CN114255999A - Photo-generated anti-corrosion electrode material and preparation method and application thereof - Google Patents
Photo-generated anti-corrosion electrode material and preparation method and application thereof Download PDFInfo
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- CN114255999A CN114255999A CN202110250586.7A CN202110250586A CN114255999A CN 114255999 A CN114255999 A CN 114255999A CN 202110250586 A CN202110250586 A CN 202110250586A CN 114255999 A CN114255999 A CN 114255999A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005260 corrosion Methods 0.000 title claims description 24
- 239000000758 substrate Substances 0.000 claims abstract description 61
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 36
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 35
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- 239000007769 metal material Substances 0.000 claims description 17
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
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- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010962 carbon steel Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910003321 CoFe Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005536 corrosion prevention Methods 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
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- 239000000126 substance Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 4
- 239000000243 solution Substances 0.000 description 71
- 239000010963 304 stainless steel Substances 0.000 description 13
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 12
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to the technical field of electrode materials, and provides a preparation method of a photoproduction anticorrosion electrode material.A alpha-ferric oxide film grows on a substrate, and the alpha-ferric oxide has higher solar energy-chemical energy conversion efficiency, a proper band gap structure, can drive water oxidation reaction under the drive of visible light, and has the advantages of good light stability and the like; then, by alternately dipping the alpha-ferric oxide film in a potassium ferricyanide solution and a cobalt chloride solution, a CoFe-PB cocatalyst layer is introduced on the surface of the alpha-ferric oxide film, so that the conductivity of the electrode can be improved, and the catalytic performance of the electrode material can be improved; and the water oxidation rate of an electrode interface can be effectively driven, and the transfer efficiency of a photoproduction hole is greatly improved, so that the recombination of photoproduction electrons and the hole is inhibited, the photoproduction electrons are gathered on a photoelectrode substrate and then effectively transferred to the surface of protected metal, and the effective photocathode corrosion prevention under an open-circuit potential is realized.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a photoproduction anticorrosion electrode material and a preparation method and application thereof.
Background
The metal material has good technological properties and service properties, and is widely applied to various fields of human life, such as serving as a cathode of an electrode. However, most of metal materials are prone to corrosion in use, causing huge economic loss and serious danger, and therefore, the research of metal material corrosion prevention technology is becoming a great trend. At present, the metal corrosion prevention technology comprises the following steps: 1. structural change methods such as making various corrosion resistant alloys; 2. protective coating methods, such as spraying paint on steel surfaces; 3. the electrochemical protection method is used for protecting metal by utilizing a primary battery principle and trying to eliminate primary battery reaction causing electrochemical corrosion, and the electrochemical protection method is divided into anode protection and cathode protection; 4. protecting a sacrificial anode; 5. applied current protection, etc. However, the impressed current cathodic protection technology requires high electric energy input, environmental pollution and material consumption are caused by sacrificial anode protection, and photoelectrochemical cathodic protection only takes solar energy and water as input sources, so that the photoelectrochemical cathodic protection is concerned in the field of metal corrosion prevention.
The photoelectrochemical cathodic protection is a novel cathodic protection technology which utilizes green and clean solar energy to slow down or even inhibit the corrosion of metal materials and protect the metal materials. The principle is that the semiconductor coating can generate the effect of photo-generated electron-hole pairs under the condition of illumination radiation, and photo-generated electrons generated by the photo-excitation of the semiconductor coating are transferred to a substrate metal material, so that the technology similar to the external cathode current protection of the substrate metal is realized. The photoelectrochemical cathode protection technology is a new technology for protecting metal materials by utilizing solar energy, and the anticorrosion materials are not consumed in the protection process, so that the photoelectrochemical cathode protection technology is expected to become a permanent protective coating. Therefore, the method is a real green environment-friendly anti-corrosion technology and has wide application prospect.
To date, many semiconductor coatings have been developed as materials for photoelectrochemical cathodic protection, such as TiO2、WO3、SnO2、α-Fe2O3/Fe3O4And the like. Due to alpha-Fe2O3Has higher solar energy-chemical energy conversionThe organic silicon quantum dot/organic semiconductor material has the advantages of conversion efficiency, proper band gap structure (Eg ≈ 2.1eV), can be driven by visible light. However, due to α -Fe2O3The hole diffusion length of (2) is short, the conductivity is poor, and the activity of photoelectrocatalysis for decomposing water is still low. Therefore, it is desirable to provide an electrode material that has excellent photocatalytic activity and can protect the cathode from photoelectrochemistry.
Disclosure of Invention
The invention aims to provide a photoproduction anticorrosion electrode material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a photoproduction anticorrosion electrode material, which comprises the following steps:
(1) growing alpha-Fe on the surface of a substrate2O3Film to obtain a film containing alpha-Fe2O3A substrate of a thin film;
(2) the alpha-Fe contained in the product obtained in the step (1)2O3And alternately dipping the substrate of the film in a potassium ferricyanide solution and a cobalt chloride solution to obtain the photoproduction anticorrosion electrode material.
Preferably, the substrate in the step (1) comprises FTO glass, a titanium plate or a copper plate.
Preferably, the concentration of the potassium ferricyanide solution in the step (2) is 0.01-1 mol/L.
Preferably, the concentration of the cobalt chloride solution in the step (2) is 0.02-2 mol/L.
Preferably, the step (2) is performed by using alpha-Fe2O3The soaking time of the film in the potassium ferricyanide solution is 5-20 min/time.
Preferably, the step (2) is performed by using alpha-Fe2O3The time for soaking the film in the cobalt chloride solution is 5-20 min/time.
Preferably, the number of times of the alternate dipping in the step (2) is repeated is 2-19 times.
The invention also provides a photoproduction anti-corrosion electrode material prepared by the preparation method of the technical scheme, which comprises a substrate and alpha-Fe loaded on the substrate2O3Film and supported on alpha-Fe2O3A CoFe Prussian blue film on the film.
The invention also provides an application of the photogeneration anticorrosion electrode material in photogeneration cathode anticorrosion, which comprises the following steps:
a. placing a photoproduction anticorrosion electrode material in a photoanode cell, and placing a cathode metal material in a corrosion cell; the photo-anode pool and the corrosion pool are connected through a salt bridge;
b. and c, connecting the photoproduction anticorrosion electrode material in the step a with a cathode metal material through a lead to obtain a coupling electrode, and placing the coupling electrode under the condition of visible light irradiation for illumination.
Preferably, the cathode metal material comprises stainless steel, carbon steel or titanium plate.
The invention provides a preparation method of a photoproduction anticorrosion electrode material, which comprises the following steps: growing alpha-Fe on the surface of a substrate2O3Film to obtain a film containing alpha-Fe2O3A substrate of a thin film; the obtained alpha-Fe-containing2O3And alternately dipping the substrate of the film in a potassium ferricyanide solution and a cobalt chloride solution to obtain the photoproduction anticorrosion electrode material. The invention firstly grows alpha-Fe on a substrate2O3Film of alpha-Fe2O3The solar energy-chemical energy conversion efficiency is high, a proper band gap structure is provided, the water oxidation reaction can be driven under the drive of visible light, and the light stability is good; then alternately dipping in potassium ferricyanide solution and cobalt chloride solution to obtain alpha-Fe2O3The CoFe Prussian blue (CoFe-PB for short) film is introduced to the surface of the film, so that the conductivity of the electrode can be improved, and the catalytic performance of the electrode material can be improved; and, the CoFe-PB cocatalyst layer can effectively drive the water oxygen of the electrode interfaceThe conversion rate greatly improves the transfer efficiency of the photo-generated holes, so that the recombination rate of photo-generated electrons and the photo-generated holes is inhibited, the photo-generated electrons are directly gathered on the photoelectrode substrate and then effectively transferred to the surface of the protected metal, and the open-circuit potential effective photocathode corrosion prevention is realized. Experimental results show that the photoproduction anticorrosion electrode material prepared by the invention can obviously improve the water oxidation reaction rate and has more excellent anticorrosion effect on 304 stainless steel.
Drawings
FIG. 1 shows α -Fe prepared in example 1 of the present invention2O3Film and alpha-Fe2O3XRD pattern of/CoFe-PB film electrode;
FIG. 2 shows α -Fe prepared in example 1 of the present invention2O3Film and alpha-Fe2O3Raman spectrum of the/CoFe-PB film electrode;
FIG. 3 shows α -Fe prepared in example 2 of the present invention2O3SEM image of the film;
FIG. 4 shows α -Fe prepared in example 2 of the present invention2O3SEM image of/CoFe-PB film electrode;
FIG. 5 shows α -Fe prepared in example 2 of the present invention2O3And alpha-Fe2O3The ultraviolet visible absorption spectrum of the/CoFe-PB film electrode;
FIG. 6 shows α -Fe prepared in example 3 of the present invention2O3And alpha-Fe2O3A photocurrent-time curve graph of the/CoFe-PB film electrode under the irradiation of visible light;
FIG. 7 shows α -Fe in example 4 of the present invention2O3304 stainless steel coupling electrode and alpha-Fe2O3Open circuit potential-time curve diagram of/CoFe-PB-304 stainless steel coupling electrode under dark state and illumination.
Detailed Description
The invention provides a preparation method of a photoproduction anticorrosion electrode material, which comprises the following steps:
(1) growing alpha-Fe on the surface of a substrate2O3Film to obtain a film containing alpha-Fe2O3Base of thin filmA bottom;
(2) the alpha-Fe contained in the product obtained in the step (1)2O3And alternately dipping the substrate of the film in a potassium ferricyanide solution and a cobalt chloride solution to obtain the photoproduction anticorrosion electrode material.
The invention grows alpha-Fe on the surface of the substrate2O3Film to obtain a film containing alpha-Fe2O3A substrate for the film.
In the present invention, the substrate preferably comprises FTO glass, titanium plate or copper plate. The source of the substrate is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the present invention, the substrate is capable of supporting alpha-Fe2O3A film.
The invention grows alpha-Fe on the surface of the substrate2O3The method of film formation is not particularly limited, and α -Fe is grown on a substrate by a method well known to those skilled in the art2O3And (3) a film method. In the present invention, the growing of α -Fe on a substrate2O3The method of the film is preferably: FeCl is added3·6H2Mixing O, urea and water to obtain a mixed solution, placing a substrate in the mixed solution, and carrying out hydrothermal reaction to obtain a precursor; calcining the precursor to obtain the precursor containing alpha-Fe2O3A substrate for the film.
FeCl is preferably used in the invention3·6H2Mixing O, urea and water to obtain a mixed solution, placing the substrate in the mixed solution, and carrying out hydrothermal reaction to obtain a precursor. In the present invention, the FeCl3·6H2The ratio of the mass of O, the mass of urea and the volume of water is preferably (0.14 to 0.41) g: (0.09-0.27) g: (10-30) mL, more preferably 0.27 g: 0.18 g: 20 mL. In the present invention, the FeCl3·6H2O provides a source of iron, the urea acts as a precipitant, and the water, preferably deionized water, acts as a solvent. In the present invention, the FeCl3·6H2The mass of O, urea and water form FeOOH precipitates under hydrothermal conditions when the FeCl precipitates3·6H2When the ratio of the mass of O, the mass of urea and the volume of water is within the above rangeA precipitate can be sufficiently formed on the surface of the substrate.
The invention is directed to the FeCl3·6H2The operation of mixing O, urea and water is not particularly limited, and FeCl can be mixed by a mixing method well known to those skilled in the art3·6H2Dissolving O and urea in water.
In the invention, the temperature of the hydrothermal reaction is preferably 90-120 ℃, and more preferably 100 ℃; the time of the hydrothermal reaction is preferably 2-8 h, and more preferably 4 h. In the present invention, the hydrothermal reaction can be sufficiently performed when the temperature and time of the hydrothermal reaction are within the above ranges. The apparatus for the hydrothermal reaction in the present invention is not particularly limited, and an apparatus for hydrothermal reaction known to those skilled in the art may be used.
After the hydrothermal reaction is finished, the product obtained by the hydrothermal reaction is preferably washed and dried in sequence to obtain a precursor. In the invention, the precursor comprises a substrate and FeOOH precipitates deposited on the surface of the substrate. The washing and drying operation method of the present invention is not particularly limited, and a washing and drying operation method known to those skilled in the art may be used. In the present invention, the washing reagent is preferably ultrapure water. In the invention, the drying temperature is preferably 20-60 ℃, and more preferably 30-40 ℃. The drying time is not particularly limited, and the washed product can be dried.
After the precursor is obtained, the precursor is preferably calcined to obtain the alpha-Fe-containing material2O3A substrate for the film.
In the present invention, the calcination is preferably low-temperature calcination and high-temperature calcination performed in this order. In the invention, the temperature of the low-temperature calcination is preferably 400-600 ℃, and more preferably 500 ℃; the time of the low-temperature calcination is preferably 1-8 h, and more preferably 3 h. In the invention, the high-temperature calcination temperature is preferably 700-850 ℃, and more preferably 750 ℃; the high-temperature calcination time is preferably 5-120 min, and more preferably 20 min. In the present invention, the calcination is a low-temperature calcination and a high-temperature calcination performed in this order, enabling α -Fe2O3The film is uniformly and densely distributed on the surface of the substrate.
The invention is directed to the alpha-Fe-containing2O3alpha-Fe on a substrate for thin films2O3The thickness of the film is not particularly limited, and may be adjusted as necessary. In the present invention, the alpha-Fe2O3The thickness of the thin film is preferably 10nm to 10 μm, more preferably 200nm to 500 nm. In the present invention, the alpha-Fe2O3When the thickness of the thin film is within the above range, the catalytic activity of the electrode can be more advantageously improved.
To obtain a catalyst containing alpha-Fe2O3After the substrate of the film, the invention contains alpha-Fe2O3And alternately dipping the substrate of the film in a potassium ferricyanide solution and a cobalt chloride solution to obtain the photoproduction anticorrosion electrode material.
In the present invention, the solvent of the potassium ferricyanide solution is preferably deionized water. The method for preparing the potassium ferricyanide solution is not particularly limited in the present invention, and a method for preparing a solvent well known to those skilled in the art may be used.
In the invention, the concentration of the potassium ferricyanide solution is preferably 0.01-1 mol/L, more preferably 0.05-0.5 mol/L, and most preferably 0.1-0.5 mol/L. In the present invention, when the concentration of the potassium ferricyanide solution is within the above range, it is more advantageous to control the reaction rate.
In the present invention, the alpha-Fe-containing compound2O3The soaking time of the substrate of the film in the potassium ferricyanide solution is preferably 5-20 min/time, and more preferably 10-15 min/time. In the present invention, the soaking causes potassium ferricyanide to be adsorbed to α -Fe2O3The surface of the film.
In the present invention, the solvent of the cobalt chloride solution is preferably deionized water. The method for preparing the cobalt chloride solution is not particularly limited in the present invention, and a method for preparing a solvent well known to those skilled in the art may be used.
In the invention, the concentration of the cobalt chloride solution is preferably 0.02-2 mol/L, and more preferably 0.1-1 mol/L. In the present invention, when the concentration of the cobalt chloride solution is within the above range, it is more advantageous to control the reaction rate.
In the present invention, the alpha-Fe-containing compound2O3The soaking time of the substrate of the film in the cobalt chloride solution is preferably 5-20 min/time, and more preferably 10-15 min/time. In the invention, cobalt chloride is adsorbed on alpha-Fe in the soaking process2O3The potassium ferricyanide on the surface of the film reacts to form a CoFe-PB layer.
The invention preferably comprises alpha-Fe after each impregnation2O3The substrate of the film is washed and then dipped again. In the present invention, the washing is capable of non-adsorbing α -Fe2O3And the potassium ferricyanide solution or cobalt chloride solution on the surface of the film is removed, so that the compactness of the CoFe-PB layer is improved.
In the present invention, the alpha-Fe-containing compound2O3The alternate immersion of the substrate of the film in the potassium ferricyanide solution and the cobalt chloride solution can be in alpha-Fe2O3CoFe-PB is formed on the surface of the film.
In the present invention, the number of times of the alternate dipping is preferably 2 to 19 times, and more preferably 5 to 15 times. In the present invention, the number of repetitions determines the thickness of CoFe-PB. In the present invention, when the number of repetitions is in the above range, the resulting CoFe-PB has a thickness of preferably 1nm to 200nm, more preferably 5nm to 50 nm. In the present invention, when the thickness of CoFe-PB is in the above range, the electrocatalytic performance and the photo-generated corrosion resistance of the electrode material can be further improved.
In the present invention, the alpha-Fe-containing compound2O3The alternate immersion of the substrate of the film in the potassium ferricyanide solution and the cobalt chloride solution is preferably carried out with stirring. In the present invention, the stirring enables the potassium ferricyanide solution or cobalt chloride solution to be uniformly distributed over α -Fe2O3The surface of the film. The stirring speed is not particularly limited, and the potassium ferricyanide solution or the cobalt chloride solution can be stirred in the alpha-Fe solution2O3The film surface is uniformly distributed.
The preparation method provided by the invention grows alpha-Fe on the surface of the substrate2O3Film, then will contain alpha-Fe2O3And alternately dipping the substrate of the film in a potassium ferricyanide solution and a cobalt chloride solution to obtain the photoproduction anticorrosion electrode material. The method can be used in alpha-Fe2O3CoFe-PB is formed on the surface of the film and serves as a promoter layer.
The invention also provides a photoproduction anti-corrosion electrode material prepared by the preparation method of the technical scheme, which comprises a substrate and alpha-Fe loaded on the substrate2O3Film and supported on alpha-Fe2O3CoFe-PB on the film.
In the invention, alpha-Fe in the photoproduction anti-corrosion electrode material2O3As an active material, the CoFe-PB is a cocatalyst layer, so that the interface hole transfer rate of the photoproduction anticorrosion electrode material can be improved, the recombination of photoproduction charges is further inhibited, and the electrocatalytic activity of the photoproduction anticorrosion electrode material is improved; and has the effect of improving the corrosion resistance of the photocathode.
The invention also provides an application of the photoproduction anticorrosion electrode material in photoproduction cathodic anticorrosion, and the application method of the photoproduction anticorrosion electrode material in photoproduction cathodic anticorrosion preferably comprises the following steps:
a. placing a photoproduction anticorrosion electrode material in a photoanode cell, and placing a cathode metal material in a corrosion cell; the photo-anode pool and the corrosion pool are connected through a salt bridge;
b. and c, connecting the photoproduction anticorrosion electrode material in the step a with a cathode metal material through a lead to obtain a coupling electrode, and placing the coupling electrode under the condition of visible light irradiation for illumination.
In the invention, the electrolyte in the corrosion tank is preferably a NaCl solution, and the mass concentration of the NaCl solution is preferably 2-4%, and more preferably 3.5%. In the present invention, when the electrolyte in the corrosion cell is of the above-described type, the reduction reaction is facilitated.
The operation mode of salt bridge connection is not particularly limited in the invention, and the operation mode of salt bridge connection known to those skilled in the art can be adopted.
In the present invention, the cathode metal material preferably includes a stainless steel, carbon steel or titanium plate. The source of the stainless steel, carbon steel or titanium plate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
The connection mode of the photoproduction anticorrosion electrode material and the cathode metal material through the lead is not particularly limited, and the connection mode known by the technicians in the field is adopted.
In the invention, the electrolyte in the photo-anode cell is preferably a NaOH solution, and the concentration of the NaOH solution is preferably 0.1-5 mol/L, and more preferably 1 mol/L. In the present invention, the electrolyte in the photoanode cell is of the above type, which facilitates the oxidation reaction.
In the invention, visible light can drive the water oxidation reaction, and the coupling electrode can provide a light source for the water oxidation reaction when being placed under the visible light irradiation condition for illumination.
The photoproduction anticorrosion electrode material provided by the invention has excellent electrocatalytic activity and can improve the anticorrosion effect of a photocathode, so that the photoproduction anticorrosion electrode material can be used for photoproduction cathodic anticorrosion.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 0.27g FeCl was weighed3·6H2Dissolving O and 0.18g of urea in 20mL of distilled water, stirring at room temperature to completely dissolve the O and the urea, transferring the solution into a dyeing tank inserted with FTO glass, sealing, placing the solution into an oven at 100 ℃, and carrying out hydrothermal reaction for 4 hours. After the reaction is finished, taking out the membrane, cleaning the membrane by using ultrapure water, drying the membrane, calcining the membrane in a muffle furnace at 500 ℃ for 3h, and calcining the membrane in the muffle furnace at 750 ℃ for 20min to obtain the membrane containing alpha-Fe2O3A substrate for the film.
(2) Respectively preparing potassium ferricyanide solution and cobalt chloride solution. The concentration of the potassium ferricyanide solution is 0.02mol/L, and the concentration of the cobalt chloride solution is 0.04 mol/L.
(3) Will contain alpha-Fe under slow stirring2O3Immersing the substrate of the film into potassium ferricyanide solution for 10min, washing the electrode with distilled water, immersing the electrode into cobalt chloride solution for 10min, and repeating the step for 4 times to obtain the photoproduction anticorrosion electrode material, alpha-Fe for short2O3a/CoFe-PB film electrode.
The composition prepared in this example and containing alpha-Fe was subjected to X-ray diffractometry2O3Film substrate (in figure 1, alpha-Fe for short)2O3) And alpha-Fe2O3the/CoFe-PB film electrode is tested, and the XRD pattern is shown in figure 1.
The prepared product containing alpha-Fe in the example is processed by Raman spectroscopy2O3Film substrate (in FIG. 2, alpha-Fe for short)2O3) And alpha-Fe2O3the/CoFe-PB film electrode is tested, and the obtained Raman spectrum is shown in figure 2.
As can be seen from fig. 1, the signals of the diffraction peaks at 35.6 °, 54.1 ° and 64.0 ° 2 θ and α -Fe2O3(JCPDS No.33-0664) and the remaining diffraction signals are well matched to the FTO substrate (JCPDS No. 46-1088). The XRD can prove that the alpha-Fe synthesized by the preparation method provided by the invention2O3Is phase-pure and contains no other impurity phases. alpha-Fe2O3CoFe-PB and alpha-Fe could not be observed in the/CoFe-PB film electrode2O3The diffraction peak of (a) indicates that the obtained CoFe-PB is amorphous, and the content of the CoFe-PB is too high to cause alpha-Fe2O3And (4) covering.
As can be seen from FIG. 2, it contains α -Fe2O3The base of the film is 1323cm-1The absorption peak is Fe-O stretching vibration, while alpha-Fe2O3Raman signal of/CoFe-PB film electrode and alpha-Fe-containing2O3The film had a large difference in base of 552cm-1And 1090cm-1The peak at (A) may be caused by CoFe-PB.
Example 2
(1) Prepared according to the method of example 1 to contain alpha-Fe2O3Film substrate (alpha-Fe for short)2O3A film);
(2) respectively preparing potassium ferricyanide solution and cobalt chloride solution. The concentration of the potassium ferricyanide solution is 0.02mol/L, and the concentration of the cobalt chloride solution is 0.04 mol/L.
(3) Will contain alpha-Fe under slow stirring2O3Immersing the substrate of the film into potassium ferricyanide solution for 10min, washing the electrode with distilled water, immersing the electrode into cobalt chloride solution for 10min, repeating the step for 2 times to obtain the photoproduction anticorrosion electrode material, alpha-Fe for short2O3a/CoFe-PB film electrode.
Scanning electron microscope is adopted to carry out the preparation of the alpha-Fe prepared in the embodiment2O3Testing the film to obtain an SEM image as shown in FIG. 3;
scanning electron microscope is adopted to carry out the preparation of the alpha-Fe prepared in the embodiment2O3the/CoFe-PB was tested and the SEM image is shown in FIG. 4.
As can be seen from FIG. 3, alpha-Fe having an average diameter of about 30nm2O3The nanorod arrays are grown on the FTO substrate. As can be seen from FIG. 4, α -Fe2O3Scanning electron microscope results of/CoFe-PB film electrode and alpha-Fe alone2O3Compared with the rough surface, the CoFe-PB is shown to be successfully adsorbed on the alpha-Fe2O3The outer surface of the nanorods.
Example 3
(1) Prepared according to the method of example 1 to contain alpha-Fe2O3Film substrate (alpha-Fe for short)2O3A film);
(2) respectively preparing potassium ferricyanide solution and cobalt chloride solution. The concentration of the potassium ferricyanide solution is 0.02mol/L, and the concentration of the cobalt chloride solution is 0.04 mol/L.
(3) The alpha-Fe is stirred slowly2O3Immersing the film into potassium ferricyanide solution for 15min, washing the electrode with distilled water, immersing the electrode into cobalt chloride solution for 15min, and repeating the steps for 4 times to obtain the photoproduction anticorrosion electrodeMaterials, alpha-Fe for short2O3a/CoFe-PB film electrode.
The alpha-Fe-containing material prepared in this example was subjected to diffuse reflectance spectroscopy for ultraviolet and visible light2O3Film and alpha-Fe2O3The obtained ultraviolet-visible absorption spectrogram of the/CoFe-PB film electrode is shown in figure 5.
From FIG. 5, it can be seen that the difference of light absorption of the two photoelectrodes is small, which indicates that the CoFe-PB loading is low, and the load is alpha-Fe2O3Has less influence on light absorption.
Respectively to alpha-Fe under the irradiation of visible light2O3alpha-Fe of/CoFe-PB film electrode2O3The photocurrent of the film was tested and the resulting photocurrent curve is shown in figure 6.
As can be seen from FIG. 6, α -Fe2O3alpha-Fe alone/photocurrent ratio of CoFe-PB2O3The film is large, which shows that the introduction of CoFe-PB can improve the alpha-Fe2O3The hole transfer efficiency of the reaction system, and further the water oxidation reaction rate is improved. Furthermore, we can also note α -Fe2O3Initial potential ratio of/CoFe-PB electrode to pure alpha-Fe2O3Low, indicating that CoFe-PB acts to significantly reduce the activation energy of water oxidation, which is responsible for increasing alpha-Fe2O3The current carrier separation efficiency of the photoelectrode has an important function, and is beneficial to inhibiting the recombination of photo-generated electrons and holes, so that the service life of the photo-generated electrons is prolonged, and a good foundation is laid for the application of the photoelectrode in corrosion prevention.
Example 4
(1) Prepared according to the method of example 1 to contain alpha-Fe2O3Film substrate (alpha-Fe for short)2O3A film);
(2) respectively preparing potassium ferricyanide solution and cobalt chloride solution. The concentration of the potassium ferricyanide solution is 0.06mol/L, and the concentration of the cobalt chloride solution is 0.08 mol/L.
(3) The alpha-Fe is stirred slowly2O3Immersing the film in potassium ferricyanide solution for 10min, washing the electrode with distilled water, and immersing the electrodeAdding cobalt chloride solution for 10min, repeating the step for 4 times to obtain alpha-Fe2O3a/CoFe-PB film electrode.
Subjecting the obtained alpha-Fe2O3the/CoFe-PB film electrode is connected with 304 stainless steel through a copper wire to prepare alpha-Fe2O3a/CoFe-PB-304 stainless steel coupling electrode, in which alpha-Fe2O3the/CoFe-PB film electrode is arranged in a photo-anode pool, and the electrolyte in the photo-anode pool is 1mol/LNaOH solution; the 304 stainless steel is placed in a corrosion tank, and the electrolyte in the corrosion tank is 3.5 wt% of NaCl solution; the photo-anode pool and the corrosion pool are connected through a salt bridge.
Using alpha-Fe2O3Preparation of alpha-Fe by connecting thin film with 304 stainless steel2O3304 stainless steel coupling electrodes as control group.
α-Fe2O3304 stainless steel coupling electrode and alpha-Fe2O3The open circuit potential-time curve of the/CoFe-PB stainless steel coupling electrode in the dark state and under illumination is shown in FIG. 7.
As can be seen from FIG. 7, after illumination, the open-circuit potentials of the two coupling electrodes are respectively shifted to-0.11 and-0.27V in a negative mode, which indicates that after illumination, the photo-generated electrons generated on the semiconductor electrode can be transferred to the 304 stainless steel, so that the open-circuit potential is shifted in a negative mode. Since electrons can be efficiently transferred to 304 stainless steel, corrosion protection of 304 stainless steel can be achieved by all three electrodes. In general, the more negative the open circuit potential under illumination, the more photogenerated electrons collect, the more electrons are transferred to the protected metal, and the stronger the protection. Based on this, we can see that the treated alpha-Fe2O3The electrode possesses better corrosion protection for 304 stainless steel.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a photogeneration anticorrosive electrode material comprises the following steps:
(1) growing alpha-Fe on the surface of a substrate2O3Film to obtain a film containing alpha-Fe2O3A substrate of a thin film;
(2) the alpha-Fe contained in the product obtained in the step (1)2O3And alternately dipping the substrate of the film in a potassium ferricyanide solution and a cobalt chloride solution to obtain the photoproduction anticorrosion electrode material.
2. The method according to claim 1, wherein the substrate in the step (1) comprises FTO glass, a titanium plate or a copper plate.
3. The method according to claim 1, wherein the concentration of the potassium ferricyanide solution in the step (2) is 0.01 to 1 mol/L.
4. The preparation method according to claim 1, wherein the concentration of the cobalt chloride solution in the step (2) is 0.02-2 mol/L.
5. The method according to claim 1, wherein the step (2) is performed by using α -Fe2O3The soaking time of the film in the potassium ferricyanide solution is 5-20 min/time.
6. The method according to claim 1, wherein the step (2) is performed by using α -Fe2O3The time for soaking the film in the cobalt chloride solution is 5-20 min/time.
7. The method according to claim 1, wherein the step (2) of alternately dipping is repeated 2 to 19 times.
8. The photogeneration anticorrosive electrode material prepared by the preparation method of any one of claims 1 to 7, which comprises a substrate and alpha-Fe loaded on the substrate2O3Film and supported on alpha-Fe2O3A CoFe Prussian blue film on the film.
9. The use of a photogenerated anticorrosion electrode material as claimed in claim 8 in photogenerated cathodic anticorrosion, comprising the steps of:
a. placing a photoproduction anticorrosion electrode material in a photoanode cell, and placing a cathode metal material in a corrosion cell; the photo-anode pool and the corrosion pool are connected through a salt bridge;
b. and c, connecting the photoproduction anticorrosion electrode material in the step a with a cathode metal material through a lead to obtain a coupling electrode, and placing the coupling electrode under the condition of visible light irradiation for illumination.
10. Use according to claim 9, wherein the cathodic metal material comprises stainless steel, carbon steel or titanium plate.
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| US20030121543A1 (en) * | 2000-07-29 | 2003-07-03 | Michael Gratzel | Photocatalytic film of iron oxide, electrode with such a photocatalytic film, method of producing such films, photoelectrochemical cell with the electrode and photoelectrochemical system with the cell, for the cleavage of water into hydrogen and oxygen |
| CN105601124A (en) * | 2016-01-08 | 2016-05-25 | 福州大学 | Method for preparing porous alpha-Fe2O3 photo-anode |
| CN108411309A (en) * | 2018-03-28 | 2018-08-17 | 中国石油大学(北京) | A kind of preparation method of iron oxide composite titanium dioxide thin film light anode for photoproduction cathodic protection |
| CN110387559A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030121543A1 (en) * | 2000-07-29 | 2003-07-03 | Michael Gratzel | Photocatalytic film of iron oxide, electrode with such a photocatalytic film, method of producing such films, photoelectrochemical cell with the electrode and photoelectrochemical system with the cell, for the cleavage of water into hydrogen and oxygen |
| CN105601124A (en) * | 2016-01-08 | 2016-05-25 | 福州大学 | Method for preparing porous alpha-Fe2O3 photo-anode |
| CN108411309A (en) * | 2018-03-28 | 2018-08-17 | 中国石油大学(北京) | A kind of preparation method of iron oxide composite titanium dioxide thin film light anode for photoproduction cathodic protection |
| CN110387559A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115125565A (en) * | 2022-06-29 | 2022-09-30 | 北京化工大学 | Method for resisting electrolytic seawater anodic corrosion |
| CN115125565B (en) * | 2022-06-29 | 2024-03-26 | 北京化工大学 | Method for resisting electrolytic seawater anode corrosion |
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