination2When membrane electrode is coupled, 304 stainless corrosion electricity
Potential drop plays certain photoproduction cathodic protection effect to about -250mV.When coupling with composite membrane, stainless electrode potential can
- 580mV is fallen to approximately, with the prolongation of light application time, current potential is gradually reduced.When light source is cut off, stainless electrode potential
Begin to ramp up, but now 304 stainless steel electrode current potentials are far below and pure TiO2Rustless steel current potential during coupling.Light is carried out again
According to the stainless electrode potential being now connected with composite membrane is rapidly decreased to -580mV or so, shows the stability of composite membrane again
Well.
Claims (7)
1. a kind of preparation method of the nano composite membrane for photoproduction cathodic protection, it is characterised in that：Pass through anodic oxidation first
Method obtains TiO2Film of Nano tube array, then passes through hydro-thermal method again by ZnFe2O4Nano-particle is carried on TiO2Film of Nano tube array
On.
2. the preparation method of the nano composite membrane of photoproduction cathodic protection is used for as described in claim 1, it is characterised in that：The sun
Pole oxidizing process refers to be to electrode with platinized platinum in the electrolytic solution, and pretreated Titanium base is carried out under 20～30V voltages anode
0.5～1h of oxidation, is cooled to room temperature after then calcining at 400～450 DEG C, you can TiO is obtained on titanium surface2Nano-tube array
Film.
3. the preparation method of the nano composite membrane of photoproduction cathodic protection is used for as described in claim 2, it is characterised in that：The electricity
Solution liquid is containing 0.5～0.6wt%NH4The ethylene glycol solution of F, 1～1.3vol% ultra-pure water.
4. the preparation method of the nano composite membrane of photoproduction cathodic protection is used for as described in claim 2, it is characterised in that：The titanium
The pretreatment of matrix is：By Titanium base successively in methanol, acetone, isopropanol, polishing fluid, Titanium base is surpassed in deionized water
Sound is cleaned.
Wherein, the proportioning of polishing fluid is HF:HNO3:H2O=1:4:5～1:5:6 (vol ratios).
5. the preparation method of the nano composite membrane of photoproduction cathodic protection is used for as described in claim 1, it is characterised in that：The water
Full-boiled process refers to Zn (NO3)2With Fe (NO3)3Press 1:2～1:3 molar concentration rate mixing, then adjust mixed liquor ph values for 9～
11, by the TiO2Film of Nano tube array is soaked in mixed liquor, is then placed in reactor, heat treatment at 100～180 DEG C
10～12h, after cooling, is rinsed repeatedly with dehydrated alcohol and deionized water, dries 3～4h, that is, obtain at 60～80 DEG C
ZnFe2O4/TiO2Nano composite membrane.
6. the preparation method of the nano composite membrane of photoproduction cathodic protection is used for as described in claim 5, it is characterised in that：The tune
Section mixed liquor ph values use the NaOH solution of 3～5M.
7. a kind of preparation method of the nano composite membrane for utilizing claim 1 to be used for photoproduction cathodic protection obtains nano composite membrane
Application, it is characterised in that：The acquisition ZnFe2O4/TiO2Nano composite membrane can as photoproduction cathodic protection composite membrane in should
With.
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