A modified titanium-based coating electrode and a preparation method and application thereof

Abstract

This invention belongs to the field of electrocatalytic oxidation technology, specifically disclosing a modified titanium-based coated electrode, its preparation method, and its application. The electrode, from bottom to top, consists of a titanium substrate etched with mixed acid, a zirconium tin oxide intermediate layer constructed by thermal decomposition, and an electrodeposited lead dioxide active layer. The modified titanium-based coated electrode is applied to the electrocatalytic oxidation degradation of organic dye wastewater. The modified titanium-based coated electrode provided by this invention has low manufacturing cost. The lead dioxide active layer has a dense tetrahedral pyramidal structure, which effectively prevents reactive oxygen species from penetrating the electrode surface, protects the outer layer from detachment, improves electrode performance, extends electrode lifespan, and provides abundant active sites for efficient electrocatalytic degradation of organic pollutants.

Description

Technical Field

[0001] This invention relates to the field of electrocatalytic oxidation technology, specifically to a modified titanium-based coated electrode, its preparation method, and its application. Background Technology

[0002] The performance of electrocatalytic oxidation systems largely depends on the performance of the electrode materials, and the preparation method and process of these materials are the most important factors determining their performance. The active layer on the surface of the anode material is crucial for the degradation reaction. Lead dioxide coated electrodes with titanium as the substrate are widely used in electrocatalytic oxidation due to their advantages such as low cost and high oxygen evolution potential, making them one of the most important electrode materials. However, traditional Ti / PbO2 electrodes suffer from high interfacial stress during electrolysis, which easily leads to coating peeling and shortened lifespan, severely limiting their practical applications.

[0003] Adding a suitable intermediate layer can effectively enhance the adhesion between coatings. The strength of the adhesion between the coating and the substrate material directly affects the service life. This adhesion is mainly determined by mechanical adhesion, which depends on the surface roughness of the substrate material, the coverage area of ​​the coating, and its mechanical strength. Currently, the intermediate layers of Ti / PbO2 electrodes are generally composed of platinum palladium oxide, tin antimony oxide, iridium oxide, and ruthenium oxide. Adding an intermediate layer can significantly improve the electrocatalytic oxidation activity and service life of titanium-based coated electrodes.

[0004] To date, there are few reports of introducing Zr and its oxides as intermediate layers into coated titanium electrodes. Summary of the Invention

[0005] In view of the above-mentioned shortcomings, the present invention provides a modified titanium-based coated electrode, its preparation method and application. The modified titanium-based coated electrode provided by the present invention has low manufacturing cost, and the lead dioxide active layer is a dense tetragonal pyramidal structure. This structure can effectively prevent reactive oxygen from penetrating the electrode surface, protect the outer layer of the electrode from falling off, improve electrode performance, extend electrode life, and provide abundant active sites for efficient electrocatalytic degradation of organic pollutants.

[0006] To achieve the above objectives, the present invention provides a modified titanium-based coated electrode, which, from bottom to top, consists of a titanium substrate etched by mixed acid, a zirconium tin oxide intermediate layer constructed by thermal decomposition, and an electrodeposited lead dioxide active layer.

[0007] Based on the same inventive concept, the present invention also provides a method for preparing the above-mentioned modified titanium-based coated electrode, comprising the following steps:

[0008] S1. Titanium matrix pretreatment:

[0009] A mixed acid solution was prepared and heated to the etching temperature. The solution was then placed into an ultrasonically treated titanium substrate for etching to obtain a pretreated titanium substrate.

[0010] S2. Construction of zirconium tin oxide intermediate layer by thermal decomposition method:

[0011] An intermediate layer impregnation solution was prepared and coated onto the pretreated titanium substrate using a repeated impregnation-drying thermal decomposition method. After the final impregnation, the impregnated titanium substrate was placed in a vacuum tube furnace for high-temperature sintering to obtain a zirconium tin oxide solid solution intermediate layer.

[0012] S3, Electrodeposited lead dioxide active layer:

[0013] A lead dioxide electroplating solution was prepared, and the intermediate layer of zirconium tin oxide solid solution was electrodeposited in the lead dioxide electroplating solution. The electrode was then washed with deionized water to obtain a Ti / Zr-SnO2 / β-PbO2 electrode.

[0014] According to one aspect of the invention, in step S1, the mixed acid solution comprises sulfuric acid and tartaric acid.

[0015] According to one aspect of the present invention, in step S2, the Zr, Sn, and O elements in the zirconium tin oxide intermediate layer are uniformly distributed on the surface of the titanium substrate.

[0016] It should be noted that the intermediate layer of zirconium tin oxide solid solution is constructed by thermal decomposition, so that Zr, Sn and O elements are uniformly covered on the surface of titanium substrate, which effectively avoids the formation of titanium dioxide on the surface of titanium substrate and causes problems such as easy peeling of coating.

[0017] According to one aspect of the present invention, in step S2, the molar ratio of Sn to Zr in the intermediate layer impregnation solution is 8 to 10:1.

[0018] According to one aspect of the present invention, in step S2, the repeated impregnation-drying thermal decomposition method specifically involves: impregnating the pretreated titanium substrate with an intermediate impregnation solution, then transferring it to an oven at 160-190°C for heat treatment for 4-8 minutes, and after the surface is dry, continuing the impregnation-drying process. The entire operation needs to be repeated 14-16 times; the high-temperature sintering temperature is 430-470°C, and the time is 50-80 minutes.

[0019] According to one aspect of the present invention, in step S2, the intermediate layer impregnation solution includes a zirconium salt and a tin salt, wherein the zirconium salt is one of anhydrous zirconium tetrachloride and tetrabutyl zirconate, and the tin salt is one of stannous chloride and alkoxytin.

[0020] According to one aspect of the present invention, in step S3, β-PbO2 is prepared by electrodeposition.

[0021] According to one aspect of the present invention, in step S3, the electrodeposition specifically involves: at 50–70°C and at an electrodeposition rate of 30–50 mA / cm. 2 Electrodeposition at a current density for 15–25 minutes.

[0022] Based on the same inventive concept, the present invention also provides the application of the modified titanium-based coated electrode or the modified titanium-based coated electrode prepared by any of the above preparation methods in the electrocatalytic oxidation degradation of organic dye wastewater.

[0023] The principle of this invention:

[0024] This invention selects zirconium-tin oxide as the intermediate layer, uniformly coating Zr, Sn, and O elements onto the surface of a titanium substrate to increase the coating coverage area and improve the adhesion between the titanium substrate and the lead dioxide active layer. Zirconium and titanium are in the same group, as are tin and lead, and both PbO2 and SnO2 are tetragonal with similar crystal structures. Constructing the zirconium-tin oxide solid solution intermediate layer via thermal decomposition effectively reduces the internal stress between the titanium substrate and the lead dioxide active layer, effectively preventing the diffusion of oxygen molecules or atoms to the titanium substrate surface and avoiding the formation of titanium dioxide on the titanium substrate surface, which would cause the coating to peel off. Using Zr-SnO2 as the intermediate layer can significantly increase the adhesion between the titanium substrate and the lead dioxide active layer, increase the conductivity of the electrode, reduce the electrode resistance, improve electrode stability, and extend the electrode's lifespan, demonstrating great application potential in the field of electrocatalytic oxidation.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] (1) The present invention performs mixed acid etching on the titanium substrate to obtain a titanium substrate material with dense and uniform surface pores, thereby increasing the contact area with zirconium tin oxide.

[0027] (2) In this invention, zirconium salt and tin salt are uniformly impregnated on the surface of the etched titanium substrate by impregnation-drying and then sintered at high temperature to obtain the zirconium tin oxide intermediate layer with irregular crack structure generated by the alternating high temperature and room temperature changes that is unique to the intermediate layer prepared by thermal decomposition method. The particles are relatively uniform in size and have good crystallinity, which can provide sufficient nucleus growth sites for electrodeposition of lead dioxide, which is conducive to rapid electrodeposition of lead dioxide active layer, so that the lead dioxide active layer is more firmly bonded to the titanium substrate.

[0028] (3) The zirconium in the zirconium tin oxide intermediate layer of the present invention is a group element with titanium in the titanium matrix, and the tin in the zirconium tin oxide intermediate layer is a group element with lead in the lead dioxide active layer. Moreover, PbO2 and SnO2 are both tetragonal crystal systems and have similar crystal structures. By selecting zirconium tin oxide as the intermediate layer, the internal stress between the titanium matrix and the lead dioxide active layer can be effectively reduced, the bonding force between the titanium matrix and the lead dioxide active layer can be significantly increased, the electrode stability can be improved, and the electrode service life can be enhanced.

[0029] (4) The manufacturing principle of the zirconium tin oxide intermediate layer modified titanium-based coating electrode of the present invention is scientific and reliable, the preparation process is simple, no complicated equipment is required, and the electrode has excellent electrocatalytic oxidation performance, which greatly reduces the difficulty of preparing complex titanium-based coating electrodes. Attached Figure Description

[0030] Figure 1 The cyclic voltammetry curves of the titanium-based coated electrodes prepared in Example 1 and Comparative Example 1 of this invention are shown below.

[0031] Figure 2 The accelerated lifetime test curves of the titanium-based coated electrodes prepared in Example 1 and Comparative Example 1 of the present invention are shown.

[0032] Figure 3 This is a scanning electron microscope image of the titanium-based coated electrode prepared in Comparative Example 1 of the present invention;

[0033] Figure 4 This is a scanning electron microscope image of the titanium-based coated electrode prepared in Example 1 of the present invention;

[0034] Figure 5 The image shows the elemental mapping of the Ti / SnO2 electrode prepared in Example 1 of this invention; where A represents Ti, B represents Sn, C represents Zr, and D represents O. Detailed Implementation

[0035] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0036] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0037] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0038] To enhance the bonding force between Ti / PbO2 electrode coatings in the electrocatalytic oxidation system, and to enable the titanium-based coated electrode to have excellent electrocatalytic activity, higher stability and longer service life, the inventors of this application provide a modified titanium-based coated electrode, which consists of a titanium substrate etched by mixed acid, a zirconium tin oxide intermediate layer constructed by thermal decomposition, and an electrodeposited lead dioxide active layer from bottom to top.

[0039] The embodiments of this application also provide a method for preparing the above-mentioned modified titanium-based coated electrode, including the following steps:

[0040] S1. Titanium matrix pretreatment:

[0041] A mixed acid solution was prepared and heated to the etching temperature. The solution was then placed into an ultrasonically treated titanium substrate for etching to obtain a pretreated titanium substrate.

[0042] S2. Construction of zirconium tin oxide intermediate layer by thermal decomposition method:

[0043] An intermediate layer impregnation solution was prepared and coated onto the pretreated titanium substrate using a repeated impregnation-drying thermal decomposition method. After the final impregnation, the impregnated titanium substrate was placed in a vacuum tube furnace for high-temperature sintering to obtain a zirconium tin oxide solid solution intermediate layer.

[0044] S3, Electrodeposited lead dioxide active layer:

[0045] A lead dioxide electroplating solution was prepared, and the intermediate layer of zirconium tin oxide solid solution was electrodeposited in the lead dioxide electroplating solution. The electrode was then washed with deionized water to obtain a Ti / Zr-SnO2 / β-PbO2 electrode.

[0046] As an optional implementation, in step S1, the mixed acid solution includes sulfuric acid and tartaric acid.

[0047] As an optional implementation, in step S2, the Zr, Sn, and O elements in the zirconium tin oxide intermediate layer are uniformly distributed on the surface of the titanium substrate.

[0048] As an optional implementation, in step S2, the molar ratio of Sn to Zr in the intermediate layer impregnation solution is 8 to 10:1.

[0049] As an optional implementation, in step S2, the repeated impregnation-drying thermal decomposition method specifically involves: impregnating the pretreated titanium substrate with an intermediate impregnation solution, then transferring it to an oven at 160-190°C for heat treatment for 4-8 minutes. After the surface is dry, the impregnation-drying process is repeated 14-16 times. The high-temperature sintering temperature is 430-470°C, and the time is 50-80 minutes.

[0050] As an optional implementation, in step S2, the intermediate layer impregnation solution includes zirconium salt and tin salt, wherein the zirconium salt is one of anhydrous zirconium tetrachloride and tetrabutyl zirconate, and the tin salt is one of stannous chloride and alkoxytin.

[0051] As an optional implementation, in step S3, β-PbO2 is prepared by electrodeposition.

[0052] As an optional implementation, in step S3, the electrodeposition specifically involves: at 50–70°C and an electrodeposition rate of 30–50 mA / cm. 2 Electrodeposition at a current density for 15–25 minutes.

[0053] The embodiments of this application also provide the application of the modified titanium-based coated electrode or the modified titanium-based coated electrode prepared by any of the above preparation methods in the electrocatalytic oxidation degradation of organic dye wastewater.

[0054] The specific implementation methods of this application have been described above. In order to objectively illustrate the technical effects produced by this application, the following examples and comparative examples will be used to describe them.

[0055] Example 1

[0056] The specific process for preparing a zirconium tin oxide intermediate layer modified titanium-based coated electrode according to this embodiment includes three steps: titanium substrate pretreatment, thermal decomposition to construct the zirconium tin oxide intermediate layer, and electrodeposition of the lead dioxide active layer.

[0057] (1) Titanium matrix pretreatment

[0058] First, cut the titanium substrate into 2cm×4cm pieces, place them in acetone for ultrasonic cleaning for 40 minutes, then remove them with tweezers and let them air dry for later use.

[0059] Then, prepare 100 mL each of 20% sulfuric acid and 15% tartaric acid solutions, seal them for later use, and mix the sulfuric acid and tartaric acid solutions at a volume ratio of 2:1 to prepare mixed acid.

[0060] Finally, the mixed acid solution was heated to 100°C and placed into the titanium substrate for etching. The etching time was 60 minutes. After etching, the titanium substrate was removed with tweezers and rinsed several times with deionized water. It was then placed on filter paper, dried at room temperature, and sealed for storage.

[0061] (2) Construction of Zr-SnO2 intermediate layer by thermal decomposition method

[0062] First, according to the molar ratio of Sn to Zr of 9:1 and the total mass of metal elements of 10mg, SnCl2·2H2O and ZrCl4 were weighed and dissolved in ethanol, and 0.5mL of concentrated hydrochloric acid was added to inhibit hydrolysis. Ethanol was then added to make up to a volume of 5.0mL to prepare the intermediate layer impregnation solution for the titanium matrix (2cm×4cm).

[0063] Then, the intermediate layer solution is coated by immersion, and then it is placed in an oven for heat treatment at 180°C for 5 minutes. After the surface is dry, the immersion-drying process is repeated 14-16 times.

[0064] After the final impregnation, the electrode is placed in a vacuum tube furnace and heat-treated at 450°C for 60 minutes. After cooling to room temperature, the titanium substrate is removed to obtain an electrode coated with a zirconium tin oxide solid solution intermediate layer.

[0065] (3) Electrodeposition of β-PbO2 active layer

[0066] First, prepare 100 mL of β-PbO2 electroplating solution containing 0.5 mol / L Pb(NO3)2, 0.04 mol / L NaF, and 0.1 mol / L HNO3;

[0067] Then, using a Ti / Zr-SnO2 electrode (1cm × 1cm) with an intermediate layer as the anode and a platinum sheet electrode of the same size as the cathode, an experiment was conducted at 60°C with an A / cm² pressure of 40mA. 2 Electrodeposition was performed at a current density of 50 mL in β-PbO2 electroplating solution for 20 min.

[0068] Finally, the electrode was washed with deionized water to obtain the Ti / Zr-SnO2 / β-PbO2 electrode.

[0069] In the preparation process of the zirconium tin oxide interlayer involved in this embodiment, the interlayer solution is coated by an immersion method, which can uniformly coat Zr, Sn, and O elements on a titanium substrate with dense and uniform surface pores. This can significantly improve the bonding force between the titanium substrate and the lead dioxide active layer, avoiding the disadvantages of titanium coated electrodes such as easy coating peeling. Furthermore, the interlayer contains an irregular crack structure unique to thermal decomposition preparation, which further increases the surface area of ​​the titanium substrate. This is conducive to rapid electrodeposition and generation of a dense, pyramidal β-PbO2 active layer. This can effectively prevent oxygen molecules or oxygen atoms from diffusing to the surface of the titanium substrate, avoiding the formation of titanium dioxide on the surface of the titanium substrate and causing coating peeling. It can also increase the surface area of ​​the active layer and the electrocatalytic oxidation active sites. Zirconium and titanium are in the same group, as are tin and lead. Furthermore, PbO2 and SnO2 are both tetragonal. Constructing a zirconium-tin oxide intermediate layer through thermal decomposition can effectively reduce the internal stress between the titanium substrate and the lead dioxide active layer, significantly increase the bonding force between them, increase electrode conductivity, reduce electrode resistance, improve electrocatalytic oxidation efficiency, enhance electrode stability, and extend electrode lifespan. This method has enormous application potential in the field of electrocatalytic oxidation.

[0070] Comparative Example 1

[0071] The specific process for preparing a modified titanium-based coated electrode involved in this embodiment includes three steps: titanium substrate pretreatment and electrodeposition of a lead dioxide active layer.

[0072] (1) Titanium matrix pretreatment

[0073] First, cut the titanium substrate into 2cm×4cm pieces, place them in acetone for ultrasonic cleaning for 40 minutes, then remove them with tweezers and let them air dry for later use.

[0074] Then, prepare 100 mL each of 20% sulfuric acid and 15% tartaric acid solutions, seal them for later use, and mix the sulfuric acid and tartaric acid solutions at a volume ratio of 2:1 to prepare mixed acid.

[0075] Finally, the mixed acid solution was heated to 100°C and placed into the titanium substrate for etching. The etching time was 60 minutes. After etching, the titanium substrate was removed with tweezers and rinsed several times with deionized water. It was then placed on filter paper, dried at room temperature, and sealed for storage.

[0076] (2) Electrodeposition of β-PbO2 active layer

[0077] First, prepare 100 mL of β-PbO2 electroplating solution containing 0.5 mol / L Pb(NO3)2, 0.04 mol / L NaF, and 0.1 mol / L HNO3;

[0078] Then, using a pretreated Ti electrode (1cm × 1cm) as the anode and a platinum sheet electrode of the same size as the cathode, an anode was applied at 60°C at 40 mA / cm. 2 Electrodeposition was performed at a current density of 50 mL in β-PbO2 electroplating solution for 20 min.

[0079] Finally, the electrode was washed with deionized water to obtain the Ti / β-PbO2 electrode.

[0080] Performance testing and results analysis:

[0081] The metal oxide electrodes prepared in Example 1 and Comparative Example 1 were subjected to performance testing and analysis:

[0082] (1) Cyclic voltammetry (CV) is often used to characterize the electrochemical behavior of oxide electrodes. The cyclic voltammetry (CV) curves of Ti / β-PbO2 electrode (Comparative Example 1) and Ti / Zr-SnO2 / β-PbO2 electrode (Example 1) in 0.1 mol / L Na2SO4 (50 mL) solution are shown below. Figure 1 As shown, by Figure 1 It can be seen that the oxygen evolution overpotential of the Ti / Zr-SnO2 / β-PbO2 electrode is about 1.7V, while the oxygen evolution overpotential of the Ti / β-PbO2 electrode without the intermediate layer is only 1.5V. This indicates that the introduction of the zirconium tin oxide intermediate layer can significantly improve the oxygen evolution overpotential of the electrode, avoid the occurrence of oxygen evolution side reactions, reduce charge transfer resistance, and thus promote its electrocatalytic oxidation ability.

[0083] (2) Accelerated lifetime testing can evaluate the stability of metal oxide electrodes. Generally, electrode stability is an important performance characteristic in practical applications, and it is often used to investigate the rate at which the PbO2 active layer detaches from the titanium substrate. At a current density of 10000 A / m... 2 Accelerated life tests were conducted on the Ti / β-PbO2 electrode of Comparative Example 1 and the Ti / Zr-SnO2 / β-PbO2 electrode of Example 1 in a 15 wt.% H2SO4 aqueous solution using a DC power supply. Voltage changes were recorded to evaluate the stability and lifespan of the electrodes. The test was terminated when the battery voltage exceeded 10V. The results are as follows. Figure 2 As shown, the lifespan of the Ti / Zr-SnO2 / β-PbO2 electrode is 219.5 times that of the Ti / β-PbO2 electrode, indicating that the zirconium tin oxide interlayer can significantly improve the stability and lifespan of the electrode.

[0084] (3) Scanning electron microscopy (SEM) can be used to analyze microstructure. Scanning the prepared electrode yields results such as... Figure 3 , Figure 4The microscopic images shown reveal an irregular crack structure on the surface of the Ti / Zr-SnO2 electrode, resulting from the alternating high and low temperature variations characteristic of the intermediate layer prepared by the thermal decomposition method. The electrodeposited Ti / Zr-SnO2 / β-PbO2 electrode exhibits a dense tetrahedral structure that completely covers and protects the zirconium tin oxide intermediate layer and the titanium substrate.

[0085] (4) Elemental mapping can be used to analyze the elemental distribution on the electrode surface. Elemental mapping analysis was performed on an electrode with an intermediate layer, and the results are as follows: Figure 5 As shown, the zirconium tin oxide composite coating is uniformly covered on the etched titanium substrate surface, with Zr, Sn, and O elements evenly distributed.

[0086] (5) Using methylene blue solution as the target contaminant, the Ti / Zr-SnO2 / β-PbO2 electrode prepared in Example 1 was used as the anode, and a platinum sheet electrode of the same size was used as the cathode, at 50 mA / cm 2 When the current density decreases to degrade a methylene blue solution with an initial concentration of 50.00 mg / L, the methylene blue removal rate can reach 97% within 180 min, indicating that the Ti / Zr-SnO2 / β-PbO2 electrode has great application potential in the degradation of organic dyes and other electrocatalytic oxidation fields.

[0087] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A modified titanium-based coated electrode, characterized in that, The electrode consists of, from the inside out, a titanium substrate etched by mixed acid, a zirconium tin oxide intermediate layer constructed by thermal decomposition, and an electrodeposited β-PbO2 active layer.

2. The method for preparing the modified titanium-based coated electrode according to claim 1, characterized in that, Includes the following steps: S1. Titanium matrix pretreatment: A mixed acid solution was prepared and heated to the etching temperature. The solution was then placed into an ultrasonically treated titanium substrate for etching to obtain a pretreated titanium substrate. S2. Construction of zirconium tin oxide intermediate layer by thermal decomposition method: An intermediate layer impregnation solution was prepared and coated onto the pretreated titanium substrate using a repeated impregnation-drying thermal decomposition method. After the final impregnation, the impregnated titanium substrate was placed in a vacuum tube furnace for high-temperature sintering to obtain a zirconium tin oxide solid solution intermediate layer. S3, Electrodeposited lead dioxide active layer: A lead dioxide electroplating solution was prepared, and a zirconium tin oxide solid solution intermediate layer was electrodeposited in the lead dioxide electroplating solution. The solution was then washed with deionized water to obtain a Ti / Zr-SnO2 / β-PbO2 electrode.

3. The method for preparing the modified titanium-based coated electrode according to claim 2, characterized in that, In step S1, the mixed acid solution includes sulfuric acid and tartaric acid.

4. The method for preparing the modified titanium-based coated electrode according to claim 2, characterized in that, In step S2, the Zr, Sn, and O elements in the zirconium tin oxide intermediate layer are uniformly distributed on the surface of the titanium substrate.

5. The method for preparing the modified titanium-based coated electrode according to claim 2, characterized in that, In step S2, the molar ratio of Sn to Zr in the intermediate layer impregnation solution is 8~10:

1.

6. The method for preparing the modified titanium-based coated electrode according to claim 2, characterized in that, In step S2, the repeated impregnation-drying thermal decomposition method specifically involves: impregnating the pretreated titanium substrate with an intermediate impregnation solution, then transferring it to an oven at 160~190℃ for heat treatment for 4~8 minutes. After the surface is dry, the impregnation-drying process is repeated 14~16 times. The high-temperature sintering temperature is 430~470℃, and the time is 50~80 minutes.

7. The method for preparing the modified titanium-based coated electrode according to claim 2, characterized in that, In step S2, the intermediate layer impregnation solution includes zirconium salt and tin salt. The zirconium salt is one of anhydrous zirconium tetrachloride and tetrabutyl zirconate, and the tin salt is one of stannous chloride and alkoxytin.

8. The method for preparing the modified titanium-based coated electrode according to claim 2, characterized in that, In step S3, the electrodeposition specifically involves: at 50~70°C and at a rate of 30~50 mA / cm 2 Electrodeposition at a current density for 15-25 minutes.

9. The application of a modified titanium-based coated electrode as described in claim 1 or a modified titanium-based coated electrode prepared by any of the preparation methods described in claims 2-8 in the electrocatalytic oxidation degradation of organic dye wastewater.

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