CN114249394A - Preparation method of stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode - Google Patents
Preparation method of stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode Download PDFInfo
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Abstract
The invention relates to a preparation method of a stannum-antimony doped titanium suboxide intermediate layer micropore ruthenium dioxide electrode, which takes micropore titanium as a substrate, prepares a titanium dioxide nanotube by adopting an anodic oxidation method, prepares the titanium suboxide nanotube by adopting a high-temperature reduction method, prepares a solution by tin salt and antimonous salt according to a certain proportion as a precursor, forms a stannum-antimony doped titanium suboxide intermediate layer by high-temperature decomposition after being induced to the titanium suboxide nanotube in vacuum, and finally adopts a vacuum induction technology and a sol-gel technology to prepare a ruthenium dioxide catalyst layer on the prepared intermediate layer. The obtained electrode has the advantages of large specific surface area and strong stability. Meanwhile, the electrode has high mass transfer efficiency due to the microporous structure, and the prepared active layer has the advantages of compact surface, no crack and long service life. The electrode has simple preparation process, can be industrially produced, is suitable for the field of treating wastewater by an electrochemical oxidation technology, can also be used for a chlor-alkali production process, and has good application prospect.
Description
Technical Field
The invention relates to a preparation method of a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode, belonging to the technical field of electrode materials.
Background
Organic wastewater, especially chemical organic wastewater, often contains organic pollutants difficult to degrade, such as organic pollutants of cyproconazole in pesticide wastewater, organic pollutants of pyrimidine in medical wastewater, and organic pollutants of heterocyclic ring in printing and dyeing wastewater. The pollutants are characterized by stable chemical structure and are difficult to naturally degrade, and the conventional wastewater treatment means such as a biological method cannot realize efficient removal. The electrochemical oxidation method can realize the degradation of the refractory organic pollutants through hydroxyl free radicals (. OH) generated in the reaction process, so as to mineralize the pollutants. The electrochemical oxidation technology is an environment-friendly technology, has the characteristics of high removal rate, simplicity and convenience in operation, easiness in automation, small occupied space and easiness in large-scale use, and is concerned by researchers in recent years. The key for promoting the development of the electrochemical oxidation technology lies in the development of an anode material, and the anode material has high catalytic efficiency and good conductivity and stability.
A common anode material is mainly ruthenium dioxide (RuO)2) Iridium pentoxide (Ir)2O5) Manganese dioxide (MnO)2) Tin dioxide (SnO)2) Lead dioxide (PbO)2) Boron-doped diamond (BDD) and titanium (Ti) oxide4O7) And a composite electrode with several coatings doped with each other. Electrodes can be generally divided into "active" and "inactive" electrodes, depending on the oxygen evolution potential of the electrode material. Of the several electrodes listed above, the first three are "active" electrodes and the last four are "inactive" electrodes. The "active" electrode interacts with OH during the reaction to form a higher valence oxidantFollowed by the degradation of the contaminants. Whereas "inactive" electrodes have a weaker interaction with OH, which exists on the electrode surface only by virtue of weak physical adsorption, so that the degradation of contaminants is mainly accomplished by OH. Thus, the "inactive" electrode has a greater ability to degrade contaminants than the "active" electrode, and the contaminants are degraded more thoroughly. However, these four common "inactive" electrodes have drawbacks that limit their utility. For example, SnO2The stability of the electrode is poor, the service life is short, and the electrode cannot bear industrial application; PbO2The layer is easy to fall off, and the preparation of the microporous electrode is difficult, so that the industrial production is difficult; BDD has high material cost or preparation cost and cannot be popularized; ti4O7The stability under the anode condition is insufficient and the titanium dioxide is easily converted, so that the catalytic activity is reduced. In addition, the wastewater treatment is not necessarily completely degraded, and only needs to be converted into small molecular acid or alcohol with strong biodegradability, and the complete degradation is not necessary and can increase energy consumption, so that the active electrode has own advantages to a certain extent.
Disclosure of Invention
The invention aims to solve the performance defects of the existing electrode material, and provides a preparation method of a stannum-antimony doped titanium oxide intermediate layer microporous ruthenium dioxide electrode, which has the advantages of simple process and strong operability, and the prepared electrode has high mass transfer efficiency, large active area, good conductivity, stability and electrocatalytic activity, and has good degradation effect on organic pollutants.
Technical scheme
The invention takes a microporous titanium plate as a substrate, prepares titanium dioxide nanotubes on the surface and in the surface of the microporous titanium plate by adopting an anodic oxidation method, prepares the titanium dioxide nanotubes by adopting a high-temperature reduction method in a hydrogen atmosphere, then brush coats a prepared mixed solution of tin salt and antimonite on an intermediate layer, prepares the titanium dioxide nanotube by utilizing a thermal decomposition method, and prepares a ruthenium dioxide catalyst layer by utilizing a vacuum induction and thermal decomposition method. The specific scheme is as follows:
a method for preparing a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode comprises the following steps:
(1) taking a pretreated microporous titanium plate as an anode, wherein the aperture of the microporous titanium plate is 10-60 mu m, taking a stainless steel or metal platinum sheet as a cathode, carrying out anodic oxidation in a mixed solution containing ethylene glycol, deionized water and sodium fluoride under the voltage of 20-60V, taking out after the anodic oxidation is finished, and calcining in a muffle furnace to obtain a titanium dioxide nanotube;
(2) adding the titanium dioxide nanotube into a tube furnace for reduction treatment to obtain a titanium suboxide nanotube;
(3) adding a titanium protoxide nanotube into a container, adding a mixed solution of tin tetrachloride and antimony trichloride, vacuumizing until the pressure in the container is 0.5-1.0 MPa, and taking out to sinter to obtain the tin-antimony doped titanium protoxide nanotube;
(4) adding the tin-antimony doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, vacuumizing until the pressure in a container is 0.5-1.0 MPa, taking out, drying, sintering, repeating for 8-16 times, and finally calcining at 550 ℃ for 60-70 min for shaping to obtain the tin-antimony doped titanium dioxide interlayer microporous ruthenium dioxide electrode;
in the step (4), in the mixed solution, the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1: (10-20), wherein the dosage of the hydrochloric acid accounts for 0.1-0.5% of the mass of the mixed solution.
Further, in the step (1), the pretreatment is: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
Further, in the step (1), in the mixed solution containing ethylene glycol, deionized water and sodium fluoride, the mass ratio of ethylene glycol to deionized water is (2-20): 1, and the amount of sodium fluoride accounts for 0.1-0.5% of the mass of the mixed solution.
Further, in the step (1), the calcining temperature is 450-650 ℃, and the time is 4-6 h.
Further, in the step (2), the reducing agent adopted in the reduction treatment is H2C, Ti or Al, reduction treatmentThe temperature is 750-1050 ℃ and the time is 0.5-6 h.
Further, in the step (3), in the mixed solution of tin tetrachloride and antimony trichloride, the concentration of tin tetrachloride is 1.0-1.5 mol/L, the concentration of antimony trichloride is 0.02-0.05 mol/L, and the solvent is one of n-propanol, isopropanol or tert-butanol.
Further, in the step (3), the sintering temperature is 450-550 ℃, and the time is 30-90 min.
Further, in the step (4), the drying temperature is 100 ℃ and the drying time is 8-12 min.
Further, in the step (4), the sintering temperature is 400-500 ℃, and the time is 10-45 min.
The invention has the beneficial effects that:
(1) the electrode of the invention contains titanium dioxide nanotube, which has good conductivity, stronger conductivity than carbon, and can be compared favorably with partial metal, strong conductivity and reduced energy consumption.
(2) According to the invention, the tin-antimony doped titanium dioxide nanotube is adopted, and the tin-antimony is fully distributed in the nanotube, so that the adhesive force of the ruthenium dioxide layer can be further enhanced, the electrocatalytic activity area of the electrode is increased, and more active sites are provided for reaction.
(3) The electrode of the invention takes the microporous titanium as the substrate, the microporous titanium matrix has a large amount of available space on the surface and inside, the contact probability of pollutants and the electrode is improved, and meanwhile, the micropores provide space for mass transfer of the pollutants, so that the mass transfer efficiency of the pollutants can be improved, the treatment efficiency is further improved, and the treatment cost is reduced.
(4) The method has simple process and strong operability, and the prepared electrode has high mass transfer efficiency, large active area, good conductivity, stability and electrocatalytic activity and has good degradation effect on organic pollutants.
Drawings
FIG. 1 is an SEM image of a tin antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode made in example 5;
FIG. 2 is an XRD pattern of a tin antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode prepared in example 5;
FIG. 3 is a graph of the removal efficiency of phenol from a microporous ruthenium dioxide electrode with a tin-antimony doped titanium suboxide interlayer made in example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention are clearly and completely described below with reference to the accompanying drawings and 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.
Example 1
A method for preparing a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode comprises the following steps:
(1) taking a pretreated microporous titanium plate with the aperture of 20 mu m as an anode and stainless steel as a cathode; putting an anode and a cathode into a mixed solution of ethylene glycol, deionized water and sodium fluoride for anodic oxidation, wherein the mass ratio of ethylene glycol to deionized water in the mixed solution is 4: 1, the mass concentration of sodium fluoride is 0.2%, the voltage of anodic oxidation is 35V, and the time is 2 h; taking out and calcining in a muffle furnace at 550 ℃ for 5 hours to obtain a titanium dioxide nanotube;
the pretreatment is as follows: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
(2) Heating the titanium dioxide nanotube in a tube furnace for reduction treatment, wherein the reducing agent is H2The ventilation volume is 250mL/min, the temperature is 800 ℃, and the reduction treatment time is 2h, so that the titanium dioxide nanotube is obtained;
(3) adding a titanium monoxide nanotube into a container, and then adding a mixed solution of tin tetrachloride and antimony trichloride, wherein in the mixed solution, the concentration of the tin tetrachloride is 1.0mol/L, the concentration of the antimony trichloride is 0.04mol/L, and a solvent is n-propanol; vacuumizing until the pressure in the container is 1.0MPa, taking out the container and sintering at the sintering temperature of 500 ℃ for 50min to obtain the tin-antimony doped titanium dioxide nanotube;
(4) adding the antimony tin doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, wherein the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1:10, the amount of the hydrochloric acid accounts for 0.4% of the mass of the mixed solution, vacuumizing until the pressure in a container is 0.5MPa, taking out, drying at 100 ℃ for 10min, sintering at 400 ℃ for 40min, repeating for 8 times, and finally calcining at 550 ℃ for 60min for shaping to obtain the antimony tin doped titanium dioxide interlayer microporous ruthenium dioxide electrode.
Example 2
A method for preparing a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode comprises the following steps:
(1) taking a pretreated microporous titanium plate with the aperture of 20 mu m as an anode and stainless steel as a cathode; putting an anode and a cathode into a mixed solution of ethylene glycol, deionized water and sodium fluoride for anodic oxidation, wherein the mass ratio of the ethylene glycol to the deionized water in the mixed solution is 7: 1, the mass concentration of sodium fluoride is 0.3%, the voltage of anodic oxidation is 50V, and the time is 2 h; taking out and calcining in a muffle furnace at 550 ℃ for 5 hours to obtain a titanium dioxide nanotube;
the pretreatment is as follows: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
(2) Heating the titanium dioxide nanotube in a tube furnace for reduction treatment, wherein the reducing agent is H2The ventilation volume is 250mL/min, the temperature is 900 ℃, and the reduction treatment time is 3.5h, so as to obtain the titanium dioxide nanotube;
(3) adding a titanium monoxide nanotube into a container, and then adding a mixed solution of tin tetrachloride and antimony trichloride, wherein in the mixed solution, the concentration of the tin tetrachloride is 1.5mol/L, the concentration of the antimony trichloride is 0.02mol/L, and a solvent is n-propanol; vacuumizing until the pressure in the container is 1.0MPa, taking out the container and sintering, wherein the sintering temperature is 550 ℃, and the calcining time is 65min to obtain the tin-antimony doped titanium dioxide nanotube;
(4) adding the antimony tin doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, wherein the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1:16, the amount of the hydrochloric acid accounts for 0.4% of the mass of the mixed solution, vacuumizing until the pressure in a container is 0.5MPa, taking out, drying at 100 ℃ for 10min, sintering at 500 ℃ for 45min, repeating for 8 times, and finally calcining at 550 ℃ for 60min for shaping to obtain the antimony tin doped titanium dioxide interlayer microporous ruthenium dioxide electrode.
Example 3
A method for preparing a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode comprises the following steps:
(1) taking a pretreated microporous titanium plate with the aperture of 55 mu m as an anode and stainless steel as a cathode; putting an anode and a cathode into a mixed solution of ethylene glycol, deionized water and sodium fluoride for anodic oxidation, wherein the mass ratio of the ethylene glycol to the deionized water in the mixed solution is 18: 1, the mass concentration of sodium fluoride is 0.4%, the voltage of anodic oxidation is 45V, and the time is 2 h; taking out and calcining in a muffle furnace at 500 ℃ for 5.5 hours to obtain a titanium dioxide nanotube;
the pretreatment is as follows: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
(2) Heating the titanium dioxide nanotube in a tube furnace for reduction treatment, wherein the reducing agent is H2The ventilation volume is 250mL/min, the temperature is 850 ℃, and the reduction treatment time is 1h, so that the titanium dioxide nanotube is obtained;
(3) adding a titanium monoxide nanotube into a container, and then adding a mixed solution of tin tetrachloride and antimony trichloride, wherein in the mixed solution, the concentration of the tin tetrachloride is 1.2mol/L, the concentration of the antimony trichloride is 0.02mol/L, and a solvent is n-propanol; vacuumizing until the pressure in the container is 0.6MPa, taking out the container and sintering, wherein the sintering temperature is 525 ℃ and the calcining time is 60min to obtain the tin-antimony doped titanium dioxide nanotube;
(4) adding the antimony tin doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, wherein the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1:15, the amount of the hydrochloric acid accounts for 0.4% of the mass of the mixed solution, vacuumizing until the pressure in a container is 0.7MPa, taking out, drying at 100 ℃ for 10min, sintering at 430 ℃ for 35min, repeating for 10 times, and finally calcining at 550 ℃ for 60min for shaping to obtain the antimony tin doped titanium dioxide interlayer microporous ruthenium dioxide electrode.
Example 4
A method for preparing a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode comprises the following steps:
(1) taking a pretreated microporous titanium plate with the aperture of 55 mu m as an anode and stainless steel as a cathode; putting an anode and a cathode into a mixed solution of ethylene glycol, deionized water and sodium fluoride for anodic oxidation, wherein the mass ratio of the ethylene glycol to the deionized water in the mixed solution is 15: 1, the mass concentration of sodium fluoride is 0.4%, the voltage of anodic oxidation is 40V, and the time is 1.5 h; taking out and calcining in a muffle furnace at 600 ℃ for 4.5h to obtain a titanium dioxide nanotube;
the pretreatment is as follows: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
(2) Heating the titanium dioxide nanotube in a tube furnace for reduction treatment, wherein the reducing agent is H2The ventilation volume is 250mL/min, the temperature is 800 ℃, and the reduction treatment time is 5h, so as to obtain the titanium dioxide nanotube;
(3) adding a titanium monoxide nanotube into a container, and then adding a mixed solution of tin tetrachloride and antimony trichloride, wherein in the mixed solution, the concentration of the tin tetrachloride is 1.5mol/L, the concentration of the antimony trichloride is 0.03mol/L, and a solvent is n-propanol; vacuumizing until the pressure in the container is 0.7MPa, taking out the container and sintering, wherein the sintering temperature is 500 ℃, and the calcining time is 70min to obtain the tin-antimony doped titanium dioxide nanotube;
(4) adding the antimony tin doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, wherein the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1:15, the amount of the hydrochloric acid accounts for 0.2% of the mass of the mixed solution, vacuumizing until the pressure in a container is 0.7MPa, taking out, drying at 100 ℃ for 10min, sintering at 475 ℃ for 35min, repeating for 12 times, and finally calcining at 550 ℃ for 60min for shaping to obtain the antimony tin doped titanium dioxide interlayer microporous ruthenium dioxide electrode.
Example 5
A method for preparing a stannum-antimony doped titanium dioxide intermediate layer microporous ruthenium dioxide electrode comprises the following steps:
(1) taking a pretreated microporous titanium plate with the aperture of 60 mu m as an anode and stainless steel as a cathode; putting an anode and a cathode into a mixed solution of ethylene glycol, deionized water and sodium fluoride for anodic oxidation, wherein the mass ratio of the ethylene glycol to the deionized water in the mixed solution is 20: 1, the mass concentration of sodium fluoride is 0.3%, the voltage of anodic oxidation is 55V, and the time is 2 h; taking out and calcining in a muffle furnace at the temperature of 650 ℃ for 5 hours to obtain a titanium dioxide nanotube;
the pretreatment is as follows: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
(2) Heating the titanium dioxide nanotube in a tube furnace for reduction treatment, wherein the reducing agent is H2The ventilation volume is 250mL/min, the temperature is 950 ℃, and the reduction treatment time is 5.5h, so as to obtain the titanium dioxide nanotube;
(3) adding a titanium monoxide nanotube into a container, and then adding a mixed solution of tin tetrachloride and antimony trichloride, wherein in the mixed solution, the concentration of the tin tetrachloride is 1.5mol/L, the concentration of the antimony trichloride is 0.04mol/L, and a solvent is n-propanol; vacuumizing until the pressure in the container is 0.6MPa, taking out the container and sintering at the sintering temperature of 550 ℃ for 60min to obtain the tin-antimony doped titanium dioxide nanotube;
(4) adding the antimony tin doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, wherein the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1:15, the amount of the hydrochloric acid accounts for 0.4% of the mass of the mixed solution, vacuumizing until the pressure in a container is 0.9MPa, taking out, drying at 100 ℃ for 10min, sintering at 500 ℃ for 30min, repeating for 10 times, and finally calcining at 550 ℃ for 60min for shaping to obtain the antimony tin doped titanium dioxide interlayer microporous ruthenium dioxide electrode.
Comparative example 1
A preparation method of a plate-type ruthenium dioxide electrode comprises the following steps: adding a microporous titanium plate with the aperture of 60 mu m into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, wherein the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1:15, the amount of the hydrochloric acid accounts for 0.4% of the mass of the mixed solution, vacuumizing until the pressure in a container is 0.9MPa, taking out, drying at 100 ℃ for 10min, sintering at 500 ℃ for 30min, repeating for 10 times, and finally calcining at 550 ℃ for 60min for shaping to obtain the titanium plate.
FIG. 1 is an SEM image of a tin antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode made in example 5, from which RuO can be seen2The catalytic layer has been successfully prepared on the inner channel wall of the porous titanium matrix, and a mud-like surface microstructure is formed.
FIG. 2 is an EDS plot of the antimony tin-doped titanium monoxide intermediate microporous ruthenium dioxide electrode prepared in example 5, wherein a represents a microporous titanium plate, b represents pure ruthenium dioxide, and c represents the antimony tin-doped titanium monoxide intermediate microporous ruthenium dioxide electrode prepared in example 5, from which it can be seen that the electrode peak position matches the standard RuO2Position coincidence, proves RuO2The presence of a layer.
Testing the electrocatalytic oxidation performance of the electrode:
preparing 80mg/L phenol solution with phenol as target pollutant at current density of 3mA/cm2The electrocatalytic oxidation performance of the ruthenium dioxide electrocatalytic membrane electrode prepared in example 5 and the plate-type ruthenium dioxide electrode prepared in comparative example 1 was tested at a flow rate of 100rpm for 100min, the change in the concentration of phenol in the wastewater was measured by a high performance liquid chromatograph, and the removal rate of phenol was calculated, and the results are shown in fig. 3.
As can be seen from fig. 3, the ruthenium dioxide electrode prepared according to the example of the present invention has higher phenol removal efficiency than the ruthenium dioxide electrode prepared according to the conventional method under the same conditions, which indicates that the electrode prepared according to the present invention has better oxidation effect.
Claims (9)
1. A method for preparing a stannum-antimony doped titanium suboxide intermediate layer microporous ruthenium dioxide electrode is characterized by comprising the following steps:
(1) taking a pretreated microporous titanium plate as an anode, wherein the aperture of the microporous titanium plate is 10-60 mu m, taking a stainless steel or metal platinum sheet as a cathode, carrying out anodic oxidation in a mixed solution containing ethylene glycol, deionized water and sodium fluoride under the voltage of 20-60V, taking out after the anodic oxidation is finished, and calcining in a muffle furnace to obtain a titanium dioxide nanotube;
(2) adding the titanium dioxide nanotube into a tube furnace for reduction treatment to obtain a titanium suboxide nanotube;
(3) adding a titanium protoxide nanotube into a container, adding a mixed solution of tin tetrachloride and antimony trichloride, vacuumizing until the pressure in the container is 0.5-1.0 MPa, and taking out to sinter to obtain the tin-antimony doped titanium protoxide nanotube;
(4) adding the tin-antimony doped titanium dioxide nanotube into a mixed solution containing ruthenium trichloride trihydrate, isopropanol and hydrochloric acid, vacuumizing until the pressure in a container is 0.5-1.0 MPa, taking out, drying, sintering, repeating for 8-16 times, and finally calcining at 550 ℃ for 60-70 min for shaping to obtain the tin-antimony doped titanium dioxide interlayer microporous ruthenium dioxide electrode;
in the step (4), in the mixed solution, the mass ratio of the ruthenium trichloride trihydrate to the isopropanol is 1: (10-20), wherein the dosage of the hydrochloric acid accounts for 0.1-0.5% of the mass of the mixed solution.
2. The method for preparing the tin-antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (1), the pretreatment is: ultrasonic cleaning in deionized water for 20min, ultrasonic cleaning in isopropanol solution for 20min, and ultrasonic cleaning in sodium hydroxide solution with mass fraction of 40% for 30 min.
3. The method for preparing the tin-antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (1), in the mixed solution containing ethylene glycol, deionized water and sodium fluoride, the mass ratio of ethylene glycol to deionized water is (2-20): 1, and the amount of sodium fluoride accounts for 0.1-0.5% of the mass of the mixed solution.
4. The method for preparing the tin-antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (1), the calcination temperature is 450-650 ℃ and the calcination time is 4-6 h.
5. The method for preparing the tin-antimony doped titanium suboxide interlayer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (2), the reducing agent adopted in the reduction treatment is H2C, Ti or Al, the reduction treatment temperature is 750-1050 ℃, and the time is 0.5-6 h.
6. The method for preparing the stannum-antimony doped titanium protoxide intermediate layer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (3), in the mixed solution of tin tetrachloride and antimony trichloride, the concentration of tin tetrachloride is 1.0-1.5 mol/L, the concentration of antimony trichloride is 0.02-0.05 mol/L, and the solvent is one of n-propanol, isopropanol or tert-butanol.
7. The method for preparing the tin-antimony doped titanium monoxide interlayer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (3), the sintering temperature is 450-550 ℃ and the time is 30-90 min.
8. The method for preparing the tin-antimony doped titanium suboxide interlayer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (4), the drying temperature is 100 ℃ and the drying time is 8-12 min.
9. The method for preparing the tin-antimony doped titanium monoxide interlayer microporous ruthenium dioxide electrode as claimed in claim 1, wherein in the step (4), the sintering temperature is 400-500 ℃ and the time is 10-45 min.
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| CN116005155A (en) * | 2023-01-30 | 2023-04-25 | 江西省科学院应用物理研究所 | Preparation method of corrosion-resistant electrode |
| CN116063865A (en) * | 2023-01-18 | 2023-05-05 | 浙江理工大学 | Self-cleaning antistatic heat-insulating functional filler and preparation method and application thereof |
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