CN114249395A - Preparation method of tin-antimony embedded lead dioxide electrocatalytic membrane electrode - Google Patents
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Abstract
The invention relates to a preparation method of a tin-antimony embedded lead dioxide electrocatalytic membrane electrode, which takes a microporous titanium plate as a substrate, adopts an anodic oxidation method to prepare a rutile type titanium dioxide nanotube, then adopts a high-temperature reduction method to prepare a titanium dioxide nanotube in a hydrogen and nitrogen atmosphere, then prepares a solution of tin salt and antimonate according to a certain proportion as a precursor, forms the titanium dioxide nanotube embedded with tin-antimony through high-temperature decomposition after embedding the titanium dioxide nanotube through vacuum induction, and finally adopts a flowing electrodeposition technology to load a lead dioxide catalytic layer. The method has the advantages of simple process and strong operability, and the prepared electrode has the advantages of large specific surface area, good conductivity and strong stability. The micropore structure enables the electrode to have high mass transfer efficiency, the prepared active layer has compact surface, no crack, strong adhesive force and difficult shedding, and is particularly suitable for the field of treating wastewater by electrochemical oxidation technology.
Description
Technical Field
The invention relates to a preparation method of a tin-antimony embedded lead dioxide electrocatalytic membrane electrode, belonging to the technical field of electrode materials.
Background
The industrial organic wastewater often contains organic pollutants which are difficult to degrade, for example, pesticide wastewater often contains organic pollutants of cyproconazole, medical wastewater often contains organic pollutants of pyrimidine, and printing and dyeing wastewater often contains organic pollutants of heterocyclic. The pollutants belong to organic pollutants which are difficult to degrade, and have stable chemical structures, so the pollutants 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 degradation of refractory organic pollution through hydroxyl free radicals (. OH) generated in the reaction process so as to mineralize, and has the advantages of environmental friendliness, simplicity in operation, no need of adding extra reagents, small occupied space, easiness in automation and the like, so that the electrochemical oxidation method is favored by broad students.
The key point of the electrochemical oxidation technology lies in the development of anode materials, and ideal anode materials need to have high catalytic efficiency, excellent conductivity and stability. A common anode material is RuO2、Ir2O5、MnO2、SnO2、PbO2Boron-embedded diamond (BDD) and titanium (Ti) oxide4O7) And the like. Wherein, RuO2、Ir2O5、MnO2As "active" electrodes, SnO2、PbO2BDD and Ti4O7Are "inactive" electrodes. The 'active' electrode can interact with OH in the reaction process to generate oxidant with higher valence state and then degrade pollutants, while the 'inactive' electrode has weaker interaction with OH, OH only exists on the surface of the electrode by weak physical adsorption, and the degradation of pollutants is mainly completed by OHTherefore, compared with the active electrode, the inactive electrode has stronger degradation capability to the pollutants, and the pollutants are degraded more thoroughly. Thus, "inactive" electrodes are more advantageous in the removal of refractory organic contaminants. However, these several common "inactive" electrodes suffer from drawbacks, e.g., 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; ti4O7Stability under anodic conditions is problematic and conversion to titanium dioxide is easy, thereby reducing catalytic activity.
Disclosure of Invention
The invention aims to solve the performance defects of the existing electrode material, and provides a preparation method of a tin-antimony embedded lead dioxide electrocatalytic membrane 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.
The present invention prepares rutile type titanium dioxide nanotube on the surface and inside of microporous titanium as substrate through anode oxidation process, prepares titania nanotube through high temperature reduction process in hydrogen atmosphere, coats the mixed solution of tin salt and antimony salt onto the intermediate layer, embeds the titania nanotube inside the nanotube through thermal decomposition process, and prepares lead dioxide catalyst layer through flow electrodeposition process. The specific scheme is as follows:
a method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode comprises the following steps:
(1) taking a microporous titanium plate with the aperture of 10-60 mu m as an anode, taking a stainless steel or metal platinum sheet as a cathode, electrolyzing in a mixed solution containing ethylene glycol, deionized water and sodium fluoride, and taking out after the electrolysis to obtain an oxidized microporous titanium plate;
(2) heating the oxidized microporous titanium plate to calcine in the air atmosphere, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) putting the rutile type titanium dioxide nanotube into a tubular furnace, introducing a mixed gas of hydrogen and nitrogen, heating and reducing to obtain a titanium suboxide nanotube;
(4) adding a titanium protoxide nanotube into a mixed solution containing stannic chloride and antimony trichloride, vacuumizing until the pressure in a container is 0.5-1.0 MPa, taking out, drying and sintering to obtain the titanium protoxide nanotube embedded with tin and antimony;
(5) and (4) taking the titanium dioxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, performing electrodeposition in a lead nitrate electrolyte, and taking out after the electrodeposition to obtain the tin and antimony embedded lead dioxide electrocatalytic membrane electrode.
Further, in the step (1), the voltage of electrolysis is 20-60V, and the time is 1-6 h.
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 (2), the temperature rising rate is 2-5 ℃/min, the calcining temperature is 550-800 ℃, and the time is 2-6 h.
Further, in the step (3), in the mixed gas of hydrogen and nitrogen, the volume ratio of hydrogen to nitrogen is 1: (2-4).
Further, in the step (3), the temperature of the reduction treatment is 750-1050 ℃, and the time is 0.5-6 h.
Further, in the step (4), in the mixed solution of tin tetrachloride and antimony trichloride, the concentration of tin tetrachloride is 1.0-1.5 mol/L, and the concentration of antimony trichloride is 0.02-0.05 mol/L.
Further, in the step (4), the sintering temperature is 450-550 ℃, and the time is 30-90 min.
Further, in the step (5), the preparation method of the lead nitrate electrolyte comprises the following steps: adding 16.56g of lead nitrate into 70mL of deionized water, adding 0.168g of sodium fluoride and 7mL of pure nitric acid after completely dissolving, stirring to dissolve, and metering to 100mL to obtain the lead nitrate electrolyte.
Further, in the step (5), during the electrodeposition, the current density is controlled to be 10-30 mA/cm2The temperature of the electrolyte is 40-80 ℃, the pH of the electrolyte is 3, and the electrodeposition time is 30-70 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, and meanwhile, rutile type titanium dioxide and lead dioxide have the same crystal form, so the bonding force with lead dioxide is strong.
2) According to the invention, tin antimony is embedded into the titanium dioxide nanotube, the tin antimony is fully distributed in the nanotube, so that the adhesive force of the lead dioxide layer can be further enhanced, the electrocatalytic activity area of the electrode is increased, more active sites are provided for reaction, and the catalytic capability of the lead dioxide layer is enhanced.
3) The micropore titanium plate substrate adopted by the invention has a large amount of available space on the surface and inside, so that the contact probability of pollutants and the electrode is improved, and simultaneously, the micropore provides 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 embedded lead dioxide electrocatalytic membrane electrode prepared in example 5;
FIG. 2 is an EDS diagram of a tin-antimony embedded lead dioxide electrocatalytic membrane electrode prepared in example 5;
fig. 3 is a graph showing the removal efficiency of the tin-antimony embedded lead dioxide electrocatalytic membrane electrode prepared in example 5 on phenol.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Example 1
A method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode comprises the following steps:
(1) taking a microporous titanium plate with the aperture of 20 mu m as an anode and stainless steel as a cathode, and electrolyzing in a mixed solution containing glycol, deionized water and sodium fluoride, wherein the mass ratio of the glycol to the deionized water in the mixed solution is 2: 1, the mass concentration of sodium fluoride is 0.1%, the voltage of electrolysis is 40V, the time is 2h, and the titanium plate is taken out after the electrolysis is finished to obtain an oxidized microporous titanium plate;
(2) in the air atmosphere, heating the oxidized microporous titanium plate to 600 ℃ at the speed of 3 ℃/min, calcining for 4h, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) placing the rutile type titanium dioxide nanotube into a tube furnace, and introducing a mixed gas (H) of hydrogen and nitrogen at a speed of 125mL/min2/N2The volume ratio is 1:4), the temperature is raised to 950 ℃ at the speed of 5 ℃/min, the reduction treatment is carried out for 2.5h, and then the titanium dioxide nanotube is obtained after the temperature is cooled to the room temperature;
(4) preparing a mixed solution of tin tetrachloride and antimony trichloride by taking ethanol as a solvent, wherein the concentration of the tin tetrachloride is 1.0mol/L and the concentration of the antimony trichloride is 0.04mol/L, and 2mL of hydrochloric acid solution with the mass concentration of 20% is added into every 250mL of the mixed solution; adding the titanium suboxide nanotube into the mixed solution, vacuumizing until the pressure in the container is 1.0MPa, taking out, drying at 100 ℃ for 10min, heating to 550 ℃ at the speed of 5 ℃/min, and sintering for 60min to obtain the titanium suboxide nanotube embedded with tin and antimony;
(5) weighing 16.56g of lead nitrate in 70ml of ultrapure water, adding 0.168g of sodium fluoride and 7ml of pure nitric acid after completely dissolving, and fixing the volume to 100ml after completely dissolving to obtain lead nitrate electrolyte; taking the titanium protoxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, carrying out electrodeposition in lead nitrate electrolyte, and controlling the current density to be 30mA/cm2And performing electrodeposition for 45min at 80 ℃, controlling the rotating speed of a magnetic stirrer to be 500r/min and the pH of the electrolyte to be 3, and taking out the electrolyte after the electrodeposition to obtain the tin-antimony embedded lead dioxide electrocatalytic membrane electrode.
Example 2
A method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode comprises the following steps:
(1) taking a microporous titanium plate with the aperture of 20 mu m as an anode and stainless steel as a cathode, and electrolyzing in a mixed solution containing glycol, deionized water and sodium fluoride, wherein the mass ratio of the glycol to the deionized water in the mixed solution is 8: 1, the mass concentration of sodium fluoride is 0.3%, the voltage of electrolysis is 60V, the time is 3h, and the titanium plate is taken out after the electrolysis is finished to obtain an oxidized microporous titanium plate;
(2) in the air atmosphere, heating the oxidized microporous titanium plate to 650 ℃ at the speed of 5 ℃/min, calcining for 4h, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) placing the rutile type titanium dioxide nanotube into a tube furnace, and introducing a mixed gas (H) of hydrogen and nitrogen at a speed of 100mL/min2/N2The volume ratio is 1:4), the temperature is raised to 750 ℃ at the speed of 5 ℃/min, reduction treatment is carried out for 1h, and then the titanium dioxide nanotube is obtained after cooling to the room temperature;
(4) preparing a mixed solution of tin tetrachloride and antimony trichloride by taking ethanol as a solvent, wherein the concentration of the tin tetrachloride is 1.5mol/L and the concentration of the antimony trichloride is 0.02mol/L, and 2mL of hydrochloric acid solution with the mass concentration of 20% is added into every 250mL of the mixed solution; adding the titanium dioxide nanotube into the mixed solution, vacuumizing until the pressure in the container is 1.0MPa, taking out, drying at 100 ℃ for 10min, heating to 500 ℃ at the speed of 5 ℃/min, and sintering for 60min to obtain the titanium dioxide nanotube embedded with tin and antimony;
(5) weighing 16.56g of lead nitrate in 70ml of ultrapure water, adding 0.168g of sodium fluoride and 7ml of pure nitric acid after completely dissolving, and fixing the volume to 100ml after completely dissolving to obtain lead nitrate electrolyte; taking the titanium protoxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, carrying out electrodeposition in lead nitrate electrolyte, and controlling the current density to be 30mA/cm2And performing electrodeposition for 45min at 80 ℃, controlling the rotating speed of a magnetic stirrer to be 500r/min and the pH of the electrolyte to be 3, and taking out the electrolyte after the electrodeposition to obtain the tin-antimony embedded lead dioxide electrocatalytic membrane electrode.
Example 3
A method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode comprises the following steps:
(1) taking a microporous titanium plate with the aperture of 30 mu m as an anode and stainless steel as a cathode, and electrolyzing in a mixed solution containing ethylene glycol, deionized water and sodium fluoride, wherein the mass ratio of the ethylene glycol to the deionized water in the mixed solution is 16: 1, the mass concentration of sodium fluoride is 0.1%, the voltage of electrolysis is 25V, the time is 6h, and the titanium plate is taken out after the electrolysis is finished to obtain an oxidized microporous titanium plate;
(2) in the air atmosphere, heating the oxidized microporous titanium plate to 750 ℃ at the speed of 5 ℃/min, calcining for 6 hours, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) placing the rutile type titanium dioxide nanotube into a tube furnace, and introducing a mixed gas (H) of hydrogen and nitrogen at a speed of 100mL/min2/N2The volume ratio is 1:3), the temperature is raised to 750 ℃ at the speed of 5 ℃/min, the reduction treatment is carried out for 0.5h, and then the titanium dioxide nanotube is obtained after the temperature is cooled to the room temperature;
(4) preparing a mixed solution of tin tetrachloride and antimony trichloride by taking ethanol as a solvent, wherein the concentration of the tin tetrachloride is 1.5mol/L and the concentration of the antimony trichloride is 0.02mol/L, and 2mL of hydrochloric acid solution with the mass concentration of 20% is added into every 250mL of the mixed solution; adding the titanium suboxide nanotube into the mixed solution, vacuumizing until the pressure in the container is 1.0MPa, taking out, drying at 100 ℃ for 10min, heating to 450 ℃ at the speed of 5 ℃/min, and sintering for 30min to obtain the titanium suboxide nanotube embedded with tin and antimony;
(5) weighing 16.56g of lead nitrate in 70ml of ultrapure water, adding 0.168g of sodium fluoride and 7ml of pure nitric acid after completely dissolving, and fixing the volume to 100ml after completely dissolving to obtain lead nitrate electrolyte; taking the titanium protoxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, carrying out electrodeposition in lead nitrate electrolyte, and controlling the current density to be 15mA/cm2Electrodepositing at 70 ℃ for 65min, controlling the rotating speed of a magnetic stirrer to be 300r/min and the pH value of the electrolyte to be 3, and taking out after the operation is finished to obtain the tin-antimony embedded lead dioxide electrocatalytic membraneAnd (4) a pole.
Example 4
A method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode comprises the following steps:
(1) taking a microporous titanium plate with the aperture of 50 mu m as an anode and stainless steel as a cathode, and electrolyzing in a mixed solution containing glycol, deionized water and sodium fluoride, wherein the mass ratio of the glycol to the deionized water in the mixed solution is 3: 1, the mass concentration of sodium fluoride is 0.5%, the voltage of electrolysis is 30V, the time is 5h, and the titanium plate is taken out after the electrolysis is finished to obtain an oxidized microporous titanium plate;
(2) in the air atmosphere, heating the oxidized microporous titanium plate to 550 ℃ at the speed of 2 ℃/min, calcining for 5 hours, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) placing the rutile type titanium dioxide nanotube into a tube furnace, and introducing a mixed gas (H) of hydrogen and nitrogen at a speed of 100mL/min2/N2The volume ratio is 1:3), the temperature is raised to 1050 ℃ at the speed of 5 ℃/min, reduction treatment is carried out for 1h, and then the titanium dioxide nanotube is obtained after cooling to room temperature;
(4) preparing a mixed solution of tin tetrachloride and antimony trichloride by taking ethanol as a solvent, wherein the concentration of the tin tetrachloride is 1.2mol/L and the concentration of the antimony trichloride is 0.04mol/L, and 2mL of hydrochloric acid solution with the mass concentration of 20% is added into every 250mL of the mixed solution; adding the titanium suboxide nanotube into the mixed solution, vacuumizing until the pressure in the container is 1.0MPa, taking out, drying at 100 ℃ for 10min, heating to 550 ℃ at the speed of 5 ℃/min, and sintering for 30min to obtain the titanium suboxide nanotube embedded with tin and antimony;
(5) weighing 16.56g of lead nitrate in 70ml of ultrapure water, adding 0.168g of sodium fluoride and 7ml of pure nitric acid after completely dissolving, and fixing the volume to 100ml after completely dissolving to obtain lead nitrate electrolyte; taking the titanium protoxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, carrying out electrodeposition in lead nitrate electrolyte, and controlling the current density to be 20mA/cm2Electrodepositing at 50 ℃ for 60min, controlling the rotating speed of a magnetic stirrer to be 400r/min and the pH value of the electrolyte to be 3, and taking out after the end to obtain the tin-antimony embedded dioxideA lead electrocatalytic membrane electrode.
Example 5
A method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode comprises the following steps:
(1) taking a microporous titanium plate with the aperture of 40 mu m as an anode and stainless steel as a cathode, and electrolyzing in a mixed solution containing glycol, deionized water and sodium fluoride, wherein the mass ratio of the glycol to the deionized water in the mixed solution is 12: 1, the mass concentration of sodium fluoride is 0.4%, the voltage of electrolysis is 45V, the time is 6h, and the titanium plate is taken out after the electrolysis is finished to obtain an oxidized microporous titanium plate;
(2) in the air atmosphere, heating the oxidized microporous titanium plate to 600 ℃ at the speed of 5 ℃/min, calcining for 6 hours, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) placing the rutile type titanium dioxide nanotube into a tube furnace, and introducing a mixed gas (H) of hydrogen and nitrogen at a speed of 100mL/min2/N2The volume ratio is 1:3), the temperature is raised to 850 ℃ at the speed of 5 ℃/min, the reduction treatment is carried out for 0.5h, and then the titanium dioxide nanotube is obtained after the temperature is cooled to the room temperature;
(4) preparing a mixed solution of tin tetrachloride and antimony trichloride by taking ethanol as a solvent, wherein the concentration of the tin tetrachloride is 1.0mol/L and the concentration of the antimony trichloride is 0.03mol/L, and 2mL of hydrochloric acid solution with the mass concentration of 20% is added into every 250mL of the mixed solution; adding the titanium suboxide nanotube into the mixed solution, vacuumizing until the pressure in the container is 1.0MPa, taking out, drying at 100 ℃ for 10min, heating to 550 ℃ at the speed of 5 ℃/min, and sintering for 45min to obtain the titanium suboxide nanotube embedded with tin and antimony;
(5) weighing 16.56g of lead nitrate in 70ml of ultrapure water, adding 0.168g of sodium fluoride and 7ml of pure nitric acid after completely dissolving, and fixing the volume to 100ml after completely dissolving to obtain lead nitrate electrolyte; taking the titanium protoxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, carrying out electrodeposition in lead nitrate electrolyte, and controlling the current density to be 20mA/cm2Electrodepositing at 40 deg.C for 60min, controlling the rotation speed of magnetic stirrer to 200r/min and pH of electrolyte to 3, and taking out to obtain tinAntimony embedded lead dioxide electrocatalytic membrane electrode.
Comparative example 1
A preparation method of a plate-type lead dioxide electrode comprises the following steps: weighing 16.56g of lead nitrate in 70ml of ultrapure water, adding 0.168g of sodium fluoride and 7ml of pure nitric acid after completely dissolving, and fixing the volume to 100ml after completely dissolving to obtain lead nitrate electrolyte; taking a microporous titanium plate with the aperture of 40 mu m as an anode and stainless steel as a cathode, carrying out electrodeposition in a lead nitrate electrolyte, and controlling the current density to be 20mA/cm2And carrying out electro-deposition for 60min at 40 ℃, controlling the rotating speed of a magnetic stirrer to be 200r/min and the pH to be 3, and taking out after the operation is finished to obtain the tin-antimony embedded lead dioxide electro-catalytic membrane electrode.
FIG. 1 is an SEM picture of a Sn-Sb embedded lead dioxide electrocatalytic membrane electrode prepared in example 5, and PbO can be seen from the SEM picture2The catalytic layer is successfully prepared on the inner pore channel wall of the porous titanium matrix, and a diamond-like surface microstructure is formed.
Fig. 2 is an EDS of a tin-antimony embedded lead dioxide electrocatalytic membrane electrode prepared in example 5, from which it can be seen that the constituent elements of the electrode are Pb, O and Ti, further demonstrating the presence of a lead dioxide layer, so that the electrode has good electrocatalytic properties.
Testing of electrocatalytic oxidation performance:
taking phenol as a target pollutant, preparing a 100mg/L phenol solution, and controlling the current density to be 3mA/cm2Next, the electrocatalytic oxidation performance of the tin-antimony embedded lead dioxide electrocatalytic membrane electrode prepared in example 5 and the plate-type lead dioxide electrode prepared in comparative example 1 was tested, the experimental time was 100min, the change of the concentration of phenol in the sewage was measured by a high performance liquid chromatograph, and the removal rate of phenol was calculated, and the result is shown in fig. 3.
As can be seen from fig. 3, under the same conditions, the tin-antimony embedded lead dioxide electrocatalytic membrane electrode prepared by the embodiment of the invention has higher phenol removal efficiency than that prepared by the conventional method, which indicates that the electrode prepared by the method of the invention has better oxidation effect.
Claims (10)
1. A preparation method of a tin-antimony embedded lead dioxide electrocatalytic membrane electrode is characterized by comprising the following steps:
(1) taking a microporous titanium plate with the aperture of 10-60 mu m as an anode, taking a stainless steel or metal platinum sheet as a cathode, electrolyzing in a mixed solution containing ethylene glycol, deionized water and sodium fluoride, and taking out after the electrolysis to obtain an oxidized microporous titanium plate;
(2) heating the oxidized microporous titanium plate to calcine in the air atmosphere, and cooling to obtain a rutile type titanium dioxide nanotube;
(3) putting the rutile type titanium dioxide nanotube into a tubular furnace, introducing a mixed gas of hydrogen and nitrogen, heating and reducing to obtain a titanium suboxide nanotube;
(4) adding a titanium protoxide nanotube into a mixed solution containing stannic chloride and antimony trichloride, vacuumizing until the pressure in a container is 0.5-1.0 MPa, taking out, drying and sintering to obtain the titanium protoxide nanotube embedded with tin and antimony;
(5) and (4) taking the titanium dioxide nanotube embedded with tin and antimony prepared in the step (4) as an anode and stainless steel as a cathode, performing electrodeposition in a lead nitrate electrolyte, and taking out after the electrodeposition to obtain the tin and antimony embedded lead dioxide electrocatalytic membrane electrode.
2. The preparation method of the tin-antimony embedded lead dioxide electrocatalytic membrane electrode as claimed in claim 1, wherein in the step (1), the voltage of electrolysis is 20-60V, and the time is 1-6 h.
3. The preparation method of the tin-antimony embedded lead dioxide electrocatalytic membrane electrode as set forth in claim 1, wherein in the step (1), the mass ratio of ethylene glycol to deionized water in the mixed solution containing ethylene glycol, deionized water and sodium fluoride is (2-20): 1, and the amount of sodium fluoride is 0.1-0.5% of the mass of the mixed solution.
4. The preparation method of the tin-antimony embedded lead dioxide electrocatalytic membrane electrode as set forth in claim 1, wherein in the step (2), the rate of temperature rise is 2-5 ℃/min, the temperature of calcination is 550-800 ℃, and the time is 2-6 h.
5. The method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode as set forth in claim 1, wherein in the step (3), the volume ratio of hydrogen to nitrogen in the mixed gas of hydrogen and nitrogen is 1: (2-4).
6. The method for preparing the tin-antimony embedded lead dioxide electrocatalytic membrane electrode as claimed in claim 1, wherein in the step (3), the temperature of the reduction treatment is 750-1050 ℃ and the time is 0.5-6 h.
7. The method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode as recited in claim 1, wherein in the step (4), in the mixed solution of tin tetrachloride and antimony trichloride, the concentration of tin tetrachloride is 1.0-1.5 mol/L, and the concentration of antimony trichloride is 0.02-0.05 mol/L.
8. The method for preparing the tin-antimony embedded lead dioxide electrocatalytic membrane electrode as recited in claim 1, wherein in the step (4), the sintering temperature is 450-550 ℃ and the time is 30-90 min.
9. The method for preparing a tin-antimony embedded lead dioxide electrocatalytic membrane electrode as recited in claim 1, wherein in the step (5), the method for preparing the lead nitrate electrolyte comprises the following steps: adding 16.56g of lead nitrate into 70mL of deionized water, adding 0.168g of sodium fluoride and 7mL of pure nitric acid after completely dissolving, stirring to dissolve, and metering to 100mL to obtain the lead nitrate electrolyte.
10. The method for preparing the tin-antimony embedded lead dioxide electrocatalytic membrane electrode as claimed in any one of claims 1 to 9, wherein in the step (5), the current density is controlled to be 10-30 mA/cm during electrodeposition2The temperature of the electrolyte is 40-80 ℃, the pH of the electrolyte is 3, and electrodeposition is carried outThe time is 30-70 min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186205A (en) * | 2016-07-18 | 2016-12-07 | 南京理工大学 | A kind of micropore titanio tubular type multidimensional nano-pore embeds stannum antimony membrane electrode and preparation method thereof |
| CN112250145A (en) * | 2020-10-30 | 2021-01-22 | 南京理工大学 | Preparation and application of porous titanium-based titanium suboxide nanotube lead dioxide electrode |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186205A (en) * | 2016-07-18 | 2016-12-07 | 南京理工大学 | A kind of micropore titanio tubular type multidimensional nano-pore embeds stannum antimony membrane electrode and preparation method thereof |
| CN112250145A (en) * | 2020-10-30 | 2021-01-22 | 南京理工大学 | Preparation and application of porous titanium-based titanium suboxide nanotube lead dioxide electrode |
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