CN112981415A - Preparation method and application of layered double-metal hydroxide-based composite film - Google Patents

Preparation method and application of layered double-metal hydroxide-based composite film Download PDF

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CN112981415A
CN112981415A CN202110212081.1A CN202110212081A CN112981415A CN 112981415 A CN112981415 A CN 112981415A CN 202110212081 A CN202110212081 A CN 202110212081A CN 112981415 A CN112981415 A CN 112981415A
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胡吉明
周明杰
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Zhejiang University ZJU
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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
    • C23F13/14—Material for sacrificial anodes
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors

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Abstract

The invention discloses a preparation method and application of a layered double-metal hydroxide-based composite film, which comprises the following steps: (1) deposition of layered double hydroxide: immersing a metal matrix in a solution containing specific different types of mixed metal salts, taking the metal matrix as a working electrode and a platinum sheet electrode as an auxiliary electrode, applying a cathode potential on the metal matrix by an electrochemical auxiliary deposition method, and depositing an LDH film on the metal surface; (2) loading of corrosion inhibitor: soaking the sample obtained by deposition in a solution containing an anionic corrosion inhibitor capable of slowing down the metal corrosion rate, and loading the anionic corrosion inhibitor by utilizing the interlayer anion exchange capacity of LDH (layered double hydroxide); (3) preparing a composite film: preparing ZnO and TiO on the surface of the LDH film loaded with the corrosion inhibitor by an electrodeposition method2Or SnO2And (3) a semiconductor material film to obtain a composite film of the two materials. The composite film has the advantages of two materialsGood corrosion protection of the metal can be achieved.

Description

Preparation method and application of layered double-metal hydroxide-based composite film
Technical Field
The invention relates to the field of metal corrosion protection, in particular to a preparation method and application of a layered double-metal hydroxide-based composite film.
Background
The photo-generated cathodic protection technology is widely applied in the field of metal corrosion protection in recent years due to the advantages of environmental friendliness, no need of external current and the like. In which TiO is2Because of the advantages of stable acid and alkali, wide source and the like, the material has been applied to photo-generated cathode protectionIn the field of protection. However, the existing photoproduction cathodic protection technology rarely has the protection capability on a metal matrix under the condition of no light, and in actual use, the metal can be effectively protected only within 10 hours of illumination every day, and the protection effect is not realized in the absence of illumination. The existence of the problem causes the photoproduction cathodic protection to have certain limitation in practical application, and limits the development of the photoproduction cathodic protection.
Layered Double Hydroxides (LDH), also known as hydrotalcites, belong to anionic Layered compounds and are a class of anionic clays, with interlamellar anions being exchangeable. Trivalent M3+Cation passage to some divalent M in brucite layer2+Isomorphous substitution of cations results in positively charged sheet-like structures, which are balanced by the insertion of anions in the hydrated interlayer channels between these sheet-like structures. LDH can release anionic corrosion inhibitor and adsorb corrosion medium Cl due to its own anion exchangeability-It has been widely used in the field of metal corrosion prevention. However, the general LDH film can only protect corrosion through passive barrier action and corrosion inhibitor, and the effect is single.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and application of a layered double hydroxide-based composite film. We tried to combine two materials to obtain a dual-functional composite film. The LDH film at the bottom layer of the composite film has the functions of releasing the corrosion inhibitor and adsorbing corrosive medium chloride ions, and can realize the protection of metal in the absence of illumination. The existence of the semiconductor material in the semiconductor film material enables the composite film to have the capacity of light absorption, and can excite photo-generated electrons under the illumination condition, thereby playing a role in cathodic protection on metal.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a layered double metal hydroxide-based composite film comprises the following steps:
(1) deposition of Layered Double Hydroxides (LDH):
polishing, deoiling, cleaning and drying a metal matrix; adding 0.1-5 g of metal M nitrate and metal N nitrate into 50-100 mL of deionized water, and stirring, wherein M and N are different; adding the prepared mixed metal salt solution into a three-electrode electrolytic tank, taking Ag/AgCl as a reference electrode, taking a metal matrix as a working electrode, and taking a platinum net as a counter electrode for electrodeposition. After electrodeposition, washing the metal surface by deionized water, and drying;
(2) loading of corrosion inhibitor:
preparing a solution with the corrosion inhibitor concentration of 0.01-1M, adjusting the pH to 9-14 by NaOH or KOH, and uniformly stirring for later use; soaking the sample obtained by deposition in the step (1) in a solution of a corrosion inhibitor, cleaning the surface of the sample by using deionized water after treatment, and drying;
(3) preparing a composite film: preparing an electrodeposition solution with the concentration of 0.01-1M, adding the prepared electrodeposition solution into a three-electrode electrolytic cell, taking Ag/AgCl as a reference electrode, taking the sample treated in the step (2) as a working electrode, taking a platinum net as a counter electrode for electrodeposition, cleaning the metal surface with deionized water after electrodeposition, and drying;
the combination of metals M, N described in step (1) includes: the metal matrix is iron, copper, nickel and alloy of the metals, the electrodeposition is cathodic electrodeposition, the deposition potential is-0.7 to-1.9V, the deposition time is 1 to 5 min, and the deposition temperature is 20 to 60 ℃.
The corrosion inhibitor used in the step (2) is one or more of tungstate, molybdate, silicate, phosphate, metavanadate and chromate, the treatment time is 0.5-48 h, and the treatment temperature is 20-140 ℃.
The electrodeposition solution used in the step (3) contains Zn2+、Ti4+、Sn4+The electrodeposition is cathode electrodeposition, the deposition potential is-0.5 to-1.5V, the deposition time is 1 to 5 min, the deposition temperature is 0 to 80 ℃, and the components of the film obtained by electrodeposition are ZnO and TiO2Or SnO2。
The metal matrix with the layered double hydroxide-based composite film is obtained according to the method.
The method is used for corrosion protection of a metal matrix, and a composite film of an LDH film with a corrosion inhibition function and a semiconductor film with a photoproduction cathode protection function is prepared on the surface layer of the metal matrix.
The invention has the beneficial effects that:
existing pure TiO2And ZnO and other photoproduction cathode protection materials can rarely protect a metal matrix under the condition of no light passing, the invention synthesizes a dual-function composite film, and semiconductor materials ZnO and TiO are adopted under the condition of light passing2Or SnO2Has the function of photo-generated cathode protection, and can realize the protection of the metal matrix. The LDH can be released by ion-exchanging the supported corrosion inhibitor ions to achieve the effect of reducing the metal corrosion rate even when light is not passed.
The composite film can reduce the corrosion rate of the substrate to 20% of the original corrosion rate when not being irradiated, and further reduce the corrosion rate under the condition of being irradiated, and the protection effect is far better than that before being compounded.
Drawings
FIG. 1 is a Tafel plot for samples of NiAl-LDH after bare 304SS and tungstate-exchanged in example 1.
FIG. 2 is an SEM photograph of a composite film obtained in example 1.
FIG. 3 is a graph showing the change in open circuit potential before and after light-on of the composite film obtained in example 1.
Detailed Description
Example 1
The method for preparing the composite film on the surface of the 304 stainless steel substrate comprises the following steps:
(1) mechanically polishing a 304 stainless steel substrate by using 100-mesh sand paper, 320-mesh sand paper, 800-mesh sand paper and No. 14 metallographic sand paper in sequence, then putting the polished substrate into deoiling liquid at 60 ℃ for deoiling for 10 min, then sequentially cleaning the substrate by using deionized water and absolute ethyl alcohol, quickly drying the substrate by using hot air, and placing the substrate in a drying box for 24 h for later use; the NiAl mixed solution is prepared by adding 0.6 g of Ni (NO) into 100 mL of deionized water3)2·6H2O and 0.5g Al (NO)3)3·9H2O; stirring for 2 hours at room temperature; in a three-electrode electric machineAdding the prepared NiAl mixed solution into the electrolytic bath, taking Ag/AgCl as a reference electrode, taking a polished metal matrix as a working electrode and a platinum net as a counter electrode, and carrying out electrodeposition, wherein the potential of the electrodeposition is controlled at-1.7V, the deposition time is 2.5 min, and the deposition temperature is 30 ℃. And after deposition, the surface of the 304 stainless steel is cleaned by deionized water, and then the stainless steel is dried in an oven at the temperature of 45 ℃, and a sample is marked as NiAl-LDH.
(2) Preparing 0.3M Na2WO4The solution was adjusted to pH 11.0 with 1M NaOH and stirred well for use. NiAl-LDH in Na2WO4Soaking in the solution at 60 deg.C for 4 hr. After the treatment, the sample wafer is washed twice with deionized water and dried for later use by nitrogen blow. The sample was designated as NiAl-W-LDH. The corrosion rate of the NiAl-W-LDH obtained by the Tafel test is shown in the attached figure 1.
(3) 0.15M Zn (NO) is prepared3)2And (4) electrodepositing the solution, and uniformly stirring for later use. The NiAl-W-LDH is used as a working electrode, a platinum sheet is used as a counter electrode, saturated Ag/AgCl is used as a reference electrode, and the electrodeposition process is carried out in a constant-temperature water bath at 60 ℃. The cathode deposition potential was set at-1.0V and the deposition time was fixed at 150 s. And (3) after the deposition is finished, cleaning the sample wafer twice by using deionized water, drying the sample wafer in a 45 ℃ oven, and then carrying out heat treatment at 120 ℃ for 24 hours, wherein the sample is marked as NiAl-W-LDH/ZnO (the appearance is shown in the attached figure 2).
(4) The back and side of the 304 stainless steel with the deposited composite film was sealed with epoxy, leaving only 1.5 cm by 1.5 cm of the front side as the test area. A three-electrode system is used for testing the photoproduction cathodic protection effect, 304 stainless steel deposited with a composite film is used as a working electrode, Ag/AgCl is used as a reference electrode, a Pt sheet electrode is used as a counter electrode in an electrolytic cell and is placed in NaCl solution with the mass fraction of 3.5%, a 500W high-pressure Xe lamp is adopted to simulate a sunlight source, the current of the light source is 15A, light penetrates through a quartz window of an electrolytic cell to irradiate the surface of a film material, and then a CHI 630D type electrochemical workstation is used for testing the open-circuit potential change of the working electrode before and after illumination under the bias voltage of 0V (shown in figure 3). Fig. 3 shows that the electrode potential of the 304 stainless steel deposited with the composite film is reduced to-310 mV and lower than the natural corrosion potential of the stainless steel when being irradiated by visible light, which indicates that the composite film can perform cathodic polarization on the stainless steel under the illumination condition, reduce the corrosion rate of the 304 stainless steel, and have a significant cathodic protection effect.
Example 2
The method for preparing the composite film on the surface of the copper substrate comprises the following steps:
(1) the copper matrix is sequentially mechanically polished by 100-mesh sand paper, 320-mesh sand paper, 800-mesh sand paper and No. 14 metallographic sand paper, then placed in 60 ℃ deoiling liquid to remove oil for 10 min, then sequentially cleaned by deionized water and absolute ethyl alcohol, quickly dried by hot air, and placed in a drying box for 24 h for later use; the formulation of the CoFe mixed solution is 50 mL deionized water with 0.06 g Co (NO) added3)2·6H2O and 0.04 g Fe (NO)3)3·9H2O; stirring for 2 hours at room temperature; adding the prepared CoFe mixed solution into a three-electrode electrolytic cell, taking Ag/AgCl as a reference electrode, taking a polished metal matrix as a working electrode and a platinum net as a counter electrode, and carrying out electrodeposition, wherein the potential of the electrodeposition is controlled at-1.9V, the deposition time is 5 min, and the deposition temperature is 60 ℃. After deposition, the surface of 304 stainless steel was cleaned with deionized water and then dried in an oven at 45 ℃ to obtain a sample designated CoFe-LDH.
(2) Preparing 0.01M Na2WO4The solution was adjusted to pH 11.0 with 1M NaOH and stirred well for use. CoFe-LDH over Na2WO4Soaking in the solution at 20 deg.C for 48 h. And after the exchange is finished, cleaning the sample wafer twice by using deionized water, and blow-drying by using nitrogen for later use to obtain a sample marked as CoFe-W-LDH.
(3) Preparation of 0.01M Zn (NO)3)2And (4) electrodepositing the solution, and uniformly stirring for later use. And (3) taking the sample obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode, and saturated Ag/AgCl as a reference electrode, and carrying out the electrodeposition process in a constant-temperature water bath at 80 ℃. Setting cathode deposition potential-1.5V, and fixing deposition time for 5 min. And after the deposition is finished, cleaning the sample wafer twice by using deionized water, drying the sample wafer in a 45 ℃ oven, and then carrying out heat treatment at 120 ℃ for 24 hours, wherein the sample is marked as CoFe-W-LDH/ZnO.
Example 3
The method for preparing the composite film on the surface of the copper substrate comprises the following steps:
(1) copper matrix is in turnMechanically polishing with 100-mesh, 320-mesh, 800-mesh and 14-mesh metallographic abrasive paper, removing oil in deoiling liquid at 60 ℃ for 10 min, sequentially cleaning with deionized water and absolute ethyl alcohol, rapidly drying with hot air, and standing in a drying box for 24 h; the formulation of the CoFe mixed solution is 100 mL deionized water with 0.38 g Co (NO) added3)2·6H2O and 0.28 g Fe (NO)3)3·9H2O; stirring for 2 hours at room temperature; adding the prepared CoFe mixed solution into a three-electrode electrolytic cell, taking Ag/AgCl as a reference electrode, taking a polished metal matrix as a working electrode and a platinum mesh as a counter electrode, and carrying out electrodeposition, wherein the potential of the electrodeposition is controlled at-1.5V, the deposition time is 2.5 min, and the deposition temperature is 30 ℃. After deposition, the surface of the 304 stainless steel was cleaned with deionized water and then dried in an oven at 45 ℃ and the sample was designated as CoFe-LDH.
(2) Preparation of 1M Na2SiO3The solution was adjusted to pH 14.0 with 1M NaOH and stirred well for use. CoFe-LDH over Na2SiO3Soaking in the solution at 140 deg.C for 0.5 h. After the exchange was completed, the sample wafer was washed twice with deionized water, and dried with nitrogen for use, and the sample was recorded as CoFe-Si-LDH.
(3) Preparation of 0.1M SnCl4The electrodeposition solution is stirred uniformly for standby. And (3) taking the sample obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode, and saturated Ag/AgCl as a reference electrode, and carrying out the electrodeposition process in a constant-temperature water bath at 30 ℃. The cathode deposition potential was set at-1.2V and the deposition time was 150 s. After deposition, the sample wafer is washed twice by deionized water, dried in a 45 ℃ oven and then heat treated at 120 ℃ for 24 hours, and the sample is marked as CoFe-Si-LDH/SnO2。
Example 4
The method for preparing the composite film on the surface of the stainless steel substrate comprises the following steps:
(1) mechanically polishing a 304 stainless steel substrate by using 100-mesh sand paper, 320-mesh sand paper, 800-mesh sand paper and No. 14 metallographic sand paper in sequence, then placing the polished substrate into degreasing liquid at 60 ℃ for 10 min to remove oil, then sequentially cleaning the substrate by using deionized water and absolute ethyl alcohol, quickly drying the substrate by using hot air, and placing the substrate in a drying box for 24 h for later use; the NiFe mixed solution is prepared by adding 3.33 g Ni (NO) into 100 mL deionized water3)2·6H2O and 1.67 g Fe (NO)3)3·9H2O; stirring for 2 hours at room temperature; adding the prepared NiFe mixed solution into a three-electrode electrolytic cell, taking Ag/AgCl as a reference electrode, taking a polished metal matrix as a working electrode and a platinum net as a counter electrode, and carrying out electrodeposition, wherein the potential of the electrodeposition is controlled at-0.7V, the deposition time is 1 min, and the deposition temperature is 40 ℃. After deposition, the surface of the 304 stainless steel is cleaned by deionized water and then dried in an oven at 45 ℃, and the sample is recorded as NiFe-LDH.
(2) Preparing 0.01M Na3PO4The solution was adjusted to pH 9.0 with 1M NaOH and stirred well for use. NiFe-LDH over Na3PO4Soaking in the solution at 60 deg.C for 12 h. After the treatment, the sample wafer was washed twice with deionized water, and dried with nitrogen for use, and the sample was recorded as NiFe-P-LDH.
(3) Preparation of 0.1M TiCl4The electrodeposition solution is stirred uniformly for standby. And (3) taking the sample obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode, and saturated Ag/AgCl as a reference electrode, and carrying out the electrodeposition process in a constant-temperature water bath at 0 ℃. The cathode deposition potential was set at-0.5V and the deposition time was 150 s. After deposition, the sample wafer is washed twice by deionized water, dried in a baking oven at 45 ℃ and then heat-treated at 120 ℃ for 24 hours, and the sample is recorded as NiFe-P-LDH/TiO2。
Example 5
The method for preparing the composite film on the surface of the copper substrate comprises the following steps:
(1) the copper matrix is sequentially mechanically polished by 100-mesh sand paper, 320-mesh sand paper, 800-mesh sand paper and No. 14 metallographic sand paper, then placed in 60 ℃ deoiling liquid to remove oil for 10 min, then sequentially cleaned by deionized water and absolute ethyl alcohol, quickly dried by hot air, and placed in a drying box for 24 h for later use; the preparation scheme of the MgFe mixed solution is that 50 mL of deionized water is added with 0.6 g of Mg (NO)3)2·6H2O and 0.4 g Fe (NO)3)3·9H2O; stirring for 2 hours at room temperature; adding the prepared MgFe mixed solution into a three-electrode electrolytic tank, taking Ag/AgCl as a reference electrode, taking a polished metal matrix as a working electrode and a platinum net as a counter electrode, and carrying out electrodepositionThe deposition time is 2 min and the deposition temperature is 20 ℃ under the control of-1.5V. And cleaning the surface of the 304 stainless steel by using deionized water after deposition, and drying in a 45 ℃ oven to obtain a sample recorded as MgFe-LDH.
(2) Preparing 0.01M Na2WO4The solution was adjusted to pH 11.0 with 1M NaOH and stirred well for use. MgFe-LDH over Na2WO4Soaking in the solution at 20 deg.C for 48 h. And after the exchange is finished, cleaning the sample wafer twice by using deionized water, and blow-drying by using nitrogen for later use to obtain a sample recorded as MgFe-W-LDH.
(3) Preparation of 1M Zn (NO)3)2And (4) electrodepositing the solution, and uniformly stirring for later use. And (3) taking the sample obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode and saturated Ag/AgCl as a reference electrode, and carrying out the electrodeposition process in a constant-temperature water bath at 20 ℃. Setting cathode deposition potential-0.7V, and fixing deposition time for 1 min. And after the deposition is finished, cleaning the sample wafer twice by using deionized water, drying the sample wafer in a 45 ℃ oven, and then carrying out heat treatment at 120 ℃ for 24 hours, wherein the sample is recorded as MgFe-W-LDH/ZnO.
The embodiments in the above description can be further combined or replaced, and the embodiments are only described as preferred examples of the present invention, and do not limit the concept and scope of the present invention, and it is within the protection scope of the present invention that various changes and modifications of the technical solution of the present invention, such as the composite of other materials on the composite film of two layers, can be made by those skilled in the art without departing from the design concept of the present invention. The scope of the invention is given by the appended claims and any equivalents thereof.

Claims (5)

1. A preparation method of a layered double metal hydroxide-based composite film is characterized by comprising the following steps:
(1) deposition of Layered Double Hydroxides (LDH):
polishing, deoiling, cleaning and drying a metal matrix; adding 0.1-5 g of metal M nitrate and metal N nitrate into 50-100 mL of deionized water, and stirring, wherein M and N are different; adding the prepared mixed metal salt solution into a three-electrode electrolytic tank, taking Ag/AgCl as a reference electrode, taking a metal matrix as a working electrode, and taking a platinum mesh as a counter electrode for electrodeposition; after electrodeposition, washing the metal surface by deionized water, and drying;
(2) loading of corrosion inhibitor:
preparing a solution with the corrosion inhibitor concentration of 0.01-1M, adjusting the pH to 9-14 by NaOH or KOH, and uniformly stirring for later use; soaking the sample obtained by deposition in the step (1) in a solution of a corrosion inhibitor, cleaning the surface of the sample by using deionized water after treatment, and drying;
(3) preparing a composite film: preparing an electrodeposition solution with the concentration of 0.01-1M, adding the prepared electrodeposition solution into a three-electrode electrolytic cell, taking Ag/AgCl as a reference electrode, taking the sample treated in the step (2) as a working electrode, taking a platinum net as a counter electrode for electrodeposition, cleaning the metal surface with deionized water after electrodeposition, and drying;
the combination of metals M, N described in step (1) includes: the metal matrix is iron, copper, nickel and alloy of the metals, the electrodeposition is cathodic electrodeposition, the deposition potential is-0.7 to-1.9V, the deposition time is 1 to 5 min, and the deposition temperature is 20 to 60 ℃.
2. The method according to claim 1, wherein the corrosion inhibitor used in step (2) is one or more of tungstate, molybdate, silicate, phosphate, metavanadate and chromate, the treatment time is 0.5-48 h, and the treatment temperature is 20-140 ℃.
3. The method of claim 1, wherein the electrodeposition solution component used in step (3) comprises Zn2+、Ti4+、Sn4+The electrodeposition is cathode electrodeposition, the deposition potential is-0.5 to-1.5V, the deposition time is 1 to 5 min, the deposition temperature is 0 to 80 ℃, and the components of the film obtained by electrodeposition are ZnO and TiO2Or SnO2。
4. A metal substrate having a layered double hydroxide-based composite film obtained by the method of claim 1.
5. Use of the method according to claim 1 for corrosion protection of metal substrates, wherein a composite film of an LDH film with corrosion inhibition and a semiconductor film with photo-generated cathodic protection is prepared on the surface layer of the metal substrate.
CN202110212081.1A 2021-02-25 2021-02-25 Preparation method and application of layered double-metal hydroxide-based composite film Pending CN112981415A (en)

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CN114789000A (en) * 2022-05-25 2022-07-26 南开大学 Modified cation exchange membrane for electrodialysis desalination of high-salt-content glycol solution, modification method, electrodialysis device and desalination method
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CN109411244A (en) * 2018-10-12 2019-03-01 中国矿业大学 A kind of preparation method of titanium dioxide/double-metal hydroxide combination electrode
CN110965074A (en) * 2019-12-16 2020-04-07 陕西易莱德新材料科技有限公司 Method for preparing composite film photoelectrode
CN111235582A (en) * 2020-01-16 2020-06-05 浙江大学 Preparation method and application of photoproduction cathode protection layered double-metal hydroxide film
CN111593353A (en) * 2020-05-29 2020-08-28 深圳大学 Photoelectrochemistry anti-corrosion protection composite photo-anode and preparation method and application thereof

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CN113846364A (en) * 2021-09-04 2021-12-28 桂林理工大学 In-situ grown nickel-cobalt layered double hydroxide material for corrosion prevention of 304 stainless steel
CN113846364B (en) * 2021-09-04 2023-12-19 桂林理工大学 In-situ growth nickel-cobalt layered double hydroxide material for corrosion prevention of 304 stainless steel
CN114789000A (en) * 2022-05-25 2022-07-26 南开大学 Modified cation exchange membrane for electrodialysis desalination of high-salt-content glycol solution, modification method, electrodialysis device and desalination method
CN114789000B (en) * 2022-05-25 2024-01-30 南开大学 Modified cation exchange membrane for electrodialysis desalination of high-salt ethylene glycol solution, modification method, electrodialysis device and desalination method
CN115928123A (en) * 2022-12-09 2023-04-07 东北石油大学 Low overpotential Ni 3 Fe-based LDH (layered double hydroxide) type oxygen evolution electrocatalyst and high-efficiency preparation method and application thereof

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