CN113120995A - Titanium dioxide coating electrode and preparation method thereof - Google Patents
Titanium dioxide coating electrode and preparation method thereof Download PDFInfo
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- CN113120995A CN113120995A CN202110245464.9A CN202110245464A CN113120995A CN 113120995 A CN113120995 A CN 113120995A CN 202110245464 A CN202110245464 A CN 202110245464A CN 113120995 A CN113120995 A CN 113120995A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a titanium dioxide coating electrode and a preparation method thereof. The preparation method of the titanium dioxide coating electrode comprises the following steps: firstly coating a tin-antimony intermediate layer on a pretreated titanium substrate, and then uniformly coating titanium dioxide on the tin-antimony intermediate layer to obtain a titanium dioxide coating electrode, wherein the titanium dioxide is prepared by the following steps: tetrabutyl titanate and hydrofluoric acid are mixed according to the volume ratio of 4-8:1-2 to prepare the {001} and {101} double crystal face exposed anatase type titanium dioxide by a hydrothermal method. The preparation method provided by the invention is simple in process, easy to operate and suitable for large-scale production; meanwhile, the titanium dioxide coating electrode obtained by the method has good electrocatalytic activity and long service life, is suitable for wastewater treatment equipment and the like, and can effectively degrade organic pollutants in wastewater.
Description
The technical field is as follows:
the invention relates to the technical field of electrocatalysis, in particular to a titanium dioxide coating electrode and a preparation method thereof.
Background art:
the coating electrode is a core component of an electrocatalysis sewage treatment technology, and in recent years, the tin-antimony electrode receives more and more attention due to the advantages of low cost, high oxygen evolution potential and the like, but the defect of poor stability seriously restricts the application of industrialization. If the stability of the tin antimony electrode can be improved, the further popularization of the electro-catalysis sewage treatment technology can be facilitated.
Titanium dioxide is a commonly used photocatalyst, has good catalytic activity in photocatalytic reaction, but cannot be used as an electrode coating material generally due to low conductivity and poor anode activity. The prior art does not disclose the use of titanium dioxide to solve the problems of poor stability and low catalytic activity of the common tin-antimony electrode.
The invention content is as follows:
in order to solve the problems in the prior art, the invention provides a titanium dioxide coating electrode and a preparation method thereof, and solves the problems of poor stability and low catalytic activity of a common tin-antimony electrode.
The invention provides a titanium dioxide coating electrode, which comprises a titanium substrate, a tin-antimony intermediate layer and a titanium dioxide active layer which are connected in sequence, wherein the titanium dioxide is anatase type titanium dioxide with {001} and {101} double crystal faces exposed.
Preferably, the titanium dioxide has the conductivity of 10-3～10-4S/m, the size of titanium dioxide crystal grains is 1-100 nm, and the loading amount of titanium dioxide on the titanium dioxide coating electrode is not less than 0.01mg/cm2The thickness of the tin-antimony intermediate layer is 0.1-100 mu m.
The second purpose of the invention is to provide a preparation method of the titanium dioxide coating electrode, which comprises the following steps: firstly coating a tin-antimony intermediate layer with the thickness of 0.1-100 mu m on a pretreated titanium substrate, and then uniformly coating titanium dioxide on the tin-antimony intermediate layer to obtain a titanium dioxide coating electrode, wherein the titanium dioxide is prepared by the following steps: tetrabutyl titanate and hydrofluoric acid are mixed according to the volume ratio of 4-8:1-2 to prepare the {001} and {101} double crystal face exposed anatase type titanium dioxide by a hydrothermal method.
Preferably, the pretreatment of the titanium substrate comprises the following steps of firstly, repeatedly polishing or sand blasting by using 40-800-mesh sand paper to remove an oxide layer on the surface of the titanium substrate; secondly, placing the titanium substrate with the oxide layer removed in a NaOH solution with the mass fraction of 20-40% and heating the solution at the temperature of 80-95 ℃ for 1-3 hours to remove oil, or placing the titanium substrate in an acetone solution to clean for 10-30 min to remove oil; and finally, placing the degreased titanium matrix in oxalic acid with the mass fraction of 10-40% or hydrochloric acid solution with the volume fraction of 20-50%, and heating for 1-3 hours at the temperature of 80-95 ℃ until the surface of the titanium matrix is tinged and gray to obtain the pretreated titanium matrix.
Preferably, the specific steps of coating the tin-antimony interlayer on the titanium matrix are as follows: dissolving stannous chloride and antimony trioxide in absolute ethyl alcohol according to a molar ratio of 95-105:3, adding concentrated hydrochloric acid to completely dissolve antimony trioxide to obtain a tin-antimony interlayer coating liquid, coating the coating liquid on the surface of the pretreated titanium matrix, calcining the tin-antimony interlayer coating liquid in a muffle furnace at 450-600 ℃ for 3-8 minutes after drying, repeatedly coating the coating liquid for 15-20 times, calcining for 1-2 hours after the last coating, and completely oxidizing the tin-antimony interlayer to realize coating of the tin-antimony interlayer on the titanium matrix.
Preferably, the coating method for coating the tin-antimony interlayer on the titanium substrate is one selected from a brush coating method, a spray pyrolysis method, an electrodeposition method, a dip-coating method and an evaporation method.
Preferably, the hydrothermal reaction temperature is 180-200 ℃, and the hydrothermal reaction time is 24-36 hours.
Preferably, the specific step of uniformly coating titanium dioxide on the tin-antimony intermediate layer is to uniformly disperse the titanium dioxide into the Nafion ethanol mixed solution according to the concentration of 0.1mg/mL to obtain a coating solution, and coating the coating solution on the tin-antimony intermediate layer to obtain the titanium dioxide coated electrode.
Preferably, the coating method of the coating liquid on the tin-antimony intermediate layer is a dripping method, a brushing method or a spraying method.
The invention also protects the application of the titanium dioxide coating electrode in the electrocatalysis sewage treatment.
Compared with the prior art, the invention has the following advantages: the preparation method provided by the invention is simple in process, easy to operate and suitable for large-scale production; meanwhile, the titanium dioxide coating electrode obtained by the method has good electrocatalytic activity and long service life, is suitable for wastewater treatment equipment and the like, and can effectively degrade organic pollutants in wastewater.
Description of the drawings:
FIG. 1 shows the dual crystal face exposed TiO {001} and {101} planes obtained in example 12A micro-topography of the powder;
FIG. 2 is a graph showing the enhanced life test of the electrodes in comparative example and example 1.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art. The room temperature proposed by the present invention means 25 ℃.
A titanium dioxide coating electrode comprises a titanium substrate, a tin-antimony intermediate layer and a titanium dioxide active layer which are sequentially connected, wherein the titanium dioxide is anatase type titanium dioxide with {001} and {101} double crystal faces exposed. The conductivity of the titanium dioxide is 10-3～10- 4S/m, the size of titanium dioxide crystal grains is 1-100 nm, and the loading amount of titanium dioxide on the titanium dioxide coating electrode is not less than 0.01mg/cm2The thickness of the tin-antimony intermediate layer is 0.1-100 mu m.
The preparation method of the titanium dioxide coating electrode comprises the following steps:
(1) pretreatment of a titanium substrate: firstly, repeatedly polishing or sandblasting by using 40-800-mesh sand paper to remove an oxide layer on the surface of a titanium substrate; secondly, placing the titanium substrate with the oxide layer removed in a NaOH solution with the mass fraction of 20-40% and heating the solution at the temperature of 80-95 ℃ for 1-3 hours to remove oil, or placing the titanium substrate in an acetone solution to clean for 10-30 min to remove oil; finally, placing the degreased titanium matrix in oxalic acid with the mass fraction of 10% -40% or hydrochloric acid solution with the mass fraction of 10% -40%, and heating for 1-3 hours at the temperature of 80-95 ℃ until the surface of the titanium matrix is tinged and gray to obtain the pretreated titanium matrix;
(2) coating a tin-antimony interlayer on the titanium substrate: dissolving stannous chloride and antimony trioxide in absolute ethyl alcohol according to a molar ratio of 95-105:3, adding concentrated hydrochloric acid to completely dissolve antimony trioxide to obtain a tin-antimony intermediate layer coating solution, wherein the molar concentration of tin ions in the tin-antimony intermediate layer coating solution is 0.475-0.525mol/L, and the molar concentration of antimony ions is 0.015mol/L, coating the coating solution on the surface of a pretreated titanium substrate, calcining the tin-antimony intermediate layer coating solution in a muffle furnace at 450-600 ℃ for 3-8 minutes after drying, repeatedly coating the coating solution for 15-20 times, calcining for 1-2 hours after the last coating, and completely oxidizing the tin-antimony intermediate layer to realize the coating of the tin-antimony intermediate layer on the titanium substrate;
(3) coating the titanium dioxide active layer to the tin-antimony interlayer: mixing tetrabutyl titanate and hydrofluoric acid according to the volume ratio of 4-6:1, preparing anatase titanium dioxide powder with exposed {001} and {101} double crystal faces through a hydrothermal reaction, uniformly dispersing the obtained titanium dioxide powder into a Nafion ethanol mixed solution according to the concentration of 0.1mg/mL to obtain a coating solution, and coating the coating solution on a tin-antimony intermediate layer to obtain the titanium dioxide coating electrode. The mass fraction of Nafion in the Nafion ethanol mixed solution is 0.05%.
In the present invention, the coating method of coating the tin-antimony interlayer on the titanium substrate is one selected from a brush coating method, a spray pyrolysis method, an electrodeposition method, a dip-draw method, and an evaporation method. The specific parameters of the brush coating method, the spray pyrolysis method, the electrodeposition method, the dip-coating method and the evaporation method are not particularly limited, and the methods and parameters known to those skilled in the art can be adopted as long as the tin-antimony intermediate layer can be coated on the titanium substrate. In the following examples, a tin-antimony intermediate layer is preferably coated on a titanium substrate using a brush coating method.
In the invention, the hydrothermal reaction temperature is 180-200 ℃, and the hydrothermal reaction time is 24-36 hours. In the following examples, the hydrothermal reaction temperature is preferably 180 ℃ and the hydrothermal reaction time is preferably 24 hours.
In the present invention, the coating method of applying the titanium dioxide coating liquid to the tin-antimony intermediate layer is a drop coating method, a brush coating method or a spray coating method. The invention is not particularly limited with respect to the specific parameters of the drop coating method, the brush coating method and the spray coating method, and any method and parameters known to those skilled in the art may be used as long as the titanium dioxide coating solution can be applied to the tin-antimony intermediate layer.
Example 1
The preparation method of the titanium dioxide coating electrode comprises the following steps:
(1) pretreatment of a titanium substrate: mixing 3X 3cm2And repeatedly polishing the titanium plate by using 80-mesh and 400-mesh sand paper in sequence until the titanium plate shows metallic luster. And (3) carrying out ultrasonic treatment on the polished titanium plate for 10 minutes by using deionized water, then placing the titanium plate into a 40 wt% NaOH solution, and heating the titanium plate for 1 hour under the condition of a water bath at 95 ℃. After alkali washing, the titanium plate is taken out and is subjected to ultrasonic treatment for 10 minutes by using deionized water, and then the titanium plate is placed in 50 vol% HCl solution and is kept for 1 hour under the condition of 90 ℃ water bath. And ultrasonically cleaning the steel plate by using deionized water after acid cleaning, and blow-drying the steel plate by using nitrogen flow for later use.
(2) Preparing a tin-antimony interlayer: accurately weighing 0.4373g Sb2O3And 11.2825g SnCl2·2H2Dissolving O in 50mL of absolute ethyl alcohol, dripping a few drops of concentrated hydrochloric acid while stirring until the solution is colorless and transparent, transferring the solution to a volumetric flask, adding ethanol to a constant volume of 100mL to obtain a precursor solution, wherein the molar concentration of tin ions and antimony ions in the precursor solution is 0.5mol/L and 0.015mol/L, dipping the prepared precursor solution by using a brush, uniformly coating the prepared precursor solution on the surface of the titanium plate pretreated in the step (1), drying the titanium plate in a drying box at 100 ℃ for 5 minutes, taking out the titanium plate, and then annealing the titanium plate in a muffle furnace at 550 ℃ for 5 minutes, repeating the coating and annealing processes for 15 times, and finally, annealing for 1 hourAnd completely oxidizing the tin-antimony intermediate layer, taking out the tin-antimony intermediate layer, and naturally cooling to coat the tin-antimony intermediate layer on the titanium matrix.
(3) Preparation of titanium dioxide active layer: slowly dripping 5mL of hydrofluoric acid with the mass fraction of 40% into 25mL of tetrabutyl titanate solution, stirring the solution at the speed of 500rpm, mixing, continuing stirring for 30min, transferring the solution into a 100mL stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a drying oven at 180 ℃ for heat preservation for 24 h. And after the reaction is finished, centrifuging the precipitate, then repeatedly washing the precipitate by using 0.1M NaOH solution, absolute ethyl alcohol and deionized water in sequence, placing the cleaned product in a vacuum drying oven for drying for 12 hours, fully grinding the dried product into titanium dioxide powder for later use, wherein the microscopic morphology of the {001} and {101} double-crystal-face exposed anatase type titanium dioxide is shown in figure 1.
And (3) ultrasonically dispersing 1mg of titanium dioxide powder into 10mL of Nafion ethanol mixed solution with the mass fraction of 0.05%, sucking 0.1mL of mixed solution by a liquid shifter, dripping the mixed solution on the surface of a tin-antimony intermediate layer on the electrode, continuously dripping the mixed solution after the solvent ethanol in the Nafion ethanol mixed solution is volatilized, repeatedly dripping the mixed solution for 10 times, and naturally drying to obtain the titanium dioxide coated electrode.
Comparative example 1
Referring to example 1, the titanium dioxide powder was not coated (i.e., step (3)).
The obtained electrode was subjected to a life strengthening test with the electrode of example 1, and the results are shown in fig. 2.
As can be seen from comparison of example 1 and comparative example 1 in fig. 2, the addition of the titanium dioxide layer can improve the service life of the electrode.
Example 2
The preparation method of the titanium dioxide coating electrode comprises the following steps:
(1) pretreatment of a titanium substrate: mixing 3X 3cm2And repeatedly polishing the titanium plate by using 80-mesh and 400-mesh sand paper in sequence until the titanium plate shows metallic luster. And (3) carrying out ultrasonic treatment on the ground titanium plate for 10 minutes by using deionized water, then placing the titanium plate into a 20 wt% NaOH solution, and heating the titanium plate for 3 hours under the condition of a water bath at 80 ℃. After alkali washing, taking out the titanium plate, performing ultrasonic treatment for 30 minutes by using deionized water, and then placing the titanium plate in a position of 20vol% HCl solution, at 95 ℃ for 1 hour in a water bath. And ultrasonically cleaning the steel plate by using deionized water after acid cleaning, and blow-drying the steel plate by using nitrogen flow for later use.
(2) Preparing a tin-antimony interlayer: weighing Sb2O3And SnCl2·2H2O in 50mL of absolute ethanol, SnCl2·2H2O and Sb2O3The molar ratio of the tin-antimony intermediate layer to the titanium substrate is 95:3, a few drops of concentrated hydrochloric acid are dripped into the solution while stirring the solution until the solution is colorless and transparent, the solution is transferred to a volumetric flask, ethanol is added to the volumetric flask to achieve a constant volume of 100mL to obtain a precursor solution, the molar concentration of tin ions in the precursor solution is 0.475mol/L, the molar concentration of antimony ions is 0.015mol/L, the prepared precursor solution is dipped by a brush and evenly coated on the surface of the titanium plate pretreated in the step (1), the titanium plate is dried in a drying oven at 100 ℃ for 5 minutes, the titanium plate is taken out and then placed in a muffle furnace at 450 ℃ for annealing for 5 minutes, the coating and annealing processes are repeated for 20 times, the last annealing is kept for 2 hours, the tin-antimony intermediate layer is thoroughly oxidized, and the titanium substrate is naturally cooled after being taken out, so that.
(3) Preparation of titanium dioxide active layer: slowly dripping 5mL of hydrofluoric acid with the mass fraction of 40% into 20mL of tetrabutyl titanate solution, stirring the solution at the speed of 500rpm, mixing, continuing stirring for 30min, transferring the solution into a 100mL stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a 190 ℃ drying oven for heat preservation for 30 h. Centrifuging the precipitate after the reaction is finished, then repeatedly washing the precipitate by using 0.1M NaOH solution, absolute ethyl alcohol and deionized water in sequence, drying the cleaned product in a vacuum drying oven for 12 hours, and fully grinding the dried product into titanium dioxide powder for later use;
and (3) ultrasonically dispersing 1mg of titanium dioxide powder into 10mL of Nafion ethanol mixed solution with the mass fraction of 0.05%, sucking 0.1mL of mixed solution by a liquid shifter, dripping the mixed solution on the surface of a tin-antimony intermediate layer on the electrode, continuously dripping the mixed solution after the solvent ethanol in the Nafion ethanol mixed solution is volatilized, repeatedly dripping the mixed solution for 10 times, and naturally drying to obtain the titanium dioxide coated electrode.
Example 3
The preparation method of the titanium dioxide coating electrode comprises the following steps:
(1) pretreatment of a titanium substrate: mixing 3X 3cm2And repeatedly polishing the titanium plate by using 80-mesh and 400-mesh sand paper in sequence until the titanium plate shows metallic luster. And (2) carrying out ultrasonic treatment on the polished titanium plate for 10 minutes by using deionized water, then placing the titanium plate into a 40 wt% NaOH solution, heating the titanium plate for 1 hour under the condition of a water bath at 95 ℃, taking out the titanium plate after alkali cleaning, carrying out ultrasonic treatment on the titanium plate for 30 minutes by using the deionized water, then placing the titanium plate into a 40 vol% HCl solution, and keeping the titanium plate for 3 hours under the condition of a water bath at 80 ℃. And ultrasonically cleaning the steel plate by using deionized water after acid cleaning, and blow-drying the steel plate by using nitrogen flow for later use.
(2) Preparing a tin-antimony interlayer: weighing Sb2O3And SnCl2·2H2O in 50mL of absolute ethanol, SnCl2·2H2O and Sb2O3The molar ratio of the tin to the antimony is 105:3, dropwise adding a few drops of concentrated hydrochloric acid while stirring until the solution is colorless and transparent, transferring the solution to a volumetric flask, adding ethanol to achieve a constant volume of 100mL to obtain a precursor solution, wherein the molar concentration of tin ions in the precursor solution is 0.525mol/L, the molar concentration of antimony ions is 0.015mol/L, dipping the prepared precursor solution by a brush, uniformly coating the prepared precursor solution on the surface of the titanium plate pretreated in the step (1), then placing the titanium plate in a drying box at 100 ℃ for drying for 5 minutes, taking out the titanium plate, then placing the titanium plate in a muffle furnace at 600 ℃ for annealing for 5 minutes, repeating the coating and annealing processes for 20 times, keeping the last annealing for 2 hours to completely oxidize the tin-antimony intermediate layer, taking out the titanium-based intermediate layer and naturally cooling to realize the coating of the tin-antimony intermediate layer on the titanium-.
(3) Preparation of titanium dioxide active layer: slowly dripping 5mL of hydrofluoric acid with the mass fraction of 40% into 30mL of tetrabutyl titanate solution, stirring the solution at the speed of 500rpm, mixing, continuing stirring for 30min, transferring the solution into a 100mL stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a drying oven at 200 ℃ for heat preservation for 24 h. Centrifuging the precipitate after the reaction is finished, then repeatedly washing the precipitate by using 0.1M NaOH solution, absolute ethyl alcohol and deionized water in sequence, drying the cleaned product in a vacuum drying oven for 12 hours, and fully grinding the dried product into titanium dioxide powder for later use;
and (3) ultrasonically dispersing 1mg of titanium dioxide powder into 10mL of Nafion ethanol mixed solution with the mass fraction of 0.05%, sucking 0.1mL of mixed solution by a liquid shifter, dripping the mixed solution on the surface of a tin-antimony intermediate layer on the electrode, continuously dripping the mixed solution after the solvent ethanol in the Nafion ethanol mixed solution is volatilized, repeatedly dripping the mixed solution for 10 times, and naturally drying to obtain the titanium dioxide coated electrode.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A titanium dioxide coating electrode is characterized by comprising a titanium substrate, a tin-antimony intermediate layer and a titanium dioxide active layer which are sequentially connected, wherein the titanium dioxide is anatase type titanium dioxide with {001} and {101} double crystal faces exposed.
2. The titanium dioxide coated electrode of claim 1, wherein the titanium dioxide has an electrical conductivity of 10-3～10-4S/m, the size of titanium dioxide crystal grains is 1-100 nm, and the loading amount of titanium dioxide on the titanium dioxide coating electrode is not less than 0.01mg/cm2The thickness of the tin-antimony intermediate layer is 0.1-100 mu m.
3. The method of preparing a titania-coated electrode according to claim 1, comprising the steps of: firstly coating a tin-antimony intermediate layer with the thickness of 0.1-100 mu m on a pretreated titanium substrate, and then uniformly coating titanium dioxide on the tin-antimony intermediate layer to obtain a titanium dioxide coating electrode, wherein the titanium dioxide is prepared by the following steps: tetrabutyl titanate and hydrofluoric acid are mixed according to the volume ratio of 4-8:1-2 to prepare the {001} and {101} double crystal face exposed anatase type titanium dioxide by a hydrothermal method.
4. The method for preparing the titanium dioxide coated electrode according to claim 3, wherein the pretreatment of the titanium substrate comprises the following steps of firstly, repeatedly grinding or sand blasting 40-800 meshes of sand paper in sequence to remove an oxide layer on the surface of the titanium substrate; secondly, placing the titanium substrate with the oxide layer removed in a NaOH solution with the mass fraction of 20-40% and heating the solution at the temperature of 80-95 ℃ for 1-3 hours to remove oil, or placing the titanium substrate in an acetone solution to clean for 10-30 min to remove oil; and finally, placing the degreased titanium matrix in oxalic acid with the mass fraction of 10-40% or hydrochloric acid solution with the volume fraction of 20-50%, and heating for 1-3 hours at the temperature of 80-95 ℃ until the surface of the titanium matrix is tinged and gray to obtain the pretreated titanium matrix.
5. The method for preparing the titanium dioxide coated electrode according to claim 3, wherein the step of coating the tin-antimony interlayer on the titanium substrate comprises the following steps: dissolving stannous chloride and antimony trioxide in absolute ethyl alcohol according to a molar ratio of 95-105:3, adding concentrated hydrochloric acid to completely dissolve antimony trioxide to obtain a tin-antimony interlayer coating liquid, coating the coating liquid on the surface of the pretreated titanium matrix, calcining the tin-antimony interlayer coating liquid in a muffle furnace at 450-600 ℃ for 3-8 minutes after drying, repeatedly coating the coating liquid for 15-20 times, calcining for 1-2 hours after the last coating, and completely oxidizing the tin-antimony interlayer to realize coating of the tin-antimony interlayer on the titanium matrix.
6. The method for preparing the titanium dioxide coated electrode according to claim 5, wherein the coating method for coating the tin-antimony interlayer on the titanium substrate is one selected from a brush coating method, a spray pyrolysis method, an electrodeposition method, a dip-coating method and an evaporation method.
7. The method for preparing the titanium dioxide coating electrode according to claim 3, wherein the hydrothermal reaction temperature is 180-200 ℃ and the hydrothermal reaction time is 24-36 hours.
8. The method for preparing the titanium dioxide coated electrode according to claim 3, wherein the step of uniformly coating titanium dioxide on the tin-antimony intermediate layer comprises the steps of uniformly dispersing titanium dioxide into a Nafion ethanol mixed solution according to the concentration of 0.1mg/mL to obtain a coating solution, and coating the coating solution on the tin-antimony intermediate layer to obtain the titanium dioxide coated electrode.
9. The method for preparing a titanium dioxide coated electrode according to claim 8, wherein the coating method of the coating solution on the tin-antimony intermediate layer is a dropping coating method, a brushing coating method or a spraying coating method.
10. Use of a titanium dioxide coated electrode according to claim 1 in electrocatalytic sewage treatment.
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