CN115896814A - Triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst and preparation method and application thereof - Google Patents
Triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a triangular pyramid bismuth-lead bimetallic oxide electrocatalyst and a preparation method and application thereof. The bismuth-lead bimetallic oxide prepared by the method is triangular pyramid-shaped, the unique exposed crystal face can promote the generation of ozone, and the bismuth-lead bimetallic oxide has high efficient performance and Faraday efficiency in the process of preparing ozone by electrolyzing water, and the performance is higher than that of commercial PbO 2 And pure Bi 2 O 3 (ii) a Meanwhile, the preparation process is simple to operate, the catalyst is controllable in shape and appearance, the raw materials are low in price, the performance is excellent, the stability is high, and the efficiency of preparing ozone by electrolyzing water is greatly improved.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst, and a preparation method and application thereof.
Background
With the normalization of epidemic situations, the current disinfection product needs to be improved due to the incompleteness of the current disinfection product, ozone is widely used in the aspects of air purification, sewage treatment, sterilization and disinfection and the like as a gas with strong oxidizing property, and is reduced into oxygen without generating secondary pollution, so that the ozone becomes a disinfectant with wide attention and receives wide attention of people.
At present, the preparation of ozone in industry mainly comprises an ultraviolet irradiation method, a high-voltage discharge method, an electrochemical method and the like, wherein the ultraviolet irradiation method generates ozone by irradiating dry oxygen with high-frequency ultraviolet rays, but the energy consumption of the generated ozone is high, and the concentration of the generated ozone is low, so that the ultraviolet irradiation method cannot be applied to the industry and only can be suitable for a small amount of ozone; the corona discharge method requires a large set of production equipment, requires high investment cost, and requires high-pressure ionized air to generate Nitrogen Oxides (NO), but Nitrogen Oxides (NO) are generated at the same time x ) It is a carcinogen, which is not conducive to scale-up and application of the method. Compared with the former two methods, the electrochemical method draws attention to the advantages of smaller equipment, simple operation, no toxicity, no harm and the like.
The main anode catalyst for preparing ozone by electrolyzing water is lead dioxide, noble metal platinum and the like, but the problems of reaction inactivation, stability reduction and the like are caused by the problem of lead loss in the lead dioxide in the electrolysis process, lead is a substance with high toxicity, and the defects limit the further development of the technology for electrolyzing water to produce ozone, so that the development of the anode catalyst for electrolyzing water with high stability and high efficiency has important research significance.
The bimetallic oxide is widely applied to the fields of electro-catalysts, super capacitors and the like due to the unique double active centers and the mutual coordination effect of the bimetallic oxide, bismuth is taken as an adjacent element of lead and has an electronic structure and an energy band center similar to the lead, so that the potential possibility is provided for the interaction of the bismuth and the lead, and no relevant report is currently reported on the research of the bismuth and lead bimetallic oxide on the aspect of preparing ozone by electrolyzing water.
Disclosure of Invention
Aiming at the defects and shortcomings of the existing ozone preparation, the invention aims to provide a high-efficiency and stable triangular pyramid bismuth-lead bimetallic oxide electrocatalyst, and a preparation method and application thereof.
In order to achieve the purpose, the following technical scheme is provided:
a preparation method of a triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst comprises the following steps:
1) Dissolving a bismuth source, urea and a structure inducer in an ethylene glycol solution, stirring for 30-60 minutes at normal temperature, and performing ultrasonic dispersion for 10-30 minutes to obtain milky suspension;
2) Transferring the milky white suspension obtained in the step 1) into a polytetrafluoroethylene lining, placing the milky white suspension into a hydrothermal kettle, performing hydrothermal treatment for 6-12 hours at 120-180 ℃, naturally cooling the obtained solution to room temperature, filtering, washing the solution for 3-5 times by using deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 10-12 hours at 50-80 ℃ to obtain a bismuth oxide precursor material;
3) Placing the bismuth oxide precursor material obtained in the step 2) into a tubular furnace, and calcining for 2-6 hours at 300-500 ℃ in an air atmosphere to obtain a bismuth oxide material;
4) Dissolving the bismuth oxide material obtained in the step 3), a lead source and a sodium hypochlorite solution in an inorganic alkali solution, stirring at normal temperature for 20-40 minutes, transferring the solution to a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 60-100 ℃ for 6-10 hours, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and carrying out vacuum drying at 60-80 ℃ for 10-16 hours to obtain the bismuth-lead bimetallic oxide electrocatalyst.
Further, the bismuth source in the step 1) is bismuth nitrate or bismuth chloride.
Further, the structure inducing agent in the step 1) is polyvinylpyrrolidone or polyethylene glycol, wherein the molecular weight of the polyvinylpyrrolidone is 10000, and the molecular weight of the polyethylene glycol is 4000.
Further, the mass ratio of the bismuth source to the structure inducer is 4-5:1, the volume ratio of the mass of the bismuth source to the ethylene glycol is 1:20-30, the mass unit is g, and the volume unit is mL.
Further, the lead source in the step 4) is lead nitrate, lead acetate or lead chloride, preferably lead nitrate, and the mass ratio of bismuth oxide to the lead source is 4-5:1, preferably 4:1.
further, in the step 4), the inorganic alkali is potassium hydroxide or sodium hydroxide, the concentration is 1-2 mol/L, the mass concentration of the sodium hypochlorite is not less than 5%, and the volume ratio of the inorganic alkali solution to the sodium hypochlorite solution is 5-8:1, the volume ratio of the mass of the bismuth oxide to the inorganic alkali solution is 3-5:1, mass unit is mg, volume unit is mL.
The triangular pyramid bismuth-lead bimetallic oxide electrocatalyst prepared by the preparation method has the following atomic ratio of two metals: lead =12:1.
the application of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst in the reaction of preparing ozone by electrolyzing water comprises the following steps: controlling current and voltage by a constant current instrument, reacting in an H-shaped electrolytic cell, keeping water and gas smooth between two electrode chambers, taking saturated potassium sulfate aqueous solution as electrolyte, coating the triangular pyramid bismuth-lead bimetallic oxide electrocatalyst on carbon cloth as a working electrode in an anode chamber, taking a platinum sheet as a counter electrode in a cathode chamber, controlling the reaction current at 150mA and the cell voltage at 3-10V, and carrying out electrocatalysis to prepare ozone to obtain an ozone product.
The invention has the beneficial effects that:
1) The bismuth-lead bimetallic oxide has higher active site exposure ratio and unique molecular structure by virtue of the unique triangular pyramid structure, and can realize higher catalytic activity and current efficiency;
2) In the bimetallic oxide, the synergistic effect of the bismuth and the lead can promote the substances to better adsorb the O-intermediate in the process of producing ozone by electrocatalysis, thus being beneficial to the formation of ozone;
3) In the preparation process of the triangular pyramid-shaped bismuth-lead bimetallic oxide, a specific shape is formed under a proper hydrothermal condition, and Pb (OH) is reduced by utilizing sodium hypochlorite under an alkaline condition 2 The doping of Pb element is realized, which is beneficial to the more compact combination of two metals;
4) Compared with the traditional commercial lead dioxide catalyst, the triangular pyramid bismuth-lead bimetallic oxide electrocatalyst has the advantages of simple preparation, high electrocatalytic activity, long service life and good stability when used in the process of preparing ozone by electrolyzing water, and has wide application prospects.
Drawings
FIG. 1a is a schematic scanning electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 1 at 10 μm;
FIG. 1b is a scanning electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 1 at 5 μm;
FIG. 2a is a schematic scanning electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 2 at 10 μm;
FIG. 2b is a schematic scanning electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 2 at 5 μm;
FIG. 3a is a scanning electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 3 at 10 μm;
FIG. 3b is a schematic transmission electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 3 at 5 μm;
FIG. 4a is a schematic scanning electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 4 at 10 μm;
FIG. 4b is a schematic transmission electron microscope of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 4 at 5 μm;
FIG. 5 is a graph comparing real-time detection data of ozone concentration generated when the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalysts prepared in examples 1-4 and comparative sample 5 are used for preparing ozone by electrocatalysis.
Detailed Description
The invention will be further described with reference to the drawings and specific examples, but the scope of the invention is not limited thereto.
Example 1: the preparation method of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst comprises the following steps:
1) Dissolving 1.26g of bismuth chloride, 0.54g of urea and 300mg of polyvinylpyrrolidone with the molecular weight of 10000 in 25mL of glycol solution, stirring for 30 minutes at normal temperature, and performing ultrasonic dispersion for 10 minutes to obtain milky suspension;
2) Transferring the milky white suspension obtained in the step 1) into a polytetrafluoroethylene lining, carrying out hydrothermal treatment for 6 hours at 120 ℃, then naturally cooling the obtained solution to room temperature, filtering, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying for 10 hours at 50 ℃ to obtain a bismuth oxide precursor material;
3) Placing the bismuth oxide precursor material obtained in the step 2) into a tubular furnace, calcining at 300 ℃ in air atmosphere for 2 hours to obtain bismuth oxide;
4) Dissolving 80mg of bismuth oxide, 16mg of lead chloride and 2.5 mL of sodium hypochlorite solution with the mass concentration of 5.2% obtained in the step 3) in 20mL of 1mol/L sodium hydroxide solution, stirring at normal temperature for 20 minutes, transferring the solution into a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 60 ℃ for 10 hours, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and placing at 60 ℃ for vacuum drying for 10 hours to obtain the bismuth-lead bimetallic oxide electrocatalyst.
The schematic diagrams of the scanning electron microscope under 10 μm and the scanning electron microscope under 5 μm of the triangular pyramid bismuth-lead bimetallic oxide electrocatalyst obtained in example 1 are shown in fig. 1a and 1b, and it can be seen that the prepared catalyst has a better triangular pyramid shape, can expose a unique (310) crystal face, and is beneficial to the exposure of active sites, and meanwhile, the unique synergistic effect between bismuth and lead on the crystal face is beneficial to the generation of ozone under a lattice oxygen mechanism, so that the electrolyzed water reaction is easier to perform.
The triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 1 is used for the ozone preparation reaction by electrolyzing water:
weighing 10 mg of prepared triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst powder, mixing the powder with 1000 mu L of ethanol and 200 mu L of Nafion solution (the mass concentration of the Nafion solution is 5%), and performing ultrasonic treatment for 30 hours to ensure that the catalyst is completely dispersed in the mixed solution of the ethanol and the Nafion solution, thereby obtaining uniform catalyst slurry. Cutting the carbon cloth into a size of about 3 cm multiplied by 2 cm, uniformly dripping the catalyst slurry on the carbon cloth, and drying to be used as a working electrode (namely coating the triangular pyramid bismuth lead bimetallic oxide electrocatalyst on the carbon cloth to be used as the working electrode).
Controlling the current and voltage of the reaction by a constant current instrument, taking an H-shaped electrolytic cell as a reaction container, and coating the prepared triangular pyramid bismuth-lead bimetallic oxide electrocatalyst on carbon cloth in an anode chamber to serve as a working electrode; the platinum sheet is used as a counter electrode in the cathode chamber, the electrolyte is saturated potassium sulfate solution, an air outlet at one end of the H-shaped electrolytic cell is connected with an ozone detector to monitor the generation amount of ozone in real time and objectively reflect the catalytic performance of the catalyst, in the whole process of preparing ozone by electrocatalysis, the reaction current is controlled to be 150mA, the cell pressure is controlled to be 3-10V, the reaction time is 180 minutes, the ozone concentration can be obviously increased along with the reaction, and the ozone concentration can reach 3498 ppb after the reaction is carried out for 180 minutes.
In order to verify the catalytic stability of the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 1, the anode chamber working electrode after 1 reaction was left for 24 hours, and then the experiment for repeated electrocatalytic ozone preparation reaction was performed (the anode chamber working electrode was left for 24 hours after each use, and then used again for the next time). In the 1 st experiment of the anode chamber working electrode recycling reaction, the ozone concentration can reach 3475ppb after the reaction reaches 3 hours. In the 2 nd experiment of the anode chamber working electrode recycling reaction, the ozone concentration can reach 3391ppb after the reaction reaches 3 hours. In the 3 rd experiment of the anode chamber working electrode recycling reaction, the ozone concentration can reach 3315ppb after the reaction reaches 3 hours. It can be seen that the electrocatalysis effect is not substantially weakened in the recycling process of the working electrode of the anode chamber, which shows that the triangular pyramid shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 1 has better stability.
Example 2: the preparation method of the triangular pyramid-shaped bismuth-lead bimetallic oxide comprises the following steps:
1) Dissolving 1.5g of bismuth nitrate, 0.54g of urea and 300mg of polyethylene glycol with the molecular weight of 4000 in 30mL of ethylene glycol solution, stirring for 60 minutes at normal temperature, and performing ultrasonic dispersion for 30 minutes to obtain milky suspension;
2) Transferring the milky white suspension obtained in the step 1) into a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 140 ℃ for 8 hours, naturally cooling the obtained solution to room temperature, filtering, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and carrying out vacuum drying at 70 ℃ for 12 hours to obtain a bismuth oxide precursor material;
3) Placing the bismuth oxide precursor material obtained in the step 2) into a tubular furnace, calcining at 350 ℃ in air atmosphere for 3 hours to obtain bismuth oxide;
4) Dissolving 100mg of bismuth oxide, 20mg of lead nitrate and 5mL of sodium hypochlorite solution with the mass concentration of 5.2% obtained in the step 3) in 30mL of 1.5mol/L potassium hydroxide solution, stirring at normal temperature for 30 minutes, transferring the solution to a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 70 ℃ for 8 hours, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and placing at 70 ℃ for vacuum drying for 12 hours to obtain the bismuth-lead bimetallic oxide electrocatalyst.
The schematic scanning electron microscope at 10 μm and the schematic scanning electron microscope at 5 μm of the triangular pyramid shaped bismuth-lead bimetallic oxide electrocatalyst obtained in example 2 are shown in fig. 2a and 2b, from which it can be seen that the prepared catalyst has a better triangular pyramid shape.
The triangular pyramid shaped bismuth-lead bimetallic oxide electrocatalyst of example 2 is used for the reaction of preparing ozone by electrolyzing water:
in the case that the catalyst prepared in example 1 is used in the preparation of the electrode anode, the added catalyst prepared in example 1 is replaced by the catalyst prepared in example 2 with the same quality, the rest of the operation conditions are the same as the experimental process for preparing ozone by electrolyzing water in example 1, and the change relationship of the concentration of ozone generated by catalytic reaction of the electrolyzed water along with the reaction time is shown in fig. 5, so that the concentration of the generated gaseous ozone reaches 3094ppb after 200 minutes, and the prepared triangular pyramid-shaped bismuth-lead bimetallic oxide has good ozone generation performance.
Example 3: the preparation method of the triangular pyramid-shaped bismuth-lead bimetallic oxide comprises the following steps:
1) Dissolving 1.26g of bismuth chloride, 0.54g of urea and 300mg of polyvinylpyrrolidone with the molecular weight of 10000 in 35mL of glycol solution, stirring for 60 minutes at normal temperature, and performing ultrasonic dispersion for 30 minutes to obtain milky suspension;
2) Transferring the milky white suspension obtained in the step 1) into a polytetrafluoroethylene lining, carrying out hydrothermal treatment for 10 hours at 160 ℃, then naturally cooling the obtained solution to room temperature, filtering, washing with deionized water and absolute ethyl alcohol for 5 times respectively, and then carrying out vacuum drying for 10 hours at 80 ℃ to obtain a bismuth oxide precursor material;
3) Placing the bismuth oxide precursor material obtained in the step 2) into a tubular furnace, calcining at 400 ℃ in an air atmosphere, and calcining for 4 hours to obtain bismuth oxide;
4) Dissolving 120mg of bismuth oxide, 30mg of lead acetate and 5mL of sodium hypochlorite solution with the concentration of 5.2 percent obtained in the step 3) in 35mL of 1.5mol/L potassium hydroxide solution, stirring at normal temperature for 30 minutes, transferring the solution to a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 80 ℃ for 9 hours, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 5 times respectively, and placing at 80 ℃ for vacuum drying for 14 hours to obtain the bismuth-lead bimetallic oxide electrocatalyst.
The schematic scanning electron microscope at 10 μm and the schematic scanning electron microscope at 5 μm of the triangular pyramid shaped bismuth-lead bimetallic oxide electrocatalyst obtained in example 3 are shown in fig. 3a and 3b, from which it can be seen that the prepared catalyst has a better triangular pyramid shape.
The triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 3 is used for the ozone preparation reaction by electrolyzing water:
in the case that the catalyst prepared in example 1 is used in the preparation of the electrode anode, the added catalyst prepared in example 1 is replaced by the catalyst prepared in example 3 with the same quality, the rest of the operation conditions are the same as the experimental process for preparing ozone by electrolyzing water in example 1, and the change relationship of the concentration of ozone generated by catalytic reaction of the electrolyzed water along with the reaction time is shown in fig. 5, so that the concentration of the generated gaseous ozone reaches 2865ppb after 180 minutes, and the prepared triangular pyramid-shaped bismuth-lead bimetallic oxide has good ozone generation performance.
Example 4: the preparation method of the triangular pyramid bismuth-lead bimetallic oxide comprises the following steps:
1) Dissolving 1.5g of bismuth nitrate, 0.54g of urea and 0.3 g of polyethylene glycol with the molecular weight of 4000 in 35mL of glycol solution, stirring for 40 minutes at normal temperature, and performing ultrasonic dispersion for 20 minutes to obtain milky suspension;
2) Transferring the milky white suspension obtained in the step 1) into a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 12 hours, naturally cooling the obtained solution to room temperature, filtering, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and carrying out vacuum drying at 80 ℃ for 12 hours to obtain a bismuth oxide precursor material;
3) Placing the bismuth oxide precursor material obtained in the step 2) into a tubular furnace, calcining at 500 ℃ in air atmosphere for 6 hours to obtain bismuth oxide;
4) Dissolving 150mg of bismuth oxide, 30mg of lead nitrate and 5mL of sodium hypochlorite with the concentration of 5.2 percent obtained in the step 3) in 40mL of 2 mol/L sodium hydroxide solution, stirring at normal temperature for 30 minutes, transferring the solution to a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 100 ℃ for 10 hours, cooling the solution to room temperature, washing the solution for 5 times respectively by using deionized water and absolute ethyl alcohol, and placing the solution at 80 ℃ for vacuum drying for 16 hours to obtain the bismuth-lead bimetallic oxide electrocatalyst.
The schematic scanning electron microscope at 10 μm and the schematic scanning electron microscope at 5 μm of the triangular pyramid shaped bismuth-lead bimetallic oxide electrocatalyst obtained in example 4 are shown in fig. 4a and 4b, from which it can be seen that the prepared catalyst has a better triangular pyramid shape.
The triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared in example 4 is used for the ozone preparation reaction by electrolyzing water:
in the case that the catalyst prepared in example 1 is used in the preparation of the electrode anode, the added catalyst of example 1 is replaced by the catalyst prepared in example 3 with the same quality, the rest of the operation conditions are the same as the experimental process for preparing ozone by electrolyzing water in example 1, and the change relationship of the concentration of ozone generated by the catalytic reaction of the electrolyzed water along with the reaction time is shown in fig. 5, so that the concentration of the generated gaseous ozone reaches 3832ppb after 180 minutes, and the prepared triangular pyramid-shaped bismuth-lead bimetallic oxide has good ozone generating performance.
Comparative example 5: preparation of commercial lead dioxide catalyst and use thereof for electrocatalytic production of ozone
Weighing 16mg of commercial lead dioxide catalyst (purchased from hong kong 31066. The carbon cloth was cut to a size of about 3 cm × 2 cm, and the dispersed catalyst slurry was uniformly dropped on the carbon cloth, and dried to be used as a working electrode (i.e., a material in which the Pt/C catalyst was coated on the carbon cloth was used as a working electrode).
The voltage and current are controlled by a constant current meter, and an H-shaped electrolytic cell is adopted for reaction. In the anode chamber, a material with commercial lead dioxide catalyst coated on carbon cloth is used as a working electrode; in the cathode chamber, a platinum sheet is used as a counter electrode, and the electrolyte is saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic cell is connected with an ozone detector to detect the generation condition of ozone in real time. When the electro-catalysis is used for preparing ozone, the current is controlled at 150mA, the cell voltage is controlled between 3V and 10V, and the reaction time is 180 minutes. A real-time plot of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeded is shown in figure 5. As can be seen from FIG. 5, as the reaction proceeds, the ozone concentration is gradually increased, and the ozone concentration of the reaction time reaching 180 minutes can reach 2043 ppb.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (9)
1. A preparation method of a triangular pyramid bismuth-lead bimetallic oxide electrocatalyst is characterized by comprising the following steps:
1) Dissolving a bismuth source, urea and a structure inducer in an ethylene glycol solution, stirring for 30-60 minutes at normal temperature, and performing ultrasonic dispersion for 10-30 minutes to obtain a milky suspension;
2) Transferring the milky white suspension obtained in the step 1) into a polytetrafluoroethylene lining, placing the milky white suspension into a hydrothermal kettle, performing hydrothermal treatment for 6-12 hours at 120-180 ℃, naturally cooling the obtained solution to room temperature, filtering, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and performing vacuum drying at 50-80 ℃ for 10-12 hours to obtain a bismuth oxide precursor material;
3) Placing the bismuth oxide precursor material obtained in the step 2) into a tubular furnace, and calcining for 2-6 hours at 300-500 ℃ in an air atmosphere to obtain a bismuth oxide material;
4) Dissolving the bismuth oxide material obtained in the step 3), a lead source and a sodium hypochlorite solution in an inorganic alkali solution, stirring at normal temperature for 20-40 minutes, transferring the solution to a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 60-100 ℃ for 6-10 hours, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and carrying out vacuum drying at 60-80 ℃ for 10-16 hours to obtain the bismuth-lead bimetallic oxide electrocatalyst.
2. The method for preparing the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst according to claim 1, wherein the bismuth source in step 1) is bismuth nitrate or bismuth chloride.
3. The method of claim 1, wherein the structure inducer in step 1) is polyvinylpyrrolidone or polyethylene glycol, the molecular weight of polyvinylpyrrolidone is 10000, and the molecular weight of polyethylene glycol is 4000.
4. The method for preparing the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst according to claim 3, wherein the mass ratio of the bismuth source to the structure inducer is 4-5:1, the volume ratio of the mass of the bismuth source to the ethylene glycol is 1:20-30, the mass unit is g, and the volume unit is mL.
5. The method for preparing the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst according to claim 1, wherein the lead source in the step 4) is lead nitrate, lead acetate or lead chloride, preferably lead nitrate, and the mass ratio of bismuth oxide to the lead source is 4-5:1.
6. the method for preparing the triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst according to claim 1, wherein the inorganic base in the step 4) is potassium hydroxide or sodium hydroxide, the solution concentration is 1-2 mol/L, the mass concentration of sodium hypochlorite is not less than 5%, and the volume ratio of the inorganic alkali solution to the sodium hypochlorite solution is 5-8:1, the volume ratio of the mass of the bismuth oxide to the inorganic alkaline solution is 3-5:1, the unit of mass is mg, and the unit of volume is mL.
7. The triangular pyramid-shaped bismuth-lead bimetallic oxide electrocatalyst prepared by the preparation method according to any one of claims 1 to 6, characterized in that the atomic ratio of the two metals is bismuth: lead =12:1.
8. the use of the triangular pyramid shaped bismuth-lead bimetallic oxide electrocatalyst according to claim 7 in a reaction for preparing ozone by electrolysis of water.
9. Use according to claim 8, characterized in that it comprises the following steps: controlling current and voltage by a constant current instrument, reacting in an H-shaped electrolytic cell, keeping water and gas smooth between two electrode chambers, taking saturated potassium sulfate aqueous solution as electrolyte, coating the triangular pyramid bismuth-lead bimetallic oxide electrocatalyst on carbon cloth as a working electrode in an anode chamber, taking a platinum sheet as a counter electrode in a cathode chamber, controlling the reaction current at 150mA and the cell voltage at 3-10V, and carrying out electrocatalysis to prepare ozone to obtain an ozone product.
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