CN111593353A - Photoelectrochemistry anti-corrosion protection composite photo-anode and preparation method and application thereof - Google Patents
Photoelectrochemistry anti-corrosion protection composite photo-anode and preparation method and application thereof Download PDFInfo
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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
- 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
- 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
- C23F13/20—Conducting electric current to electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
The invention discloses a photoelectrochemical anti-corrosion protection composite photo-anode and a preparation method and application thereof, wherein the method comprises the following steps: creative Co (OH) by electrodeposition2And WO3Loaded on the TiO of the traditional photocatalytic material2Preparing the photoelectrochemistry anticorrosion protection composite photoanode on a nanotube film, wherein the Co (OH)2Can effectively promote the separation of photo-generated charges, thereby reducing the carrier recombination rate of the composite photo-anode, and the WO3The compound light anode has the capability of storing charges, so that the compound light anode can realize the photocathode protection under the dark state condition. The invention is through to TiO2The nanotube film is subjected to appropriate surface modification treatment to improve the photoelectric property of the traditional photocatalytic material and realize TiO in the marine environment2For Q235 carbon steel and other goldBelongs to high-efficiency photoelectrochemical cathodic protection, thereby efficiently inhibiting the corrosion of metals such as carbon steel and the like in the marine environment.
Description
Technical Field
The invention relates to the field of metal corrosion prevention, in particular to a photoelectrochemistry corrosion prevention protection composite photo-anode and a preparation method and application thereof.
Background
The problem of corrosion of metals in marine environments is very severe, with countless economic losses and safety problems due to corrosion of materials every year. Sacrificial anode protection has evolved as an inexpensive, scalable means of protection that produces a protective current density that meets the protection requirements of most metallic materials. The photoelectrochemical cathodic protection of the photocatalytic material is a metal protection mode with great potential, electron transition can be generated under illumination, then electrons are transferred to the surface of the metal material to inhibit the corrosion of the metal, and the characteristics of no reaction consumption and environmental friendliness of the photocatalytic material in the illumination protection process have attracted extensive attention of researchers.
However, the high carrier recombination rate and limited visible light absorption of a single photocatalytic material are always main problems which hinder the application and development of the material, and the existing photocatalytic material loses the protection function under the condition of no light and is not beneficial to uninterrupted continuous protection of metal.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a photoelectrochemical anti-corrosion protection composite photo-anode and a preparation method and application thereof, and aims to solve the problem that the application and development of a photocatalytic material in a practical environment are limited due to the defects that the existing photocatalytic material is high in carrier recombination rate, limited in visible light absorption, capable of only acting under light and the like.
The technical scheme of the invention is as follows:
a preparation method of a photoelectrochemical anti-corrosion protection composite photo-anode comprises the following steps:
with TiO2The nanotube film is used as an anode, a platinum sheet and SCE are respectively used as a counter electrode and a reference electrode, and the anode, the counter electrode and the reference electrode are added into a group consisting of soluble alkali metal tungstate and hydrogen peroxideIn the resulting electrolyte, and adjusting the electrolyte to acidity, the TiO is electrodeposited2Nanotube film surface deposition of WO3To obtain WO3Modified TiO2A nanotube film;
subjecting said WO to3Modified TiO2Adding the nanotube film into cobalt salt solution, deionized water, strong alkali solution and deionized water in sequence, circularly depositing for several times, and depositing in the WO3Modified TiO2Deposition of Co (OH) on nanotube films2And (4) granulating to obtain the photoelectrochemistry anticorrosion protection composite photo-anode.
The preparation method of the photoelectrochemical anti-corrosion protection composite photo-anode comprises the steps of applying a constant voltage of (-0.7V) - (-0.1V) to the anode and keeping the constant voltage for 1-5min to enable the TiO to be in contact with the anode2Nanotube film surface deposition of WO3。
The preparation method of the photoelectrochemistry anticorrosion protection composite photo-anode comprises the step of preparing an electrolyte, wherein the molar ratio of soluble alkali metal tungstate to hydrogen peroxide in the electrolyte is 1:3-3: 1.
The preparation method of the photoelectrochemistry anticorrosion protection composite photoanode comprises the following steps of2The nanotube film is subjected to heat treatment at 400-600 ℃.
The preparation method of the photoelectrochemistry anticorrosion protection composite photo-anode comprises the step of preparing an electrolyte, wherein the pH value of the electrolyte is 1-3.
The preparation method of the photoelectrochemical anti-corrosion protection composite photo-anode comprises the step of preparing a cobalt salt solution by using CoCl2Solution, CoCO3Solutions or CoSO4One of the solutions.
The preparation method of the photoelectrochemistry anticorrosion protection composite photo-anode comprises the step of preparing a composite photo-anode by using a solution of strong base, wherein the solution of strong base is a sodium hydroxide solution or a potassium hydroxide solution.
The preparation method of the photoelectrochemical anti-corrosion protection composite photoanode comprises the following steps of3Modified TiO2Adding the nanotube film into cobalt salt solution, deionized water, strong alkali solution and deionized water in sequence, and performing cyclic deposition for 3-10 times, wherein the deposition time is 4-8s each time3Modified TiO2Nano meterDeposition of Co (OH) on the surface of tube film2And (4) granulating to obtain the photoelectrochemistry anticorrosion protection composite photo-anode.
The invention discloses a photoelectrochemistry anticorrosion protection composite photo-anode, which is prepared by adopting the preparation method of the photoelectrochemistry anticorrosion protection composite photo-anode.
The invention discloses application of a photoelectrochemistry anticorrosion protection composite photo-anode, wherein the photoelectrochemistry anticorrosion protection composite photo-anode is used for metal anticorrosion.
Has the advantages that: the invention provides a preparation method of a photoelectrochemical anti-corrosion protection composite photo-anode, which creatively uses Co (OH)2And WO3Loaded on the TiO of the traditional photocatalytic material2On nanotube films, the Co (OH)2Can effectively promote the separation of photo-generated charges, thereby reducing the carrier recombination rate of the composite photo-anode, and the WO3The composite photo-anode has the capability of storing charges, so that the composite photo-anode can realize the protection of the photo-cathode under the dark state condition2The nanotube film is subjected to appropriate surface modification treatment to improve the photoelectric property of the traditional photocatalytic material and realize TiO in the marine environment2The high-efficiency photoelectrochemistry cathode protection is carried out on metals such as Q235 carbon steel, so that the corrosion of the metals such as the carbon steel in the marine environment is effectively inhibited.
Drawings
Fig. 1 is a flow chart of a preferred embodiment of the preparation method of the photoelectrochemical anticorrosion protection composite photo-anode of the present invention.
Fig. 2 is an SEM electron microscope image of the photoelectrochemical anticorrosion protection composite photo-anode prepared in example 1 of the present invention.
FIG. 3 shows Co (OH) prepared in example 1 of the present invention2/WO3/TiO2And (3) connecting the photo-anode with the aluminum alloy, placing the photo-anode in a 3.5% NaCl solution, wherein one side of the photo-anode adopts 12h illumination/12 h dark state, and a corrosion morphology graph of the aluminum alloy is obtained after 15 days.
FIG. 4 shows an unmodified TiO compound in example 2 of the present invention2Connecting the photo-anode with the aluminum alloy, placing the photo-anode in 3.5% NaCl solution, adopting 12h illumination/12 h dark state on one side of the photo-anode, and observing the corrosion of the aluminum alloy after 15 daysAnd (6) topography.
FIG. 5 shows WO in example 3 of the present invention3Modified TiO2And (3) connecting the photo-anode with the aluminum alloy, placing the photo-anode in a 3.5% NaCl solution, adopting 12h illumination/12 h dark state on one side of the photo-anode, and observing a corrosion morphology graph of the aluminum alloy after 15 days.
Detailed Description
The invention provides a photoelectrochemical anti-corrosion protection composite photo-anode and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Due to the defects of high carrier recombination rate, limited visible light absorption, capability of acting only under illumination and the like of the traditional photocatalytic material, the application and development of the photocatalytic material in the actual environment are limited, and the corrosion of metal in the marine environment cannot be effectively prevented.
Based on the problems in the prior art, the invention provides a preparation method of a photoelectrochemical anticorrosion protection composite photo-anode, which comprises the following steps of:
s10, in TiO2Using a nanotube film as an anode, using a platinum sheet and SCE as a counter electrode and a reference electrode respectively, adding the anode, the counter electrode and the reference electrode into an electrolyte consisting of soluble alkali metal tungstate and hydrogen peroxide, adjusting the electrolyte to be acidic, and enabling the TiO to be acidic by an electrodeposition method2Nanotube film surface deposition of WO3To obtain WO3Modified TiO2A nanotube film;
s20, application of the WO3Modified TiO2Adding the nanotube film into cobalt salt solution, deionized water, strong alkali solution and deionized water in sequence, circularly depositing for several times, and depositing in the WO3Modified TiO2Deposition of Co (OH) on nanotube films2And (4) granulating to obtain the photoelectrochemistry anticorrosion protection composite photo-anode.
In the embodiment, TiO with good chemical stability and wide application in the field of photocatalysis is selected2The material is used as a composite photo-anode made of TiO2From the research angle of the preparation process, the surface of the titanium dioxide is properly modified, and the attempt is made to improve the TiO from the source2The charge transfer capability of the material, the recombination rate of a current carrier are controlled, the continuity of the photocatalytic material to the cathode protection is improved through the recombination with the energy storage material, and the preparation of the light sacrificial anode material in the marine environment is realized. Specifically, this example was made by inventively combining Co (OH)2And WO3Loaded on the TiO of the traditional photocatalytic material2On nanotube films, the Co (OH)2Can effectively promote the separation of photo-generated charges, thereby reducing the carrier recombination rate of the composite photo-anode, and the WO3The composite photo-anode has the capability of storing charges, so that the composite photo-anode can realize the protection of the photo-cathode under the dark state condition2The nanotube film is subjected to appropriate surface modification treatment to improve the photoelectric property of the traditional photocatalytic material and realize TiO in the marine environment2The high-efficiency photoelectrochemistry cathode protection is carried out on metals such as Q235 carbon steel, so that the corrosion of the metals such as the carbon steel in the marine environment is effectively inhibited.
In some embodiments, the TiO2The nanotube film can be prepared by anodic oxidation. Specifically, the Ti sheet is taken out of the absolute ethyl alcohol solution, dried and connected to the anode of a direct current power supply, the platinum sheet is taken as the cathode, a potential is applied to the electrolyte for anodic oxidation, and the material is further subjected to heat treatment by using a muffle furnace at the temperature of 400-600 ℃ to obtain TiO2Photo-anode materials, i.e. said TiO2A nanotube film. In this embodiment, if the heat treatment temperature is lower than 400 ℃ or higher than 600 ℃, the TiO formation will be caused2The nanotubes are distorted and sufficient photocatalytic properties cannot be achieved.
In some embodiments, the compound is TiO2The method comprises the steps of taking a nanotube film as an anode, taking a platinum sheet and SCE (calomel) as a counter electrode and a reference electrode respectively, adding the anode, the counter electrode and the reference electrode into an electrolyte consisting of soluble alkali metal tungstate and hydrogen peroxide, adjusting the pH value of the electrolyte to be 1-3 by adopting concentrated nitric acid, and applying an electrodeposition method on the anodeAdding a constant voltage of (-0.7V) - (-0.1V) and holding for 1-5min to make the TiO2Nanotube film surface deposition of WO3To obtain WO3Modified TiO2A nanotube film. Due to WO3Has the ability to store charge, and therefore in the TiO2Nanotube film surface deposition of WO3And then, the finally prepared photoelectrochemistry anticorrosion protection composite light anode can realize the protection of a photocathode under a dark condition.
Specifically, in this example, electrodeposition was used to deposit on TiO2Nanotube film surface deposition of WO3The principle of the method is that tungsten peroxide salt is used as a precursor to generate oxidation-reduction reaction, and the reaction is as follows:
2WO4 2-+4H2O2→W2O11 2-+3H2O+2OH-
W2O11 2-+(2+x)H++xe-→2WO3+(2+x)/2H2O+(8-x)/2O2。
this example is for TiO2The applied voltage of the nanotube film is (-0.7V) - (-0.1V), and the potential difference can cause TiO2WO deposited on the surface of the electrode3The absorption spectra are different; to realize WO3In TiO2Uniform deposition of nanotube film surface, soluble alkali metal tungstate in the electrolyte and the H2O2In a molar ratio of 1:3 to 3:1, and the concentration of the soluble alkali metal tungstate is 1 to 10 mmol/L. By way of example, the soluble alkali metal tungstate may be Na2WO4·H2O。
In this example, since the reduction reaction of tungstate ions is performed under acidic conditions, concentrated nitric acid is used to adjust the pH of the electrolyte to 1 to 3.
This example uses potentiostatic method on TiO2Nanotube film surface deposition of WO3The time of (1) to (5) min, shorter deposition time, WO3Not yet completely filling the voids, long deposition times, WO3Will block TiO2Pore structure of nanotube film and even piling up into clustersAnd both the polymers can influence the absorption characteristic of the final photoelectrochemical anticorrosion protection composite photo-anode.
In some embodiments, the WO is3Modified TiO2Adding the nanotube film into cobalt salt solution, deionized water, strong alkali solution and deionized water in sequence, and performing cyclic deposition for 3-10 times, wherein the deposition time is 4-8s each time3Modified TiO2Deposition of Co (OH) on nanotube films2And (4) granulating to obtain the photoelectrochemistry anticorrosion protection composite photo-anode. Due to Co (OH)2The particles are capable of facilitating photogenerated charge separation and are therefore described in said WO3Modified TiO2Deposition of Co (OH) on nanotube films2The particles can effectively reduce the carrier recombination rate of the composite photo-anode, so that the finally prepared photoelectrochemistry anticorrosion protection composite photo-anode can effectively realize photoelectrochemistry cathodic protection on metal.
In some embodiments, the cobalt salt solution is CoCl2Solution, CoCO3Solutions or CoSO4One of the solutions, but not limited thereto.
In some embodiments, the strong alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, but is not limited thereto.
In some embodiments, the invention further provides a photoelectrochemical anticorrosion protection composite photo-anode which is prepared by the preparation method of the photoelectrochemical anticorrosion protection composite photo-anode.
In some embodiments, the invention further provides an application of the photoelectrochemistry anticorrosion protection composite photo-anode, and the photoelectrochemistry anticorrosion protection composite photo-anode provided by the invention is used for metal anticorrosion.
The preparation method and the performance of the photoelectrochemical anti-corrosion protection composite photo-anode provided by the invention are further explained by the following specific examples:
example 1
Co(OH)2/WO3Modified TiO2Preparing a composite light anode:
1) preparation of TiO by anodic oxidation2Nanotube samples, dissolved from absolute ethanolTaking out the Ti sheet, blowing to dry, connecting to the anode of a direct current power supply, taking the platinum sheet as the cathode, applying a potential in the electrolyte to carry out anodic oxidation, and carrying out heat treatment on the material at 500 ℃ by using a muffle furnace to obtain TiO2A nanotube film;
2) adopting an electrochemical workstation to prepare the TiO prepared in the step (1)2For the working electrode, the platinum plate and SCE were the counter and reference electrodes, respectively, and 80s were deposited at constant-0.5V. Electrolyte is 5mmol/L Na2WO4·2H2O and 15mmol/L H2O2The pH of the mixed solution is adjusted to 1.5 by using concentrated nitric acid. After the electrodeposition is finished, washing a sample by deionized water, drying the sample by blowing, and calcining the sample for 2 hours in a muffle furnace at 500 ℃ to obtain WO3Modified TiO2A nanotube film;
3) the WO prepared in the step (2)3Modified TiO2The nanotube film is sequentially immersed into 0.5mol/LCoSO with a certain concentration4The solution, deionized water, 0.5mol/L sodium hydroxide solution and deionized water are circulated for 5 times to obtain Co (OH)2Modified Co (OH)2/WO3/TiO2And the photo-anode is a photoelectrochemical anti-corrosion protection composite photo-anode.
4) And observing Co (OH) produced in step (3) by SEM2/WO3/TiO2The micro-topography of the photoanode is shown in figure 2. As can be seen from FIG. 2, the WO is passed3And Co (OH)2After modification, the TiO2The product of the projections around the nanotubes, description WO3And Co (OH)2Modified TiO2And (4) success.
5) Adopting conductive adhesive to mix the Co (OH) prepared in the step (3)2/WO3/TiO2The photoanode material is connected with one end of a copper wire to serve as a research electrode, the other end of the copper wire is connected with aluminum alloy, a coupling electrode formed by the photoanode material and the copper wire serves as a working electrode, a platinum sheet serves as a counter electrode, SCE serves as a reference electrode, and electrolyte is 3.5% NaCl solution; an electrochemical workstation is adopted to test the change curve of the Open Circuit Potential (OCP) along with time under illumination and dark states respectively, and the photochemical protection performance of the electrochemical workstation on the metal auxiliary electrode is researched;
6) testing and researching the change of the photoproduction current density of the electrode generated under the conditions of illumination and dark state along with the time by adopting a noise (EN) module of the electrochemical workstation;
7) co (OH) is introduced through a copper wire2/WO3/TiO2Connecting the photo-anode with the aluminum alloy, placing the photo-anode in 3.5% NaCl solution, and adopting 12h illumination/12 h dark state on one side of the photo-anode; the corrosion morphology of the aluminum alloy was observed after 15 days, and the results are shown in fig. 3.
Example 2
1) Adopting conductive adhesive to make unmodified TiO2The photoanode material is connected with one end of a copper wire to serve as a research electrode, the other end of the copper wire is connected with aluminum alloy, a coupling electrode formed by the photoanode material and the copper wire serves as a working electrode, a platinum sheet serves as a counter electrode, SCE serves as a reference electrode, and electrolyte is 3.5% NaCl solution; an electrochemical workstation is adopted to test the change curve of the Open Circuit Potential (OCP) along with time under illumination and dark states respectively, and the photochemical protection performance of the electrochemical workstation on the metal auxiliary electrode is researched;
2) testing and researching the change of the photoproduction current density of the electrode generated under the conditions of illumination and dark state along with the time by adopting a noise (EN) module of the electrochemical workstation;
3) the TiO is connected with a copper wire2Connecting the photo-anode with the aluminum alloy, placing the photo-anode in 3.5% NaCl solution, and adopting 12h illumination/12 h dark state on one side of the photo-anode; the corrosion morphology of the aluminum alloy was observed after 15 days, and the results are shown in fig. 4.
Example 3
1) WO is prepared by adopting conductive adhesive3Modified TiO2The photoanode material is connected with one end of a copper wire to serve as a research electrode, the other end of the copper wire is connected with aluminum alloy, a coupling electrode formed by the photoanode material and the copper wire serves as a working electrode, a platinum sheet serves as a counter electrode, SCE serves as a reference electrode, and electrolyte is 3.5% NaCl solution; an electrochemical workstation is adopted to test the change curve of the Open Circuit Potential (OCP) along with time under illumination and dark states respectively, and the photochemical protection performance of the electrochemical workstation on the metal auxiliary electrode is researched;
2) testing and researching the change of the photoproduction current density of the electrode generated under the conditions of illumination and dark state along with the time by adopting a noise (EN) module of the electrochemical workstation;
3) WO through copper wire3Modified TiO2Connecting the photo-anode with the aluminum alloy, placing the photo-anode in 3.5% NaCl solution, and adopting 12h illumination/12 h dark state on one side of the photo-anode; the corrosion morphology of the aluminum alloy was observed after 15 days, and the results are shown in fig. 5.
As can be seen from FIGS. 3-5, it is believed that the reaction with Co (OH)2/WO3/TiO2The surface of the aluminum alloy after coupling has only slight corrosion and is WO3Modified TiO2Photoanode coupled aluminum alloy surface and unmodified TiO2The aluminum alloy surfaces after photo-anode coupling all showed relatively severe corrosion, which indicates that Co (OH) provided in this example2/WO3/TiO2The photo-anode has good photocatalytic protection performance on metal.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a photoelectrochemistry anticorrosion protection composite photo-anode is characterized by comprising the following steps:
with TiO2Using a nanotube film as an anode, using a platinum sheet and SCE as a counter electrode and a reference electrode respectively, adding the anode, the counter electrode and the reference electrode into an electrolyte consisting of soluble alkali metal tungstate and hydrogen peroxide, adjusting the electrolyte to be acidic, and enabling the TiO to be acidic by an electrodeposition method2Nanotube film surface deposition of WO3To obtain WO3Modified TiO2A nanotube film;
subjecting said WO to3Modified TiO2Adding the nanotube film into cobalt salt solution, deionized water, strong alkali solution and deionized water in sequence, circularly depositing for several times, and depositing in the WO3Modified TiO2Deposition of Co (OH) on nanotube films2And (4) granulating to obtain the photoelectrochemistry anticorrosion protection composite photo-anode.
2. The method for preparing the photoelectrochemical anti-corrosion protection composite photoanode as claimed in claim 1, wherein a constant voltage of (-0.7V) - (-0.1V) is applied to the anode and maintained for 1-5min to make the TiO remain2Nanotube film surface deposition of WO3。
3. The preparation method of the photoelectrochemical anti-corrosion protection composite photo-anode according to claim 1, wherein a molar ratio of the soluble alkali metal tungstate to the hydrogen peroxide in the electrolyte is 1:3-3: 1.
4. The method for preparing the photoelectrochemical anti-corrosion protection composite photoanode as claimed in claim 1, wherein the TiO is selected from the group consisting of TiO, and the method is further characterized in that the method comprises the step of preparing the photoelectrochemical anti-corrosion protection composite photoa2The nanotube film is subjected to heat treatment at 400-600 ℃.
5. The method for preparing the photoelectrochemical anti-corrosion protective composite photoanode as claimed in claim 1, wherein the pH of the electrolyte is 1 to 3.
6. The method for preparing the photoelectrochemical anti-corrosion protection composite photoanode as claimed in claim 1, wherein the cobalt salt solution is CoCl2Solution, CoCO3Solutions or CoSO4One of the solutions.
7. The method for preparing the photoelectrochemical anti-corrosion protective composite photoanode as claimed in claim 1, wherein the strong alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
8. The method for preparing the photoelectrochemical anti-corrosion protection composite photoanode as claimed in claim 1, wherein the WO is applied to the preparation of the photoelectrochemical anti-corrosion protection composite photoanode3Modified TiO2Adding the nanotube film into cobalt salt solution, deionized water, strong alkali solution and deionized water in sequence, and performing cyclic deposition for 3-10 times, wherein the deposition time is 4-8s each time3Modified TiO2Deposition of Co (OH) on nanotube films2And (4) granulating to obtain the photoelectrochemistry anticorrosion protection composite photo-anode.
9. A photoelectrochemical anti-corrosion protection composite photo-anode is characterized by being prepared by the preparation method of the photoelectrochemical anti-corrosion protection composite photo-anode according to any one of claims 1 to 8.
10. The application of the photoelectrochemistry anticorrosion protection composite photo-anode is characterized in that the photoelectrochemistry anticorrosion protection composite photo-anode disclosed by claim 9 is used for metal anticorrosion.
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| CN112962557A (en) * | 2021-03-10 | 2021-06-15 | 深圳大学 | Double corrosion prevention method for marine structure |
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| CN114214703A (en) * | 2022-02-22 | 2022-03-22 | 青岛理工大学 | Z-type heterojunction composite photo-anode membrane and preparation method and application thereof |
| CN114231993A (en) * | 2021-12-20 | 2022-03-25 | 商河县寰宇智能科技中心 | Metal anticorrosive material |
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