CN114686893B - Cathode protection Z-type photo-anode material, ion layer deposition preparation method and application - Google Patents
Cathode protection Z-type photo-anode material, ion layer deposition preparation method and application Download PDFInfo
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- CN114686893B CN114686893B CN202210204820.7A CN202210204820A CN114686893B CN 114686893 B CN114686893 B CN 114686893B CN 202210204820 A CN202210204820 A CN 202210204820A CN 114686893 B CN114686893 B CN 114686893B
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- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 36
- 239000011593 sulfur Substances 0.000 claims description 36
- 229910052717 sulfur Inorganic materials 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 35
- 238000002791 soaking Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 150000000703 Cerium Chemical class 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000001621 bismuth Chemical class 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 238000004210 cathodic protection Methods 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 125000002153 sulfur containing inorganic group Chemical group 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 4
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims description 4
- DLNAGPYXDXKSDK-UHFFFAOYSA-K cerium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ce+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O DLNAGPYXDXKSDK-UHFFFAOYSA-K 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
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- RDRWXZDNMNAEAA-UHFFFAOYSA-N 2-sulfonylacetamide Chemical compound NC(=O)C=S(=O)=O RDRWXZDNMNAEAA-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
- C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
-
- 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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
-
- 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
- C23F2201/00—Type of materials to be protected by cathodic protection
- C23F2201/02—Concrete, e.g. reinforced
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The application belongs to the technical field of marine constructional engineering metal corrosion inhibition, and particularly relates to a cathode protection Z-type photo-anode material, an ion layer deposition preparation method and application. The preparation method of the ion layer deposition of the cathode protection Z-type photo-anode material comprises the following steps: (1) pretreatment of conductive glass; (2) Depositing ion layer on the surface of the conductive glass pretreated in the step (1) to obtain Ce 2 S 3 A layer; (3) At Ce 2 S 3 Deposition of ion layer on the surface of the layer to obtain Bi 2 S 3 A layer. The cathode protection Z-type photo-anode material can effectively solve or relieve the problem that the photo-anode material for photo-cathode protection in the prior art has poor anti-corrosion effect on metals used in ocean constructional engineering, can realize high-efficiency photo-cathode protection of ocean engineering structures, and improves the durability of ocean engineering structures.
Description
Technical Field
The application belongs to the technical field of marine constructional engineering metal corrosion inhibition, and particularly relates to a cathode protection Z-type photo-anode material, an ion layer deposition preparation method and application.
Background
The reinforced concrete structure is widely applied to the construction engineering project, and particularly plays a role in building factory buildings and various foundation members. However, due to the self-characteristics of reinforced concrete, the related components are prone to aging over time. The phenomenon not only brings a certain potential safety hazard to engineering projects, but also leads the internal structure to be easily damaged; and a plurality of risks are derived to a certain extent, which is unfavorable for the construction and development of related industries. The aging phenomenon is caused by the corrosion of the steel bars in the concrete. Therefore, how to ensure the corrosion resistance of the reinforced concrete foundation and ensure the basic structure of the reinforced concrete becomes a problem to be solved urgently in the building industry.
The photoelectric cathode protection technology can realize cathode protection by only utilizing solar energy, is a green and environment-friendly cathode protection technology, and is worthy of intensive research and popularization and application. In principle, the protection is provided by photoelectrons generated by a semiconductor photoanode under the excitation of incident light, if the photo-generated electron potential is more negative than the self-corrosion potential of the metal, the photoelectrons can be transferred to the metal which is electrically connected with the photo-generated electron potential, and enrichment is formed on the surface of the metal, so that the cathodic protection of the metal is realized. Thus, the reducibility of photoelectrons is one of the key factors determining the cathodic protection effect.
The photocathode protection photo-anode mostly adopts a heterojunction mode, so that the light utilization efficiency and the separation efficiency of photo-generated charges are improved, however, at present, most of the heterojunction is a type II heterojunction, but the reduction of photo-generated electrons is reduced at the cost of sacrificing the redox of a semiconductor material, and the photo-generated electrons are difficult to transfer to a steel bar to be protected, so that the cathode protection or the protection effect cannot be provided for the steel bar of the ocean building engineering concrete structure.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The application aims to provide a cathode protection Z-type photo-anode material, an ion layer deposition preparation method and application, and the cathode protection Z-type photo-anode material can effectively solve or relieve the problem that the photo-anode material for photo-cathode protection in the prior art has poor anti-corrosion effect on metals used in ocean constructional engineering.
In order to achieve the above object, the present application provides the following technical solutions: the preparation method of the ion layer deposition of the cathode protection Z-type photo-anode material comprises the following steps: (1) pretreatment of conductive glass; (2) Depositing ion layer on the surface of the conductive glass pretreated in the step (1) to obtain Ce 2 S 3 A layer; (3) At Ce 2 S 3 Deposition of ion layer on the surface of the layer to obtain Bi 2 S 3 A layer.
Preferably, the pretreatment of the conductive glass specifically comprises: and sequentially placing the conductive glass in aqueous solution containing a detergent, ethanol solution containing NaOH, ethanol and deionized water for ultrasonic cleaning, and drying after cleaning is finished.
Preferably, step (2) comprises: a. immersing the conductive glass in a solution containing cerium salt; b. immersing the sample obtained after the treatment in the step a in a solution containing a first sulfur source; c. b, after soaking, washing the sample obtained after the treatment of the step b by deionized water; d. drying; e. circularly carrying out the steps a-d; in the step a, the cerium salt is water-soluble cerium salt, and the water-soluble cerium salt is cerium-containing inorganic salt or cerium-containing organic salt; in the step b, the first sulfur source is a water-soluble sulfur-containing organic matter or a water-soluble sulfur-containing inorganic matter.
Preferably, in the step a, the cerium salt is at least one of cerium nitrate, cerium acetate, cerium citrate and cerium acetylacetonate; in the step b, the first sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; the concentration of the cerium salt and the first sulfur source are each independently selected from 1-50mmol/L; the ratio of the concentration of the cerium salt to the concentration of the first sulfur source is 1:1 or 1:3.
Preferably, in step a and step b, the time of soaking is independently selected from 0.5-5min; in the step d, the drying temperature is 60-120 ℃, and the drying time is 1-20min; the number of cycles of steps a-d is 5-30.
Preferably, step (3) comprises: A. immersing the sample obtained by the treatment in the step (2) in a solution containing bismuth salt; B. immersing the sample obtained after the treatment in the step A in a solution containing a second sulfur source; C. after the soaking in the step B is finished, washing the sample treated in the step B with deionized water; D. drying; E. the steps A-D are circularly carried out, namely the Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 A layer to obtain the cathode protection Z-type photo-anode material; in the step A, the bismuth salt is water-soluble bismuth salt, and the water-soluble bismuth salt is inorganic salt containing bismuth or organic salt containing bismuth; in the step B, the second sulfur source is water-soluble sulfur-containing organic matters or water-soluble sulfur-containing inorganic matters.
Preferably, in the step a, the bismuth salt is at least one of bismuth nitrate, bismuth acetate, bismuth citrate and bismuth acetylacetonate; in the step B, the second sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; the concentrations of the bismuth salt and the second sulfur source are each independently selected from 1-50mmol/L; the ratio of the concentrations of bismuth salt and the second sulfur source is 3:7-5:4.
Preferably, in steps a and B, the time of soaking is independently selected from 0.5-5min; in the step D, the drying temperature is 60-120 ℃, and the drying time is 1-20min; the number of steps A-D cycles is 10-30.
The application also provides a cathode protection Z-type photo-anode material, which adopts the following technical scheme: the cathode protection Z-type photo-anode material is prepared by adopting the method.
The application also provides application of the cathode protection Z-type photo-anode material, which adopts the following technical scheme: the application of the cathode protection Z-type photo-anode material in marine construction engineering metal corrosion prevention.
The beneficial effects are that:
the cathode protection Z-type photo-anode material can effectively solve or relieve the problem that the photo-anode material for photo-cathode protection in the prior art has poor anti-corrosion effect on metals used in ocean constructional engineering, can realize high-efficiency photo-cathode protection of ocean engineering structures, and improves the durability of ocean engineering structures.
The cathode protection Z-type photo-anode material (Ce) 2 S 3 -Bi 2 S 3 Cathode protection Z-type photo-anode material) is formed on the surface of conductive glass by an ion layer deposition method, and the heterojunction is in a Z-type electron transmission mode, so that the redox performance of the cathode protection Z-type photo-anode material can be remarkably improved, the separation efficiency of photo-generated charges can be improved, the high-efficiency photo-cathode protection of ocean engineering structure concrete reinforcing steel bars can be realized, and the durability of the ocean engineering concrete structure can be improved.
The cathode protection Z-type photo-anode material (Ce) 2 S 3 -Bi 2 S 3 Cathode protection Z-type photo-anode material) can enable the corrosion potential of the steel bar to be shifted negatively by 0.5V under illumination. Both photoluminescence spectra (PL) and photocurrent-time curves illustrate the cathodic protection Z-type photoanode material (Ce 2 S 3 -Bi 2 S 3 Cathode protection Z-type photoanode material) effectively improves the separation efficiency of photogenerated electron-hole pairs.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
fig. 1 shows a Ce according to an embodiment of the present application 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 An Open Circuit Potential (OCP) profile of the cathodic protection Z-type photoanode material;
fig. 2 shows Ce according to a second embodiment of the present application 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 A Motttky Schottky (MS) curve of the cathodic protection Z-type photoanode material;
FIG. 3 is a schematic view ofCe provided in embodiment III of the application 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 Alternating current impedance (EIS) curve of cathodic protection Z-type photoanode material;
fig. 4 shows Ce according to a fourth embodiment of the present application 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 Photoluminescence (PL) spectra of cathodically protected Z-type photoanode materials.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
The present application will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Aiming at the problem of poor corrosion resistance effect on metal used in ocean constructional engineering of the current photo-anode material for photocathode protection, the application provides an ion layer deposition preparation method of a cathode protection Z-type photo-anode material, which comprises the following steps: comprising the following steps: (1) pretreatment of conductive glass; (2) Depositing ion layer on the surface of the conductive glass pretreated in the step (1) to obtain Ce 2 S 3 A layer; (3) At Ce 2 S 3 Deposition of ion layer on the surface of the layer to obtain Bi 2 S 3 A layer.
Due to Ce 2 S 3 With Bi 2 S 3 With a matched energy band structure, ce 2 S 3 Has a lower conduction band potential (-0.91V vs. NHE), while Bi 2 S 3 Has higher valence band potential (1.38V vs. NHE) and Bi at the same time 2 S 3 Conduction band potential (-0.33V vs. NHE) to Ce 2 S 3 Lower valence band potential (1.19V vs. NHE), bi 2 S 3 The photo-generated electrons on the guide belt can be transferred to Ce 2 S 3 On the valence band of (2) with Ce 2 S 3 The photogenerated holes on the valence band of (2) recombine to form a Z-type electron transport. Under illumination, ce 2 S 3 -Bi 2 S 3 Is at Ce 2 S 3 The conduction band of the steel bar is enriched, has high reduction activity, is easy to transfer to the surface of the steel bar which is electrically connected with the conduction band, and provides cathode protection current for the steel bar. While at the same time, photo-generated holes remain in Bi 2 S 3 The cathode protection device has high oxidation activity on the valence band of the cathode protection device, can oxidize ambient air or water, promotes the whole charge movement loop, and improves the cathode protection effect.
In a preferred embodiment of the application, the pretreatment of the conductive glass is specifically as follows: and sequentially placing the conductive glass in aqueous solution containing a detergent, ethanol solution containing NaOH, ethanol and deionized water for ultrasonic cleaning, and drying after cleaning is finished.
In a preferred embodiment of the present application, step (2) comprises: a. immersing the conductive glass pretreated in the step (1) in a solution containing cerium salt; b. immersing the sample obtained after the treatment in the step a in a solution containing a first sulfur source; c. b, after the soaking is finished, washing the sample obtained by the treatment of the step b by deionized water; d. drying; e. circularly carrying out the steps a-d; in the step a, the cerium salt is water-soluble cerium salt, and the water-soluble cerium salt is cerium-containing inorganic salt or cerium-containing organic salt; in step b, the first sulfur source is a water-soluble sulfur-containing organic or water-soluble sulfur-containing inorganic. Wherein steps a-d are a cycle, and solid Ce can be generated on the surface of the substrate (conductive glass) in the process of performing the steps a-d 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the In the step c, the purpose of the deionized flushing is to flush away the excessive anions and cations adsorbed on the sample obtained after the soaking in the steps a and b; after multiple depositions (steps a-d are circularly carried out), ce can be obtained 2 S 3 A layer.
In a preferred embodiment of the present application, in step a, the cerium salt is at least one of cerium nitrate, cerium acetate, cerium citrate and cerium acetylacetonate; in the step b, the first sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; the concentration of the cerium salt and the first sulfur source are each independently selected from 1-50mmol/L (e.g., 1mmol/L, 5mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, or 50 mmol/L); the ratio of the concentration of the cerium salt to the concentration of the first sulfur source is 1:1 or 1:3.
In a preferred embodiment of the application, in step a and step b, the time of soaking is independently selected from 0.5-5min (e.g., 0.5min, 1.5min, 2.5min, 3.5min, 4.5min or 5 min); in step d, the drying temperature is 60-120deg.C (e.g., 60deg.C, 80deg.C, 100deg.C, or 120deg.C), and the drying time is 1-20min (e.g., 1min, 5min, 10min, 14min, 18min, or 20 min); the number of steps a-d cycles is 5-30 (e.g., 5, 10, 20, or 30).
In a preferred embodiment of the present application, step (3) comprises: A. immersing the sample obtained by the treatment in the step (2) in a solution containing bismuth salt; B. immersing the sample obtained after the treatment in the step A in a solution containing a second sulfur source; C. after the soaking in the step B is finished, washing the sample treated in the step B with deionized water; D. drying; E. the steps A-D are circularly carried out, namely the Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 A layer to obtain a cathode protection Z-type photo-anode material; in the step A, the bismuth salt is water-soluble bismuth salt, and the water-soluble bismuth salt is inorganic salt containing bismuth or organic salt containing bismuth; in step B, the second sulfur source is a water-soluble sulfur-containing organic or water-soluble sulfur-containing inorganic. Similarly, steps A-D are a cycle, and during the process of steps A-D, bi in solid form can be generated by reacting the surface of the substrate (the sample obtained after the treatment of step (1)) 2 S 3 The method comprises the steps of carrying out a first treatment on the surface of the In the step C, the purpose of the deionized flushing is to flush away the excessive anions and cations adsorbed on the sample obtained after the soaking in the steps A and B; through multiple deposition (steps A-D are circularly carried out), bi can be obtained 2 S 3 A layer.
In the preferred embodiment of the present application, in the step a, the bismuth salt is at least one of bismuth nitrate, bismuth acetate, bismuth citrate and bismuth acetylacetonate; in the step B, the second sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; the concentrations of bismuth salt and the second sulfur source are each independently selected from 1-50mmol/L (e.g., 1mmol/L, 5mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, or 50 mmol/L); the ratio of the concentrations of bismuth salt and the second sulfur source is 3:7-5:4.
In a preferred embodiment of the application, in steps A and B, the time of soaking is independently selected from 0.5-5min (e.g., 0.5min, 1.5min, 2.5min, 3.5min, 4.5min, or 5 min); step D, drying at 60-120deg.C (60 deg.C, 80 deg.C, 100 deg.C or 120deg.C) for 1-20min (1 min, 5min, 10min, 14min, 18min or 20min, for example); the number of steps a-D cycles is 10-30 (e.g., 10, 20, or 30).
The application also provides a cathode protection Z-type photo-anode material, which is prepared by adopting the method.
The application also provides application of the cathode protection Z-type photo-anode material in marine construction engineering metal corrosion prevention.
The cathode-protecting Z-type photo-anode material, the ion layer deposition preparation method and the application of the application are described in detail by specific examples.
Example 1
1. The cathode protection Z-type photo-anode material of the embodiment is prepared by the method comprising the following steps:
(1) Pretreatment of conductive glass: the conductive glass is thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. The method comprises the following specific steps: firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 10min, and is dried at 60 ℃ for standby after being washed clean by the deionized water.
(2) Depositing Ce on the surface of the conductive glass obtained by the treatment in the step (1) 2 S 3 Layer (ion layer deposition preparation of Ce) 2 S 3 ): a. immersing the conductive glass obtained in the step (1) serving as a substrate in a solution containing cerium nitrate (with the concentration of 50 mmol/L) for 30s; b. will be treated by step aThe obtained sample is soaked in a solution containing sodium sulfide (the concentration is 50 mmol/L) for 30s; c. after the soaking in the step b is finished, washing the film sample substrate (the sample obtained after the treatment in the step b) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; d. c, drying the sample obtained after the treatment in the step c at the temperature of 60 ℃ for 20min, and cooling to room temperature; e. repeating steps a-d in sequence (i.e., cycling through steps a-d); one alternate soaking (a-d) is regarded as one deposition period (one cycle), and the deposition (cycle) is carried out for 30 times to obtain Ce 2 S 3 A layer.
(3) At Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 Layer (c): A. immersing the sample obtained by the treatment in the step (2) serving as a substrate in a solution containing bismuth nitrate (with the concentration of 1 mmol/L) for 5min; B. immersing the sample obtained by the treatment in the step A in a solution containing sodium sulfide (with the concentration of 1 mmol/L) for 5min; C. after the soaking in the step B is finished, washing the film sample substrate (the sample obtained after the treatment in the step B) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying the sample obtained after the treatment in the step C at the temperature of 60 ℃ for 20min, and cooling to room temperature; E. sequentially repeating steps A-D (i.e., cyclically performing steps A-D); one alternate soaking (A-D) is regarded as a deposition period (one cycle), and after 30 times of deposition (cycle), the cathode protection Z-type photo-anode material (Ce) of the embodiment is obtained 2 S 3 -Bi 2 S 3 Cathode protection Z-type photo anode material).
2、Ce 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (3) is omitted, and the rest are kept consistent.
3、Bi 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (2) is omitted, and the rest are kept consistent.
4. Under intermittent sunlight irradiation, the potential change of the prepared photo-anode material and the reinforcing steel bar of the concrete structure of the ocean constructional engineering after coupling is tested, so that the photo-cathode protection performance of different photo-anode materials on the reinforcing steel bar is judged. The test results are shown in FIG. 1.
As can be seen from FIG. 1, ce is coupled 2 S 3 Photoanode material or Bi 2 S 3 When the photo-anode material is used, the corrosion potential of the steel bar is negatively shifted from-0.5V in a dark state to about-0.7V in illumination; coupling Ce 2 S 3 -Bi 2 S 3 When the Z-type photo-anode material is protected by the cathode, the corrosion potential of the steel bar is negatively shifted from minus 0.5V to minus 0.95V under illumination, and the corrosion potential of the steel bar is negatively shifted by 450 mV, which indicates Ce under illumination 2 S 3 -Bi 2 S 3 Can provide better cathodic protection effect for steel bars (carbon steel).
Example two
1. The cathode protection Z-type photo-anode material of the embodiment is prepared by the method comprising the following steps:
(1) Pretreatment of conductive glass: the conductive glass is thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. The method comprises the following specific steps: firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 30min, and is dried at 60 ℃ for standby after being washed clean by the deionized water.
(2) Depositing Ce on the surface of the conductive glass obtained by the treatment in the step (1) 2 S 3 Layer (ion layer deposition preparation of Ce) 2 S 3 ): a. soaking the conductive glass obtained in the step (1) serving as a substrate in a solution containing cerium citrate (with the concentration of 1 mmol/L) for 3min; b. immersing the sample obtained after the treatment in the step a in a solution containing sulfurylacetamide (with the concentration of 1 mmol/L) for 3min; c. after the soaking is finished, washing the film sample substrate (the sample obtained after the treatment of the step b) by a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; d. drying at 120deg.C for 1min, and cooling to room temperature; e. repeating steps a-d in sequence (i.e., cycling through steps a-d); one alternate soaking (a-d) is regarded as one deposition period (one cycle), and the deposition (cycle) is carried out for 5 times to obtain Ce 2 S 3 A layer.
(3) At Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 Layer (c): A. immersing the sample obtained by the treatment in the step (2) serving as a substrate in a solution containing bismuth acetate (the concentration is 50 mmol/L) for 30s; B. immersing the sample obtained by the treatment in the step A in a solution containing thiourea (the concentration is 50 mmol/L) for 30s; C. after the soaking in the step B is finished, washing the film sample substrate (the sample obtained after the treatment in the step B) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying the sample obtained after the treatment in the step C at 120 ℃ for 1min, and cooling to room temperature; E. sequentially repeating steps A-D (i.e., cyclically performing steps A-D); one alternate soaking (A-D) is regarded as a deposition period (one cycle), and after 10 times of deposition (cycle), the cathode protection Z-type photo-anode material (Ce) of the embodiment is obtained 2 S 3 -Bi 2 S 3 Cathode protection Z-type photo anode material).
2、Ce 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (3) is omitted, and the rest are kept consistent.
3、Bi 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (2) is omitted, and the rest are kept consistent.
4. For the obtained Ce 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 The flat-band potential of the cathode-protected Z-type photoanode material was tested and the Mo Texiao tex results are shown in fig. 2.
As can be seen from fig. 2: ce (Ce) 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 The slope of the motttky curves of the cathodic protection Z-type photoanode materials are all positive values, indicating that they are all n-type semiconductors. At the same time Ce 2 S 3 -Bi 2 S 3 Flat band potential of cathode protection Z-type photo-anode materialAt-0.45 Vvs. SCE, ce 2 S 3 Photoanode material and Bi 2 S 3 The flat band potentials of the photoanode materials are respectively at-0.3 Vvs. SCE and-0.1 Vvs. SCE, which indicates Ce 2 S 3 -Bi 2 S 3 The cathode protection Z-shaped photo-anode material keeps lower conduction band potential, so that the heterojunction is Z-shaped heterojunction in the application. The flat potential is far lower than the self-corrosion potential of the steel bars, so that cathode protection can be provided for the steel bars in the concrete structure of the ocean constructional engineering under illumination.
Example III
1. The cathode protection Z-type photo-anode material of the embodiment is prepared by the method comprising the following steps:
(1) Pretreatment of conductive glass: the conductive glass is thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. The method comprises the following specific steps: firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 15min, and is dried at 60 ℃ for standby after being washed clean by the deionized water.
(2) Depositing Ce on the surface of the conductive glass obtained by the treatment in the step (1) 2 S 3 Layer (ion layer deposition preparation of Ce) 2 S 3 ): a. immersing the conductive glass obtained in the step (1) serving as a substrate in a solution containing cerium acetylacetonate (with the concentration of 20 mmol/L) for 5min; b. immersing the sample obtained after the treatment in the step a in a solution containing ammonium sulfite (with the concentration of 20 mmol/L) for 5min; c. after the soaking in the step b is finished, washing the film sample substrate (the sample obtained after the treatment in the step b) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; d. c, drying the sample obtained after the treatment in the step c at the temperature of 100 ℃ for 10min, and cooling to room temperature; e. repeating steps a-d in sequence (i.e., cycling through steps a-d); one alternate soaking (a-d) is regarded as a deposition period (one cycle), and the deposition (cycle) is carried out for 10 times to obtain Ce 2 S 3 A layer.
(3) At Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 Layer (c): A. soaking the sample obtained by the treatment in the step (2) serving as a substrate in a solution containingBismuth citrate (25 mmol/L) for 2min; B. soaking the sample obtained by the treatment in the step A in a solution containing thiourea (the concentration is 20 mmol/L) for 2min; C. after the soaking in the step B is finished, washing the film sample substrate (the sample obtained after the treatment in the step B) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying the sample obtained after the treatment in the step C at 80 ℃ for 20min, and cooling to room temperature; E. sequentially repeating steps A-D (i.e., cyclically performing steps A-D); one alternate soaking (A-D) is regarded as a deposition period (one cycle), and after 15 times of deposition (cycle), the cathode protection Z-type photo-anode material (Ce) of the embodiment is obtained 2 S 3 -Bi 2 S 3 Cathode protection Z-type photo anode material).
2、Ce 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (3) is omitted, and the rest are kept consistent.
3、Bi 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (2) is omitted, and the rest are kept consistent.
4. For Ce obtained in this example 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 The cathodic protection Z-type photoanode material was subjected to an alternating current impedance test (EIS) with the test results shown in FIG. 3.
As can be seen from fig. 3, ce 2 S 3 -Bi 2 S 3 The alternating current impedance value of the cathode protection Z-type photo-anode material is far lower than that of single Ce 2 S 3 And Bi (Bi) 2 S 3 Description of Ce 2 S 3 With Bi 2 S 3 Is matched with the energy band structure of Bi 2 S 3 The photo-generated electrons on the guide belt can be transferred to Ce 2 S 3 On and react with the valence band of (2) to leave photo-generated electron holes at Ce 2 S 3 Conduction band and Bi of (2) 2 S 3 And the valence band of the electron-hole photo-generated is efficiently separated.
Example IV
1. The cathode protection Z-type photo-anode material of the embodiment is prepared by the method comprising the following steps:
(1) Pretreatment of conductive glass: the conductive glass is thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. The method comprises the following specific steps: firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 20min, and is dried at 60 ℃ for standby after being washed clean by the deionized water.
(2) Depositing Ce on the surface of the conductive glass obtained by the treatment in the step (1) 2 S 3 Layer (ion layer deposition preparation of Ce) 2 S 3 ): a. immersing the conductive glass obtained in the step (1) serving as a substrate in a solution containing cerium acetate (with the concentration of 10 mmol/L) for 2.5min; b. immersing the sample obtained after the treatment in the step a in a solution containing potassium sulfide (the concentration is 30 mmol/L) for 2.5min; c. after the soaking in the step b is finished, washing the film sample substrate (the sample obtained after the treatment in the step b) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; d. c, drying the sample obtained after the treatment in the step c at the temperature of 100 ℃ for 10min, and cooling to room temperature; e. repeating steps a-d in sequence (i.e., cycling through steps a-d); one alternate soaking (a-d) is regarded as a deposition period (one cycle), and the deposition (cycle) is carried out for 20 times to obtain Ce 2 S 3 A layer.
(3) At Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 Layer (c): A. immersing the sample obtained by the treatment in the step (2) serving as a substrate in a solution containing bismuth acetylacetonate (the concentration is 15 mmol/L) for 3.5min; B. immersing the sample obtained by the treatment in the step A in a solution containing thioacetamide (the concentration is 35 mmol/L) for 3.5min; C. after the soaking in the step B is finished, washing the film sample substrate (the sample obtained after the treatment in the step B) with a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying the sample obtained after the treatment in the step C at the temperature of 100 ℃ for 10min, and cooling to room temperature; E. sequentially repeating the stepsSteps a-D (i.e., cycling through steps a-D); one alternate soaking (A-D) is regarded as a deposition period (one cycle), and after deposition (cycle) is carried out for 25 times, the cathode protection Z-type photo-anode material (Ce) of the embodiment is obtained 2 S 3 -Bi 2 S 3 Cathode protection Z-type photo anode material).
2、Ce 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (3) is omitted, and the rest are kept consistent.
3、Bi 2 S 3 Preparation of photo-anode material: with Ce as described above 2 S 3 -Bi 2 S 3 The preparation method of the cathode protection Z-type photo-anode material is only different in that the step (2) is omitted, and the rest are kept consistent.
4. For Ce obtained in this example 2 S 3 Photoanode material, bi 2 S 3 Photoanode material and Ce 2 S 3 -Bi 2 S 3 Cathode-protected Z-type photoanode materials were tested for their photoluminescence spectra (PL) and the test results are shown in figure 4.
As can be seen from fig. 4, ce 2 S 3 -Bi 2 S 3 The strength of the cathode protection Z-type photo-anode material is far lower than that of Ce alone 2 S 3 And Bi (Bi) 2 S 3 Description of Ce 2 S 3 With Bi 2 S 3 Is matched with the energy band structure of Bi 2 S 3 The photo-generated electrons on the guide belt can be transferred to Ce 2 S 3 On and react with the valence band of (2) to leave photo-generated electron holes at Ce 2 S 3 Conduction band and Bi of (2) 2 S 3 And the valence band of the electron-hole photo-generated is efficiently separated.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. The preparation method of the cathode protection Z-type photo-anode material by ion layer deposition is characterized by comprising the following steps: (1) pretreatment of conductive glass; (2) Depositing ion layer on the surface of the conductive glass pretreated in the step (1) to obtain Ce 2 S 3 A layer; (3) At Ce 2 S 3 Deposition of ion layer on the surface of the layer to obtain Bi 2 S 3 A layer;
the step (2) comprises: a. immersing the conductive glass pretreated in the step (1) in a solution containing cerium salt; b. immersing the sample obtained after the treatment in the step a in a solution containing a first sulfur source; c. b, after soaking, washing the sample obtained after the treatment of the step b by deionized water; d. drying; e. circularly carrying out the steps a-d;
the concentration of the cerium salt and the first sulfur source are each independently selected from 1-50mmol/L, the ratio of the concentration of the cerium salt and the first sulfur source is 1:1 or 1:3;
in the step a, the cerium salt is water-soluble cerium salt, and the water-soluble cerium salt is cerium-containing inorganic salt or cerium-containing organic salt; in the step b, the first sulfur source is a water-soluble sulfur-containing organic matter or a water-soluble sulfur-containing inorganic matter; in step a and step b, the soaking time is independently selected from 0.5-5min; in the step d, the drying temperature is 60-120 ℃, and the drying time is 1-20min; the number of the steps a-d is 5-30 times;
the step (3) comprises: A. immersing the sample obtained by the treatment in the step (2) in a solution containing bismuth salt; B. immersing the sample obtained after the treatment in the step A in a solution containing a second sulfur source; C. after the soaking in the step B is finished, washing the sample treated in the step B with deionized water; D. drying; E. the steps A-D are circularly carried out, namely the Ce 2 S 3 Deposition of Bi on the surface of the layer 2 S 3 A layer to obtain the cathode protection Z-type photo-anode material;
in the step A, the bismuth salt is water-soluble bismuth salt, and the water-soluble bismuth salt is inorganic salt containing bismuth or organic salt containing bismuth; in the step B, the second sulfur source is a water-soluble sulfur-containing organic matter or a water-soluble sulfur-containing inorganic matter;
the concentrations of the bismuth salt and the second sulfur source are each independently selected from 1-50mmol/L; the ratio of the concentrations of the bismuth salt and the second sulfur source is 3:7-5:4;
in the steps A and B, the soaking time is independently selected from 0.5-5min; in the step D, the drying temperature is 60-120 ℃, and the drying time is 1-20min; the number of steps A-D cycles is 10-30.
2. The method for preparing the cathode-protection Z-type photoanode material by ion layer deposition according to claim 1, wherein the conductive glass pretreatment is specifically as follows: and sequentially placing the conductive glass in aqueous solution containing a detergent, ethanol solution containing NaOH, ethanol and deionized water for ultrasonic cleaning, and drying after cleaning is finished.
3. The method for preparing the cathode-protected Z-type photoanode material by ion layer deposition according to claim 1, wherein in the step a, the cerium salt is at least one of cerium nitrate, cerium acetate, cerium citrate and cerium acetylacetonate; in the step b, the first sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite.
4. The method for preparing the cathode-protection Z-type photoanode material by ion layer deposition according to claim 1, wherein in the step A, the bismuth salt is at least one of bismuth nitrate, bismuth acetate, bismuth citrate and bismuth acetylacetonate;
in the step B, the second sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite.
5. A cathodically protected Z-type photoanode material, prepared by the method according to any one of claims 1 to 4.
6. The use of the cathodic protection Z-type photoanode material according to claim 5 for corrosion protection of marine construction metals.
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| CN112779542A (en) * | 2020-12-24 | 2021-05-11 | 中国科学院海洋研究所 | Photoanode composite membrane material and application thereof |
| CN114059071A (en) * | 2022-01-18 | 2022-02-18 | 青岛理工大学 | Photo-anode film for reinforcing steel bar photo-cathode protection and preparation method and application thereof |
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| CN112779542A (en) * | 2020-12-24 | 2021-05-11 | 中国科学院海洋研究所 | Photoanode composite membrane material and application thereof |
| CN114059071A (en) * | 2022-01-18 | 2022-02-18 | 青岛理工大学 | Photo-anode film for reinforcing steel bar photo-cathode protection and preparation method and application thereof |
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