CN114085043B - Composite film for photoelectric cathode protection and preparation method and application thereof - Google Patents

Composite film for photoelectric cathode protection and preparation method and application thereof Download PDF

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CN114085043B
CN114085043B CN202210054912.1A CN202210054912A CN114085043B CN 114085043 B CN114085043 B CN 114085043B CN 202210054912 A CN202210054912 A CN 202210054912A CN 114085043 B CN114085043 B CN 114085043B
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conductive glass
composite film
protection
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CN114085043A (en
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金祖权
张小影
蒋继宏
王晓晴
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Qingdao University of Technology
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    • 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
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    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • 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
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/216—ZnO
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
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    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • 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
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/31—Pre-treatment
    • 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
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    • C23F2201/00—Type of materials to be protected by cathodic protection
    • C23F2201/02—Concrete, e.g. reinforced
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the technical field of corrosion prevention of concrete structure reinforcing steel bars of ocean engineering buildings, and particularly relates to a composite film for photoelectric cathode protection, and a preparation method and application thereof. The preparation method of the composite film for the photocathode protection comprises the following steps of (1) cleaning and acid treatment are carried out on conductive glass; (2) depositing ZnO nanowires on the surface of the conductive glass obtained by the treatment in the step (1) by an electrodeposition method; (3) depositing CuIn on the surface of the ZnO nanowire by a hydrothermal method5S8And obtaining the composite film for the protection of the photocathode. The composite film for the photoelectric cathode protection can be used for the high-efficiency photoelectric cathode protection of the concrete structural steel bar of the ocean engineering building, and the service life of the ocean engineering structure is prolonged.

Description

Composite film for photoelectric cathode protection and preparation method and application thereof
Technical Field
The invention belongs to the technical field of corrosion prevention of concrete structure reinforcing steel bars of ocean engineering buildings, and particularly relates to a composite film for photoelectric cathode protection and a preparation method and application thereof.
Background
The reinforced concrete is the most widely applied building and foundation engineering material all over the world at present, and plays a significant role in national economic construction and development. In recent years, with the rapid development of economic society of China and the continuous widening of engineering application fields, the reinforced concrete foundation engineering is continuously extended to severe environments such as ocean, deep sea, high saline soil, extreme severe cold and the like, and the structural corrosion and protection face unprecedented challenges.
At present, there are many corrosion protection measures, and among them, cathodic protection technology is one of the economic and effective protection measures in the concrete structure of ocean engineering construction. The conventional cathodic protection is divided into sacrificial anodic cathodic protection and impressed current cathodic protection, and has problems such as: loss of sacrificial anode, energy consumption, environmental pollution, etc. Therefore, development of new cathodic protection techniques is urgently needed.
The photoelectric cathode protection is carried out at present, and has a good effect in the field of metal protection. However, most of the semiconductor materials adopted by the current photocathode for protecting the photoanode are TiO2And ZnO, which are ultraviolet responsive and do not match well with the solar spectrum, and thus do not make efficient use of solar energy.More importantly, the potential of the conduction band of the metal is higher than or slightly lower than the self-corrosion potential of the steel bar, and photo-generated electrons cannot be transferred to the protected steel bar rapidly or cannot be transferred to the protected steel bar at all (the self-corrosion potential is lower, and the metal which is more prone to corrosion, such as Q235), so that the photoelectrochemical cathode protection effect is not ideal.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a composite film for photoelectric cathode protection and a preparation method and application thereof5S8Introduction of material, and preparation of ZnO-CuIn for photoelectric cathode protection5S8The composite film can obviously expand the light absorption and utilization efficiency and improve the separation efficiency of photo-generated charges.
In order to achieve the above purpose, the invention provides the following technical scheme: ZnO-CuIn for photocathode protection5S8The preparation method of the composite film comprises (1) cleaning and acid treating conductive glass; (2) depositing ZnO nanowires on the surface of the conductive glass obtained by the treatment in the step (1) by an electrodeposition method; (3) depositing CuIn on the surface of the ZnO nanowire by a hydrothermal method5S8Obtaining the ZnO-CuIn5S8The composite film is the composite film for protecting the photocathode.
Preferably, the cleaning comprises the steps of sequentially placing the conductive glass in a first solution, a second solution, a third solution and a fourth solution to perform ultrasonic cleaning on the conductive glass, wherein the first solution is an aqueous solution containing a detergent, the second solution is an ethanol solution of NaOH, the third solution is ethanol or acetone, and the fourth solution is deionized water; the time of ultrasonic cleaning for each time is 10-30 min.
Preferably, the acid treatment is specifically: soaking the cleaned conductive glass in the fourth solution by using an acid solution, washing the acid-treated conductive glass by using deionized water after the acid treatment, and drying the washed conductive glass after the washing is finished; the acid solution is hydrochloric acid solution, the pH of the hydrochloric acid solution is = 1-6, the soaking time is 2-3 min, and the drying temperature is 60-100 ℃.
Preferably, the conductive glass is FTO conductive glass or ITO conductive glass.
Preferably, the step (2) is specifically: and (2) adding an electrochemical deposition solution containing zinc salt, electrolyte salt and strong acid into an electrolytic cell, adopting a three-electrode system, taking the electrode obtained in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing at the temperature of 20-90 ℃ by a potentiostatic method to obtain the ZnO nanowire.
Preferably, the concentration of the zinc salt is 0.5mol L-1Or 1mol L-1The strong acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, the pH of the electrochemical deposition solution is = 1-4.5, the potential during potentiostatic deposition is-0.5-1.8V, and the deposition time is 10h or 24 h.
Preferably, the zinc salt is an inorganic or organic salt containing zinc.
Preferably, the zinc salt is at least one of zinc nitrate, zinc sulfate, zinc chloride, zinc acetate and zinc acetylacetonate.
Preferably, the electrolyte salt is at least one of potassium chloride, potassium sulfate, lithium perchlorate, sodium chloride, and sodium sulfate.
Preferably, step (3) is specifically: placing the conductive glass with the ZnO nanowires deposited on the surface, which is obtained by the treatment in the step (2), in a reaction container containing a mixed solution of a copper source, an indium source and a sulfur source, enabling the conductive surface of the conductive glass with the ZnO nanowires deposited on the surface to face downwards, carrying out hydrothermal reaction for 8-18 h at the temperature of 120-180 ℃, and after the hydrothermal reaction is finished, cleaning and drying to obtain the ZnO-CuIn for photocathode protection5S8A composite membrane.
Preferably, the copper source is an inorganic or organic salt of copper and the indium source is an inorganic or organic salt of indium.
Preferably, the copper source is selected from the group consisting of copper nitrate, copper sulfate, copper chloride, copper acetate and copper acetylacetonateThe concentration of the copper source is 100mmol L-1~500mmolL-1(ii) a The indium source is at least one of indium nitrate, indium sulfate, indium chloride and indium acetate, and the concentration of the indium source is 100mmol L-1~600mmolL-1(ii) a The sulfur source is at least one of thiourea, thioacetamide and sodium sulfite, and the concentration of the sulfur source is 1mol L-1(ii) a The concentration ratio of the copper source to the indium source is 1: 5-5: 1.
The invention also provides a composite film for photocathode protection, which adopts the following technical scheme: the composite film for the photocathode protection is prepared by the preparation method.
The invention also provides an application of the composite film for photocathode protection, which adopts the following technical scheme: the composite film for photocathode protection is applied to the corrosion prevention of the concrete structure steel bar of the ocean engineering building.
Has the advantages that: the composite film for the photocathode protection is prepared by carrying out heterojunction construction and CuIn on the surface of conductive glass5S8The material is obtained by introduction and preparation, so that the light absorption and utilization efficiency can be obviously expanded, and the separation efficiency of photo-generated charges can be improved; CuIn5S8The forbidden band width of the light absorption material is about 1.26eV, and the light absorption material can absorb all visible light and obviously expand the light absorption range. Further, CuIn5S8The position of the conduction band valence band is matched with that of ZnO, so that a Z-shaped electron transmission path is constructed, the separation efficiency of photo-generated charges is improved, a lower conduction band potential is reserved, and photo-generated electrons are conveniently transferred from the photo-anode to the surface of the steel bar. The ZnO-CuIn for the protection of photocathode of the invention5S8The composite membrane is used as a cathode protection photoanode of a concrete structure of the ocean engineering building, can realize high-efficiency photocathode protection of a steel bar of the concrete structure of the ocean engineering building, and prolongs the service life of the ocean engineering building.
The ZnO-CuIn for the protection of photocathode of the invention5S8The composite film can realize the absorption and utilization of visible light, and the edge of a light absorption band is red-shifted to about 880 nm.
Under illumination, the ZnO-CuIn for the photocathode protection of the invention5S8The composite film can make the corrosion potential of the steel bar negatively shift more than 500 millivolts.
In addition, photoluminescence spectra (PL) and current-time (J-t) curves both indicate that the composite film effectively improves the separation efficiency of photo-generated electron-hole pairs.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 shows a ZnO film for photocathode protection and a CuIn film for photocathode protection under intermittent light irradiation provided in example 1 of the present invention5S8Film and ZnO-CuIn for photocathode protection5S8Current-time (J-t) plot for composite membranes;
FIG. 2 shows a ZnO film for photocathode protection and a ZnO-CuIn film for photocathode protection, which are provided in example 2 of the present invention5S8A photo-responsive performance map of the composite film;
FIG. 3 shows a ZnO film for photocathode protection and a CuIn for photocathode protection according to embodiment 3 of the present invention5S8Film and ZnO-CuIn for photocathode protection5S8Photoluminescence (PL) spectrum of the composite film;
FIG. 4 is a diagram of a potentiodynamic polarization curve testing apparatus provided in example 4 of the present invention;
FIG. 5 shows a ZnO film for photocathode protection and a CuIn for photocathode protection according to embodiment 4 of the present invention5S8Film and ZnO-CuIn for photocathode protection5S8The composite film is coupled with a potentiodynamic polarization curve diagram of Q235 carbon steel under illumination or dark state.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a preparation method of a composite film for photocathode protection, aiming at the problem that the photoelectrochemistry cathode protection effect of a semiconductor material adopted by a photocathode protection photoanode at present is not ideal, and the preparation method comprises the following steps:
(1) cleaning and acid treatment are carried out on the conductive glass; (2) depositing ZnO nanowires on the surface of the conductive glass obtained by the treatment in the step (1) by an electrodeposition method; (3) depositing CuIn on the surface of the ZnO nanowire by a hydrothermal method5S8Obtaining the ZnO-CuIn5S8The composite film is the composite film for protecting the photocathode.
In a preferred embodiment of the present invention, the cleaning includes sequentially placing the conductive glass in a first solution, a second solution, a third solution and a fourth solution to perform ultrasonic cleaning on the conductive glass, where the first solution is an aqueous solution containing a detergent, the second solution is an ethanol solution of NaOH, the third solution is ethanol or acetone, and the fourth solution is deionized water; the time of each ultrasonic cleaning is 10-30 min (for example, 10min, 15min, 20min, 25min or 30 min). By cleaning the conductive glass, the adhesive force between the film and the glass can be improved.
In the preferred embodiment of the invention, the detergent is washing powder, soap, washing liquid, and the like.
In a preferred embodiment of the present invention, the acid treatment specifically comprises: soaking the cleaned conductive glass in the fourth solution by using an acid solution, washing the acid-treated conductive glass by using deionized water after the acid treatment, and drying the washed conductive glass after the washing is finished; the acid solution is a hydrochloric acid solution having a pH = 1-6 (e.g., pH =1, pH =2, pH = 3)pH =4, pH =5, or pH = 6) for 2 to 3min, and the temperature of the drying is 60 to 100 ℃ (for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or 100 ℃). The acid treatment can make the surface of the conductive glass adsorb a large amount of H+。
In a preferred embodiment of the present invention, the step (2) is specifically: and (2) adding an electrochemical deposition solution containing zinc salt, electrolyte salt and strong acid into an electrolytic cell, adopting a three-electrode system, taking the electrode obtained in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing at the temperature of 20-90 ℃ by a potentiostatic method to obtain the ZnO nanowire.
In a preferred embodiment of the invention, the concentration of the zinc salt is 0.5mol L-1Or 1mol L-1The strong acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, the electrochemical deposition solution has a pH = 1-4.5 (e.g., pH =1, pH =1.5, pH =2.5, pH =3.5 or pH = 4.5), the potentiostatic deposition has a potential of-0.5 to-1.8V (e.g., -0.5V, -1V, -1.5V or-1.8V), and the deposition time is 10h or 24 h; the zinc salt is an inorganic salt or an organic salt containing zinc.
In a preferred embodiment of the present invention, the zinc salt is an inorganic salt or an organic salt containing zinc.
In a preferred embodiment of the present invention, the zinc salt is at least one of zinc nitrate, zinc sulfate, zinc chloride, zinc acetate and zinc acetylacetonate.
In a preferred embodiment of the present invention, the electrolyte salt is at least one of potassium chloride, potassium sulfate, lithium perchlorate, sodium chloride, and sodium sulfate.
In a preferred embodiment of the present invention, the step (3) specifically comprises: placing the conductive glass with the ZnO nanowires deposited on the surface, which is obtained by the treatment of the step (2), in a reaction container containing a mixed solution of a copper source, an indium source and a sulfur source, enabling the conductive surface of the conductive glass with the ZnO nanowires deposited on the surface to face downwards, carrying out hydrothermal reaction at the temperature of 120-180 ℃ (such as 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃) for 8-18 h (such as 9h, 11h, 13h, 15h, 17h or 18 h), and after the hydrothermal reaction is finished, cleaning and drying to obtain the ZnO nanowires for photoelectric cathode protection-CuIn5S8A composite membrane.
In a preferred embodiment of the present invention, the copper source is an inorganic salt or an organic salt of copper, and the indium source is an inorganic salt or an organic salt of indium.
In a preferred embodiment of the present invention, the copper source is at least one of copper nitrate, copper sulfate, copper chloride, copper acetate and copper acetylacetonate.
Preferably, the concentration of the copper source is 100mmolL-1~500mmolL-1(e.g., 100mmol L-1、200mmolL-1、300mmolL-1、400mmolL-1Or 500 mmoleL-1）。
In a preferred embodiment of the present invention, the indium source is at least one of indium nitrate, indium sulfate, indium chloride and indium acetate.
Preferably, the concentration of the indium source is 100mmolL-1~600mmolL-1(e.g., 100mmol L)-1、200mmolL-1、300mmolL-1、400mmolL-1、500mmolL-1Or 600 mmoleL-1）。
In a preferred embodiment of the present invention, the sulfur source is at least one of thiourea, thioacetamide and sodium sulfite. Preferably, the concentration of the sulfur source is 1mol L-1The concentration ratio of the copper source to the indium source is 1: 5-5: 1 (for example, 1:5, 3:5, 5:3, or 5: 1).
The invention also provides a composite film for photocathode protection, which is prepared by the preparation method.
The invention also provides application of the composite film for photocathode protection, and the application of the composite film for photocathode protection in the reinforcement corrosion prevention of the concrete structure of the ocean engineering building.
The composite film for photocathode protection of the present invention, and the preparation method and application thereof are described in detail below by way of specific examples.
Example 1
1. ZnO-CuIn for photocathode protection of the present example5S8A method of making a composite membrane comprising the steps of:
(1) before a hydrothermal reaction experiment, the film needs to be thoroughly cleaned, and in order to improve the adhesive force between the film and the glass, the ITO conductive glass is sequentially placed into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, acetone and deionized water, and is cleaned by ultrasonic cleaning for 10 min. Then soaking the substrate in dilute hydrochloric acid with the pH =1 for 2-3 min to enable the surface of the substrate to adsorb a large amount of H+And washing with deionized water, and drying at 60 ℃ for later use.
(2) Adding 500mmol L of sodium hydroxide into an electrolytic cell-1And (3) adjusting the pH =1 with sulfuric acid to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the ITO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 10 hours at the temperature of 90 ℃ and under the potential of-0.5V by a potentiostatic method to obtain the ZnO nanowire.
(3) Using 100mmol L-1500mmol L of copper nitrate-1And 1mol of indium nitrate-1Putting the ITO conductive glass with the ZnO nanowires deposited on the surface of the ITO conductive glass into a thiourea mixed solution, controlling the temperature of hydrothermal reaction at 180 ℃ and the reaction time to be 8h, removing the solution after a reaction kettle is cooled, and cleaning and drying the obtained solid to obtain the ZnO-CuIn for the photocathode protection of the embodiment5S8A composite membrane.
2. The preparation method of the ZnO film for the photocathode protection comprises the following steps: adding 500mmol L into an electrolytic cell-1And (3) adjusting the pH =1 with sulfuric acid to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the ITO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 10 hours at the temperature of 90 ℃ and under the potential of-0.5V by a potentiostatic method to obtain the ZnO nanowire.
3. CuIn for photocathode protection5S8The preparation method of the film comprises the following steps: using 100mmol L-1500mmol L of copper nitrate-1And 1mol of indium nitrate-1Mixed solution of thioureaPutting the ITO conductive glass obtained by the treatment in the step (1) with the conductive surface facing downwards, controlling the temperature of hydrothermal reaction at 180 ℃ and the reaction time to be 8 hours, removing the solution after the reaction kettle is cooled, and cleaning and drying the obtained solid to obtain the CuIn for the photocathode protection of the embodiment5S8And (3) a membrane.
4. Photoinduced current-voltage curve test:
under intermittent visible light, the ZnO-CuIn prepared by the method5S8Composite film, ZnO film for photocathode protection, and CuIn for photocathode protection5S8The film was subjected to a Photo-induced current-voltage curve (Photo-induced current-time current) test, abbreviated as J-t. Research on ZnO-CuIn by J-t curve5S8The mechanism of enhancing the photoelectrochemical property of the composite photo-anode membrane composite material.
The experimental results are shown in fig. 1, and it can be seen from fig. 1 that compared to ZnO film for photocathode protection and CuIn for photocathode protection alone5S8Film, ZnO-CuIn for photocathode protection of the present example5S8The photoproduction current density of the composite membrane is improved by 2-4 times, which shows that the narrow band gap CuIn5S8The introduction of (2) and the construction of the Z-type electron transfer heterojunction effectively inhibit the recombination of photon-generated carriers.
Example 2
1. ZnO-CuIn for photocathode protection of the present example5S8A method of making a composite membrane comprising the steps of:
(1) before a hydrothermal reaction experiment, the film needs to be thoroughly cleaned, and the purpose is to improve the adhesive force between the film and the glass, the FTO conductive glass is sequentially put into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, ethanol and deionized water, and is cleaned by ultrasonic cleaning for 20 min. Then soaking the substrate in dilute hydrochloric acid with the pH =6 for 2-3 min to enable the surface of the substrate to adsorb a large amount of H+And washing with deionized water, and drying at 100 ℃ for later use.
(2) Adding 1mol L into an electrolytic cell-1Mixed solution of zinc acetate and NaCl with sulfurAcid adjusted pH =1.5 to give an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the FTO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 10 hours at the temperature of 70 ℃ under the potentiostatic method-1.5V potential to obtain the ZnO nanowire.
(3) Using a 500mmol L-1Copper acetylacetonate, 100mmol L-1And 1mol of indium nitrate-1Putting the FTO conductive glass of the ZnO nanowire with the conductive surface facing downwards into the mixed solution of thioacetamide, controlling the hydrothermal temperature to be 120 ℃ and reacting for 18 hours, removing the solution after the reaction kettle is cooled, cleaning and drying the obtained solid, and thus obtaining the ZnO-CuIn for the photocathode protection of the embodiment5S8A composite membrane.
2. The preparation method of the ZnO film for the photocathode protection comprises the following steps: adding 1mol L into an electrolytic cell-1The pH =1.5 was adjusted with sulfuric acid to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the FTO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 10 hours at the temperature of 70 ℃ under the potentiostatic method of-1.5V potential to obtain the ZnO nanowire.
3. Respectively carrying out the preparation on the ZnO-CuIn for the protection of the photocathode5S8The photoresponse performance of the composite film and the ZnO film for photocathode protection is tested, and the test result is shown in figure 2.
As can be seen from FIG. 2, the ZnO-CuIn for photocathode protection of the present embodiment5S8The absorption band edge of the composite film is obviously red shifted to about 880nm (the measured value of the light absorption band edge of a ZnO film for protecting the photocathode is about 410 nm), and the light utilization efficiency of the photoanode material is improved.
Example 3
1. ZnO-CuIn for photocathode protection of the present example5S8A method of making a composite membrane comprising the steps of:
(1) before the hydrothermal reaction experiment, it is necessary to thoroughly clean it for its purposeIn order to improve the adhesive force between the film and the glass, the FTO conductive glass is sequentially put into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, ethanol and deionized water, and is cleaned by ultrasonic for 30 min. Then soaking the substrate in dilute hydrochloric acid with the pH =4 for 2-3 min to enable the surface of the substrate to adsorb a large amount of H+And washing with deionized water, and drying at 50 ℃ for later use.
(2) Adding 1mol L into an electrolytic cell-1And (3) mixing the solution of zinc chloride and sodium sulfate, and adjusting the pH =1.5 with hydrochloric acid to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the FTO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 24 hours at the temperature of 50 ℃ under the potentiostatic method-1.8V potential to obtain the ZnO nanowire.
(3) Using 500mmol L-1Of copper acetate, 500mmol L-1And 1mol of indium nitrate-1Putting FTO conductive glass with ZnO nanowires deposited on the surface of the FTO conductive glass into a thioacetamide mixed solution in a manner that the conductive surface faces downwards, controlling the hydrothermal temperature to be 140 ℃ and the reaction time to be 14h, removing the solution after a reaction kettle is cooled, cleaning and drying the obtained solid, and thus obtaining the ZnO-CuIn for photocathode protection of the embodiment5S8A composite membrane.
2. The preparation method of the ZnO film for the photocathode protection comprises the following steps: adding 1mol L into an electrolytic cell-1And (3) adjusting the pH =1.5 with hydrochloric acid to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the FTO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 24 hours at the temperature of 50 ℃ under the potentiostatic method-1.8V potential to obtain the ZnO nanowire.
3. CuIn for photocathode protection5S8The preparation method of the membrane comprises the following steps: using 500mmol L-1Of copper acetate, 500mmol L-1And 1mol of indium nitrate-1Putting the FTO conductive glass obtained by the treatment in the step (1) with the conductive surface facing downwards into the mixed solution of thioacetamide, controlling the hydrothermal temperature at 140 ℃ and the reaction time at 14h, and cooling the reaction kettleThen the solution is removed, and the obtained solid is washed and dried to obtain the CuIn for photocathode protection of the embodiment5S8And (3) a membrane.
4. The photoluminescence spectrum of the obtained photoanode material was tested:
respectively carrying out the preparation on the prepared ZnO-CuIn for the protection of the photocathode5S8Composite film, ZnO film for photocathode protection, and CuIn for photocathode protection5S8Photoluminescence spectra (PL) of the films were tested for photo-generated charge separation efficiency, and the results are shown in fig. 3.
As can be seen from FIG. 3, the ZnO-CuIn for photocathode protection of the present embodiment5S8The strength of the composite film is far lower than that of a ZnO film for photocathode protection and a CuIn for photocathode protection5S8The membrane, illustrates that the construction of the heterojunction significantly enhances the separation efficiency of the photo-generated charges.
Example 4
1. ZnO-CuIn for photocathode protection of the present example5S8A method of making a composite membrane comprising the steps of:
(1) before a hydrothermal reaction experiment, the film needs to be thoroughly cleaned, and the purpose is to improve the adhesive force between the film and the glass, the FTO conductive glass is sequentially put into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, ethanol and deionized water, and is cleaned by ultrasonic cleaning for 25 min. Soaking the substrate in dilute hydrochloric acid with the pH =4 for 2-3 min to enable the surface of the substrate to adsorb a large amount of H+And washing with deionized water, and drying at 90 ℃ for later use.
(2) Adding 1mol L into an electrolytic cell-1With nitric acid, pH =4.5, to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the FTO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 10 hours at the temperature of 60 ℃ under the potentiostatic method-1.2V potential to obtain the ZnO nanowire.
(3) Using 500mmol L-1Copper acetylacetonate, 600mmolL-1And 1mol of indium chloride-1Putting the FTO conductive glass with the ZnO nanowires deposited on the surface into a mixed solution of sodium sulfite, controlling the hydrothermal temperature to be 150 ℃ and reacting for 15h, removing the solution after the reaction kettle is cooled, cleaning and drying the obtained solid, and preparing the ZnO-CuIn for the photocathode protection of the embodiment5S8A composite membrane.
2. The preparation method of the ZnO film for the photocathode protection comprises the following steps: adding 1mol L into an electrolytic cell-1With nitric acid, pH =4.5, to obtain an electrochemical deposition solution. And (2) adopting a three-electrode system, taking the FTO conductive glass obtained by the treatment in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing for 10 hours at the temperature of 60 ℃ under the potentiostatic method-1.2V potential to obtain the ZnO nanowire.
3. CuIn for photocathode protection5S8The preparation method of the membrane comprises the following steps:
using 500mmol L-1Copper acetylacetonate, 600mmol L-1Indium chloride and 1mol L-1Putting the FTO conductive glass obtained by the treatment in the step (1) into a mixed solution of sodium sulfite with the conductive surface facing downwards, controlling the hydrothermal temperature at 150 ℃ for reaction for 15h, removing the solution after the reaction kettle is cooled, cleaning and drying the obtained solid, and preparing the ZnO-CuIn for the photocathode protection of the embodiment5S8A composite membrane.
4. The photo-generated cathodic protection performance of the obtained photo-anode material is tested:
respectively carrying out the preparation on the prepared ZnO-CuIn for the protection of the photocathode5S8Composite film, ZnO film for photocathode protection, and CuIn for photocathode protection5S8The membrane was subjected to a photoproduction cathodic protection test: coupling the prepared photo-anode material with metal, performing a potential polarization test, and testing the prepared photo-anode material (respectively adopting the prepared ZnO-CuIn for photocathode protection) under illumination or dark state5S8Composite film, ZnO film for photocathode protection, and method for manufacturing the sameCathodically protected CuIn5S8The film is used as the photo-anode material) and the concrete structure steel bar of the ocean engineering building, so as to judge the photoelectric cathode protection performance of different photo-anode materials on the steel bar, and the testing device is shown in figure 4. The testing device is a double-electrolytic-cell system and is divided into a photolysis cell and a corrosion cell, the photolysis cell and the corrosion cell are communicated through a DuPont proton exchange membrane (N117), and the DuPont proton exchange membrane also separates two electrolytes while ensuring ion conduction. One end of the photolysis cell is provided with a quartz glass hole with the diameter of 3.5cm, and simulated sunlight irradiates on the photo-anode material. The photolysis pool and the corrosion pool both contain 3.5% of NaCl solution by mass fraction, protected metal is placed in the corrosion pool and connected by adopting a traditional three-electrode system, a Pt sheet is used as a Counter Electrode (CE), a Saturated Calomel Electrode (SCE) is used as a Reference Electrode (RE), and protected steel bars are used as Working Electrodes (WE). The photoanode material was placed in a photolysis cell and coupled to the protected metal in the etch cell using copper wires. The potentiodynamic polarization curve of the photoanode material coupled to the metal was tested with the light source turned on or off, and the results are shown in fig. 5.
As can be seen from FIG. 5, the ZnO-CuIn for photocathode protection prepared in this example was used under illumination5S8The composite film can make the corrosion potential of the steel bar negatively shift more than 500 millivolts (the ZnO film used for photoelectric cathode protection can make the corrosion potential of the steel bar negatively shift 200 millivolts, and the CuIn used for photoelectric cathode protection5S8The film can shift the corrosion potential of the steel bar negatively by 260 mv).
In summary, the experimental results of examples 1-4 all illustrate the ZnO-CuIn for photocathode protection of the present invention5S8The composite membrane can provide photoelectric cathode protection current for the concrete structural steel bar of the ocean engineering building with lower self-corrosion potential, and prolong the service life of the ocean engineering building.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the composite film for the photocathode protection is characterized by comprising the following steps:
(1) cleaning and acid treatment are carried out on the conductive glass;
(2) depositing ZnO nanowires on the surface of the conductive glass obtained by the treatment in the step (1) by an electrodeposition method;
(3) depositing CuIn on the surface of the ZnO nanowire by a hydrothermal method5S8Obtaining the ZnO-CuIn5S8The composite film is the composite film for the photoelectric cathode protection;
the step (2) is specifically as follows: adding an electrochemical deposition solution containing zinc salt, electrolyte salt and strong acid into an electrolytic cell, adopting a three-electrode system, taking the conductive glass obtained in the step (1) as a working electrode, taking saturated calomel and Pt as a reference electrode and a counter electrode respectively, and depositing at the temperature of 20-90 ℃ by a potentiostatic method to obtain ZnO nanowires;
the step (3) is specifically as follows: placing the conductive glass with the ZnO nanowires deposited on the surface, which is obtained by the treatment of the step (2), in a reaction container containing a mixed solution of a copper source, an indium source and a sulfur source, enabling the conductive surface of the conductive glass with the ZnO nanowires deposited on the surface to face downwards, carrying out hydrothermal reaction for 8-18 h at the temperature of 120-180 ℃, and after the hydrothermal reaction is finished, cleaning and drying to obtain the ZnO-CuIn for the protection of the photocathode5S8Compounding film;
in the step (2), the concentration of the zinc salt is 0.5mol L-1Or 1mol L-1The strong acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, the pH of the electrochemical deposition solution is = 1-4.5, the potential during potentiostatic deposition is-0.5-1.8V, and the deposition time is 10h or 24 h; the zinc salt is an inorganic salt or an organic salt containing zinc, and the electrolyte salt is at least one of potassium chloride, potassium sulfate, lithium perchlorate, sodium chloride and sodium sulfate;
in the step (3), the concentration of the copper source is 100mmolL-1~500mmolL-1The concentration of the indium source is 100mmolL-1~600molL-1The concentration of the sulfur source is 1mol L-1And the concentration ratio of the copper source to the indium source is 1: 5-5: 1.
2. The method for preparing the composite film for photocathode protection according to claim 1, wherein the cleaning comprises sequentially placing the conductive glass in a first solution, a second solution, a third solution and a fourth solution to ultrasonically clean the conductive glass, wherein the first solution is an aqueous solution containing a detergent, the second solution is an ethanol solution of NaOH, the third solution is ethanol or acetone, and the fourth solution is deionized water; the time of ultrasonic cleaning is 10-30 min each time.
3. The method for preparing a composite film for photocathode protection according to claim 2, wherein the acid treatment is specifically: soaking the cleaned conductive glass in the fourth solution by using an acid solution;
the step of washing the conductive glass after acid treatment by using deionized water and drying after washing is finished is also included after the acid treatment;
the acid solution is hydrochloric acid solution, the pH of the hydrochloric acid solution is = 1-6, the soaking time is 2-3 min, and the drying temperature is 60-100 ℃;
the conductive glass is FTO conductive glass or ITO conductive glass.
4. The method of claim 1, wherein the zinc salt is at least one of zinc nitrate, zinc sulfate, zinc chloride, zinc acetate, and zinc acetylacetonate.
5. The method for preparing a composite film for photocathode protection according to claim 1, wherein the copper source is an inorganic or organic salt of copper, and the indium source is an inorganic or organic salt of indium;
the copper source is at least one of copper nitrate, copper sulfate, copper chloride, copper acetate and copper acetylacetonate;
the indium source is at least one of indium nitrate, indium sulfate, indium chloride and indium acetate;
the sulfur source is at least one of thiourea, thioacetamide and sodium sulfite.
6. A composite film for photocathode protection, characterized in that the composite film for photocathode protection is prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the composite film for photocathode protection according to claim 6 for the corrosion prevention of steel bars of concrete structures of ocean engineering buildings.
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