Boron-nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst, preparation method, and application thereof

Abstract

The present invention discloses a boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst, its preparation method, and application, comprising the following steps: stirring and mixing a platinum source, a transition metal source, and a solvent to adjust the pH, and heating the mixture under a CO atmosphere to produce a metal carbonyl complex solution A; dissolving polyethylene glycol, urea, boric acid, and melamine in deionized water, drying to obtain a solid mixture, grinding the solid mixture, placing it in a tube furnace, and calcining it under a high-purity gas atmosphere to produce BNC nanotubes; ultrasonically dispersing the BNC nanotubes, a surfactant, and a solvent to obtain a solution B; pouring the metal carbonyl complex solution A and solution B into the lining of a reactor, ultrasonically dispersing them to obtain a product by hydrothermal heating; and filtering, washing, and drying to obtain the boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst. The preparation method of the present invention has low preparation cost, high electrocatalytic ozone production, high hydrogen production efficiency, and mild operating conditions for the electrocatalytic reaction process, making it environmentally friendly and pollution-free.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalysis, and in particular relates to a boron-nitrogen-carbon nanotube-loaded platinum alloy bifunctional electrocatalyst, a preparation method thereof, and an application thereof. Background Art

[0002] Ozone has strong oxidizing properties and is a stronger oxidant than oxygen. It can undergo oxidation reactions at lower temperatures and is now widely used in areas such as bacterial inactivation, fruit and vegetable disinfection, and medical and health disinfection. During use, it is reduced to oxygen and does not produce secondary pollution. These characteristics have led to its widespread application in industrial sectors such as water treatment, chemicals, food, fragrances, and pharmaceuticals, as well as in air disinfection and sterilization, and it has received widespread attention. However, the overpotential of the oxygen evolution reaction at the anode of water electrolysis is 1.23 V, while the overpotential of the ozone production reaction is 1.51 V. This means that the production of ozone requires more energy to overcome a larger reaction energy barrier. The anode and cathode reaction equations are as follows:

[0003] Anodic reaction:

[0004] 3H2O = O3 + 6H + + 6e - (E1 0 = 1.51 V)

[0005] 2H2O = O2 + 4H + + 4e - (E2 0 = 1.23 V)

[0006] Cathode reaction:

[0007] 2H + + 2e - = H2 (E3 0 = 0.00 V)

[0008] Therefore, bifunctional catalysts for electrochemical water splitting to produce ozone and hydrogen are even more scarce.

[0009] Currently, Pt-based catalysts are commonly used electrocatalysts for ozone production and hydrogen evolution reactions. They have high overpotentials and unique electronic structures, but the high price and poor stability of platinum limit its practical application. Summary of the Invention

[0010] To address the aforementioned issues in the prior art, the present invention aims to provide a bifunctional electrocatalyst comprising boron-nitrogen-carbon nanotubes (BNCs) and platinum alloys, as well as its preparation method and application. This invention incorporates another metal element, M, into the Pt-based catalyst and loads platinum alloy nanoparticles onto a BNC nanotube support via a carbonyl complex method. This reduces costs while maintaining excellent stability and reactivity. The tubular structure of the BNC nanotubes offers a large specific surface area, which helps increase electrolysis reaction efficiency. Using these as anode and cathode catalysts in SPE / electrolytic ozone and hydrogen generators, they can produce high-purity ozone and hydrogen.

[0011] A method for preparing a boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst comprises the following steps:

[0012] 1) A platinum source, a transition metal source, and a solvent are added to a two-necked flask, and an inorganic base is added to the solution under stirring to adjust the pH to 6-13. CO is then continuously introduced into the solution, and the solution is heated to 30-70° C. under a CO atmosphere for a reaction of 12-72 h to prepare a metal carbonyl complex solution A, wherein the platinum source is one of potassium chloroplatinate, sodium chloroplatinate, platinum acetylacetonate, and chloroplatinic acid; the transition metal source is cobalt acetylacetonate, iron acetylacetonate, palladium acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate, or copper acetylacetonate; the solvent is one of ethanol, methanol, tetrahydrofuran, N,N-dimethylpyrrolidone, and toluene; and the inorganic base is one of NaOH, KOH, CH3COONa, NaCO3, and ammonia solution;

[0013] 2) dissolving polyethylene glycol, urea, boric acid, and melamine in deionized water and stirring for 1-3 hours to mix uniformly. The resulting solution is dried in an oven at 80-200°C for 6-24 hours to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture is ground uniformly and placed in a tube furnace. The mixture is calcined in a high-purity nitrogen atmosphere at a temperature of 500-900°C for 2-8 hours to obtain BNC nanotubes. The mass ratio of polyethylene glycol, urea, boric acid, and melamine is 0.08-0.12: 0.8-1.2: 0.02-0.05: 0.16-0.24.

[0014] 3) ultrasonically dispersing the BNC nanotubes prepared in step 2), a surfactant, and a solvent for 30-60 min to prepare solution B, wherein the mass ratio of BNC nanotubes to surfactant is 6-10:1;

[0015] 4) pouring the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically dispersing for 10-30 minutes, and then hydrothermally heating at 100-200° C. for 6-24 hours to obtain the product;

[0016] 5) filtering the product obtained in step 4), washing it with anhydrous ethanol and deionized water 3-5 times each, and vacuum drying it at 40-60° C. for 12-24 h. After drying, collecting the product to obtain the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst.

[0017] Furthermore, in step 1), the molar ratio of the platinum source to the transition metal source is 1-5:1, preferably 1:1.

[0018] Furthermore, the surfactant in step 3) is one of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecylsulfonate, sodium hexadecylbenzenesulfonate, polyvinyl pyrrolidone, polyvinyl alcohol, 1-methyl-2-pyrrolidone, citrate and sodium ethylenediaminetetraacetate.

[0019] Furthermore, the total metal loading of platinum and transition metal is 5-50%, preferably 5%.

[0020] The application of the above-mentioned boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst in the electrocatalytic decomposition of water to produce ozone and hydrogen is as follows: the boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst is coated on the anode and cathode sides of a proton exchange membrane to prepare a membrane electrode, which is assembled into an SPE / electrolytic ozone and hydrogen generator. Deionized water is added to the electrolysis chamber to carry out the water electrolysis reaction. The electrolysis voltage is set to 5.0V and the current is set to 10.0A. Ozone is generated at the anode and hydrogen is generated at the cathode. The proton exchange membrane is Nafion N117, Nafion N115, Nafion D520, Nafion NRE211, Nafion NRE212 or NafionHP.

[0021] The application of the above-mentioned boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst in the electrolysis of water to produce ozone is characterized by controlling the voltage and current with a constant current meter, using an H-type electrolytic cell for the reaction, keeping water and air unobstructed between the two electrode chambers, using a saturated potassium sulfate solution as the electrolyte, and coating the boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst on a carbon cloth as the working electrode in the anode chamber, and a platinum sheet as the counter electrode in the cathode chamber. The reaction current is controlled at 200-300 mA, and the cell voltage is controlled at 5-7 V to electrocatalytically produce ozone.

[0022] The application of the above-mentioned boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst in the electrolysis of water to produce hydrogen is characterized by controlling the voltage and current with a constant current meter, using an H-type electrolytic cell for the reaction, keeping water and gas unobstructed between the two electrode chambers, using a 0.5M H2SO4 solution as the electrolyte, coating the boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst on carbon cloth as the working electrode in the anode chamber, an Ag / AgCl electrode as the reference electrode, and a platinum sheet as the counter electrode in the cathode chamber. The reaction voltage is set to 0.4 V, the reaction current is controlled between 100-200 mA, and hydrogen is produced by electrocatalysis. The hydrogen yield is calculated using the water displacement method.

[0023] By adopting the above technology, compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] 1) The hollow carbon nanotube structure of the BNC nanotubes in the boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst of the present invention is beneficial to the mass transfer and diffusion of the reaction raw materials and reaction products, and the tubular structure has good conductivity and a large specific surface area, which is conducive to increasing the efficiency of the electrolysis reaction;

[0025] 2) In the preparation method of the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst of the present invention, the active component of the platinum alloy nanoparticles prepared by the carbonyl complex method is supported on the BNC nanotube support. Compared with the traditional method of supporting the active component on the support, the active component particles are small in size and have a narrow particle size distribution. They are not easy to agglomerate during the reaction and have good stability and reactivity. This method provides advantages for the large-scale production of alloy nanoparticles.

[0026] 3) The boron-nitrogen-carbon nanotube-loaded platinum alloy bifunctional electrocatalyst of the present invention has low preparation cost, high reaction efficiency for producing hydrogen in electrocatalytic reactions, high ozone production, and mild operating conditions for the electrocatalytic reaction process, which is green and pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst prepared in Example 1 at 3 μm;

[0028] Figure 2 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst prepared in Example 1 at 5 nm;

[0029] Figure 3 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum-cobalt alloy bifunctional electrocatalyst prepared in Example 2 at 3 μm;

[0030] Figure 4This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum-cobalt alloy bifunctional electrocatalyst prepared in Example 2 at 5 nm;

[0031] Figure 5 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst prepared in Example 3 at 3 μm;

[0032] Figure 6 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst prepared in Example 3 at 5 nm;

[0033] Figure 7 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst prepared in Example 4 at 3 μm;

[0034] Figure 8 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst prepared in Example 4 at 5 nm;

[0035] Figure 9 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum iron alloy bifunctional electrocatalyst prepared in Example 5 at 3 μm;

[0036] Figure 10 This is a transmission electron microscope observation image of the boron nitrogen carbon nanotube-supported platinum iron alloy bifunctional electrocatalyst prepared in Example 5 at 5 nm;

[0037] Figure 11 Time-concentration diagram of ozone generation at the anode of SPE / electrolytic ozone and hydrogen generator by the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst prepared in Examples 1-5 and the commercial PbO2 catalyst in Example 6;

[0038] Figure 12 The time-concentration graph of hydrogen production at the cathode of the SPE / electrolytic ozone and hydrogen generator for the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst prepared in Examples 1-5 and the commercial Pt / C catalyst in Example 6;

[0039] Figure 13 A comparison chart of real-time detection of ozone concentrations generated when the boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst prepared in Examples 1-5 and the commercial PbO2 catalyst in Example 6 are used for electrocatalytic ozone production;

[0040] Figure 14 This is a data comparison chart of hydrogen evolution rates when the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst prepared in Examples 1-5 and the commercial Pt / C catalyst in Example 6 are used for electrocatalytic production of hydrogen. DETAILED DESCRIPTION

[0041] The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

[0042] Example 1

[0043] Preparation of a boron-nitrogen-carbon nanotube-supported platinum-nickel alloy bifunctional electrocatalyst, comprising the following steps:

[0044] 1) 4 mg of potassium chloroplatinate, 2.18 mg of nickel acetylacetonate, and 20 mL of methanol were added to a 100 mL two-necked flask. Sodium acetate was added to the solution while stirring to adjust the pH to 7. CO was then continuously introduced into the solution. The solution was heated to 30°C under a CO atmosphere and reacted for 12 h to prepare a metal carbonyl complex solution A.

[0045] 2) 0.15 g of boric acid, 5 g of urea, 0.5 g of polyethylene glycol, and 1 g of melamine were dissolved in deionized water and stirred for 1 h to mix thoroughly. The resulting solution was placed in an oven and dried at 80°C for 6 h to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture was evenly ground and placed in a tube furnace for calcination under high-purity nitrogen at 500°C for 2 h to produce BNC nanotubes.

[0046] 3) Ultrasonic dispersion of 40 mg of BNC nanotubes, 4 mg of polyvinyl pyrrolidone, and 10 mL of methanol for 30 min to prepare solution B.

[0047] 4) pouring the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically dispersing for 10 minutes, and then hydrothermally heating at 100°C for 6 hours to obtain the product;

[0048] 5) The product obtained in step 4) was filtered, washed with anhydrous ethanol and deionized water three times each, and vacuum dried at 40° C. for 12 h. After drying, the boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst was collected.

[0049] The SEM image of the boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst obtained in Example 1 at 3 μm is as follows: Figure 1 As shown in the figure, tubular BNC nanotubes were prepared, and the TEM image at 5 nm is shown in Figure 2 As shown in the figure, it can be seen that the platinum-nickel alloy nanoparticles have basically achieved good loading.

[0050] The boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst of Example 1 is used in SPE / electrolytic ozone and hydrogen generators:

[0051] The prepared boron nitrogen carbon nanotube-loaded platinum nickel alloy bifunctional electrocatalyst was used as the anode and cathode catalyst of the SPE / electrolytic ozone and hydrogen generator. The proton exchange membrane (Nafion N117) was used as the membrane electrode substrate. The boron nitrogen carbon nanotube-loaded platinum nickel alloy bifunctional electrocatalyst was coated on the anode and cathode surfaces of the proton exchange membrane to prepare the membrane electrode. The membrane electrode was assembled into an SPE / electrolytic ozone and hydrogen generator for testing the anode electrolysis ozone production performance and the cathode electrolysis hydrogen decomposition performance. Deionized water was added to the electrolysis chamber to carry out the water electrolysis reaction. The ozone produced by electrolysis was connected to the ozone detector through the anode outlet, and the hydrogen produced by electrolysis was connected to the hydrogen detector through the cathode outlet. The electrolysis voltage was set to 5.0 V and the current was set to 10.0 A. The volume and mass concentrations of the produced ozone and hydrogen changed with time, as shown in the figure. Figure 11 、 12 As shown. Figure 11 、 12 It can be seen that the ozone volume mass concentration detected by the ozone detector is stable at 241.32 g / m 3 The hydrogen gas concentration was detected by the hydrogen detector and was stable at 207.38 g / m 3 .

[0052] The boron-nitrogen-carbon nanotube-supported platinum-nickel alloy bifunctional electrocatalyst of Example 1 is used for the electrolysis of water to produce ozone:

[0053] 8 mg of the prepared boron-nitrogen-carbon nanotube-supported platinum-nickel alloy bifunctional electrocatalyst powder was weighed and mixed with 900 μL of ethanol and 100 μL of a 5% Nafion solution. The mixture was sonicated for 0.5 hours to completely disperse the catalyst in the ethanol-Nafion solution mixture, resulting in a uniform catalyst slurry. A carbon cloth was cut into approximately 2 cm × 2 cm pieces, and the dispersed catalyst slurry was evenly drop-coated on the cloth. After drying, the cloth served as the working electrode (i.e., the boron-nitrogen-carbon nanotube-supported platinum-nickel alloy bifunctional electrocatalyst was coated on the carbon cloth as the working electrode).

[0054] The voltage and current were controlled by a constant current meter, and an H-type electrolytic cell was used for the reaction. Water and air were kept unobstructed between the two electrode chambers. A saturated potassium sulfate aqueous solution was used as the electrolyte. The boron nitrogen carbon nanotube-loaded platinum nickel alloy bifunctional electrocatalyst was coated on a carbon cloth as the working electrode in the anode chamber, and a platinum sheet was used as the counter electrode in the cathode chamber. One end of the H-type electrolytic cell was connected to an ozone detector to monitor the production of ozone in real time. The reaction current was controlled at 200-300 mA, the cell voltage was controlled at 5-7 V, and ozone was produced electrocatalytically for 60 minutes. As the reaction proceeded, the real-time detection of the ozone concentration produced by the electrocatalytic reaction was as shown in the figure below. Figure 13 As shown. Figure 13It can be seen that as the reaction proceeds, the ozone concentration gradually increases, and when the reaction time reaches 60 minutes, the ozone concentration stabilizes at 6000 ppm.

[0055] In order to verify the catalytic stability of the boron nitrogen carbon nanotube-loaded platinum nickel alloy bifunctional electrocatalyst prepared in Example 1, the anode chamber working electrode after the above reaction was placed for 24 hours, and then the electrocatalytic ozone preparation reaction experiment was repeated (the anode chamber working electrode was placed for one day after each use before the next use). In the first experiment of the repeated use of the anode chamber working electrode, the ozone concentration was stable at 6000ppm after 60 minutes of reaction. In the second experiment of the repeated use of the anode chamber working electrode, the ozone concentration was stable at 6000ppm after 60 minutes of reaction. In the third experiment of the repeated use of the anode chamber working electrode, the ozone concentration was stable at 5800ppm after 60 minutes of reaction. It can be seen that the electrocatalytic effect was basically not weakened during the repeated use of the anode chamber working electrode, indicating that the boron nitrogen carbon nanotube-loaded platinum nickel alloy bifunctional electrocatalyst prepared in Example 1 has good stability.

[0056] The boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst of Example 1 is used for the electrolysis of water to produce hydrogen:

[0057] 8 mg of the prepared boron-nitrogen-carbon nanotube-supported platinum-nickel alloy bifunctional electrocatalyst powder was weighed and mixed with 900 μL of ethanol and 100 μL of a 5% Nafion solution. The mixture was sonicated for 0.5 hours to completely disperse the catalyst in the ethanol-Nafion solution mixture, resulting in a uniform catalyst slurry. A carbon cloth was cut into approximately 2 cm × 2 cm pieces, and the dispersed catalyst slurry was evenly drop-coated on the cloth. After drying, the cloth served as the working electrode (i.e., the boron-nitrogen-carbon nanotube-supported platinum-nickel alloy bifunctional electrocatalyst was coated on the carbon cloth as the working electrode).

[0058] The voltage and current were controlled by a constant current meter, and an H-type electrolytic cell was used for the reaction. Water and air were kept unobstructed between the two electrode chambers. A 0.5M H2SO4 solution was used as the electrolyte. A boron nitrogen carbon nanotube-loaded platinum-nickel alloy bifunctional electrocatalyst was coated on a carbon cloth as the working electrode in the anode chamber, an Ag / AgCl electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode in the cathode chamber. The reaction voltage was set to 0.4 V, and the reaction current was controlled between 100-200 mA. Hydrogen was produced electrocatalytically, and the hydrogen yield was calculated using the water displacement method. As the reaction proceeded, the hydrogen yield produced by the electrocatalytic reaction was detected as shown in the figure below. Figure 14 As shown. Figure 14It can be seen that as the reaction proceeds, the hydrogen production gradually increases. When the reaction time reaches 250 seconds, the hydrogen production can reach 10 mL, and the yield is stable at 2.3 mL·min -1 .

[0059] To verify the catalytic stability of the boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst prepared in Example 1, the anode chamber working electrode was left standing for 24 hours after the above reaction, and then the electrocatalytic hydrogen production reaction experiment was repeated (the anode chamber working electrode was left standing for one day after each use before the next use). In the first experiment of the anode chamber working electrode repeated use reaction, the hydrogen yield was stable at 2.3 mL·min -1 In the second experiment of the anode chamber working electrode reuse reaction, the hydrogen production rate was stable at 2.3 mL·min -1 In the third experiment of the anode chamber working electrode reuse reaction, the hydrogen production rate was stable at 2.3 mL·min -1 It can be seen that the electrocatalytic effect is substantially not weakened during the repeated use of the working electrode in the anode chamber, indicating that the boron nitrogen carbon nanotube-supported platinum nickel alloy bifunctional electrocatalyst prepared in Example 1 has good stability.

[0060] Example 2

[0061] Preparation of a boron-nitrogen-carbon nanotube-supported platinum-cobalt alloy bifunctional electrocatalyst comprises the following steps:

[0062] 1) 4.2 mg of sodium chloroplatinate, 2.2 mg of cobalt acetylacetonate, and 20 mL of ethanol were added to a 100 mL two-necked flask. Sodium hydroxide was added to the solution while stirring to adjust the pH to 8. CO was then continuously introduced into the solution. The solution was heated to 40°C under a CO atmosphere and reacted for 18 h to prepare a metal carbonyl complex solution A.

[0063] 2) 0.15 g of boric acid, 5 g of urea, 0.5 g of polyethylene glycol, and 1 g of melamine were dissolved in deionized water and stirred for 2 h to mix thoroughly. The resulting solution was dried in an oven at 100°C for 10 h to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture was evenly ground and placed in a tube furnace for calcination under high-purity nitrogen at 600°C for 3 h to produce BNC nanotubes.

[0064] 3) Ultrasonic dispersion of 40 mg of BNC nanotubes, 4.5 mg of sodium hexadecyl sulfate, and 10 mL of ethanol for 40 min to prepare solution B.

[0065] 4) Pour the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically disperse for 20 minutes, and then hydrothermally heat at 120° C. for 12 hours to obtain the product;

[0066] 5) The product obtained in step 4) was filtered, washed with anhydrous ethanol and deionized water 4 times each, and vacuum dried at 50° C. for 18 h. After drying, the boron nitrogen carbon nanotube-supported platinum-cobalt alloy bifunctional electrocatalyst was collected.

[0067] The SEM image of the boron nitrogen carbon nanotube-supported platinum cobalt alloy bifunctional electrocatalyst obtained in Example 2 at 3 μm is as follows: Figure 3 As shown in the figure, tubular BNC nanotubes were prepared, and the TEM image at 5 nm is shown in Figure 4 As shown in the figure, it can be seen that the platinum-cobalt alloy nanoparticles have basically achieved good loading.

[0068] The boron nitrogen carbon nanotube-supported platinum cobalt alloy bifunctional electrocatalyst of Example 2 is used in SPE / electrolytic ozone and hydrogen generators:

[0069] The prepared boron nitrogen carbon nanotube-loaded platinum cobalt alloy bifunctional electrocatalyst was used as the anode and cathode catalyst of the SPE / electrolytic ozone and hydrogen generator. The proton exchange membrane (Nafion N115) was used as the membrane electrode substrate. The boron nitrogen carbon nanotube-loaded platinum cobalt alloy bifunctional electrocatalyst was coated on the anode and cathode surfaces of the proton exchange membrane to prepare the membrane electrode. The membrane electrode was assembled into an SPE / electrolytic ozone and hydrogen generator for testing the anode electrolysis ozone production performance and cathode electrolysis hydrogen decomposition performance. Deionized water was added to the electrolysis chamber to carry out the water electrolysis reaction. The ozone produced by electrolysis was connected to the ozone detector through the anode outlet, and the hydrogen produced by electrolysis was connected to the hydrogen detector through the cathode outlet. The electrolysis voltage was set to 5.0 V and the current was set to 10.0 A. The volume and mass concentrations of the produced ozone and hydrogen changed with time, as shown in the figure. Figure 11 、 12 .Depend on Figure 11 、 12 It can be seen that the ozone volume mass concentration detected by the ozone detector is stable at 220.02 g / m 3 The hydrogen gas concentration was detected by the hydrogen detector and was stable at 185.84 g / m 3 .

[0070] The boron nitrogen carbon nanotube-supported platinum-cobalt alloy bifunctional electrocatalyst of Example 2 is used for the electrolysis of water to produce ozone:

[0071] In the process of preparing the electrode anode using the catalyst prepared in Example 2, the catalyst in Example 1 was replaced with the catalyst prepared in Example 2 of equal mass. The remaining operating conditions were the same as those in the experimental process of preparing ozone by electrolysis of water in Example 1. The relationship between the concentration of ozone generated by the electrolysis of water catalysis and the reaction time is shown in FIG. Figure 13 As shown, as the reaction proceeds, the ozone concentration gradually increases, and when the reaction time reaches 60 minutes, the ozone concentration is stabilized at 3000 ppm.

[0072] The boron nitrogen carbon nanotube-supported platinum cobalt alloy bifunctional electrocatalyst of Example 2 is used for the electrolysis of water to produce hydrogen:

[0073] In the process of preparing the electrode anode, the catalyst prepared in Example 2 was used to replace the catalyst in Example 1 with the catalyst prepared in Example 2 of equal mass. The other operating conditions were the same as those in the experimental process of preparing hydrogen by electrolysis of water in Example 1. The hydrogen production produced by the electrolysis of water catalytic reaction was detected as shown in the figure below. Figure 14 As shown. Figure 14 It can be seen that as the reaction proceeds, the hydrogen production gradually increases. When the reaction time reaches 380 seconds, the hydrogen production can reach 10 mL, and the yield is stable at 1.6 mL·min -1 .

[0074] Example 3

[0075] Preparation of a boron-nitrogen-carbon nanotube-supported platinum-palladium alloy bifunctional electrocatalyst, comprising the following steps:

[0076] 1) 3.5 mg of platinum acetylacetonate, 3.9 mg of palladium acetylacetonate, and 20 mL of N,N-dimethylpyrrolidone were added to a 100 mL two-necked flask. Potassium hydroxide was added to the solution while stirring to adjust the pH to 9. CO was then continuously introduced into the solution. The solution was heated to 50°C under a CO atmosphere and reacted for 24 h to prepare a metal carbonyl complex solution A.

[0077] 2) 0.15 g of boric acid, 5 g of urea, 0.5 g of polyethylene glycol, and 1 g of melamine were dissolved in deionized water and stirred for 3 h to mix thoroughly. The resulting solution was dried in an oven at 150°C for 15 h to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture was evenly ground and placed in a tube furnace for calcination under high-purity nitrogen at 700°C for 5 h to produce BNC nanotubes.

[0078] 3) Ultrasonic dispersion of 40 mg of BNC nanotubes, 5 mg of sodium hexadecylbenzenesulfonate, and 10 mL of N,N-dimethylpyrrolidone for 50 min to prepare solution B.

[0079] 4) pouring the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically dispersing for 30 minutes, and then hydrothermally heating at 140° C. for 18 hours to obtain the product;

[0080] 5) The product obtained in step 4) was filtered, washed with anhydrous ethanol and deionized water 5 times each, and vacuum dried at 60° C. for 24 h. After drying, the boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst was collected.

[0081] The SEM image of the boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst obtained in Example 3 at 3 μm is as follows: Figure 5 As shown in the figure, tubular BNC nanotubes were prepared, and the TEM image at 5 nm is shown in Figure 6 As shown in the figure, it can be seen that the platinum-palladium alloy nanoparticles have basically achieved good loading.

[0082] The boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst of Example 3 is used in SPE / electrolytic ozone and hydrogen generators:

[0083] The prepared boron nitrogen carbon nanotube-loaded platinum palladium alloy bifunctional electrocatalyst was used as the anode and cathode catalyst of the SPE / electrolytic ozone and hydrogen generator. The proton exchange membrane (Nafion D520) was used as the membrane electrode substrate. The boron nitrogen carbon nanotube-loaded platinum palladium alloy bifunctional electrocatalyst was coated on the anode and cathode surfaces of the proton exchange membrane to prepare the membrane electrode. The membrane electrode was assembled into an SPE / electrolytic ozone and hydrogen generator for testing the ozone production performance of the anode electrolysis and the hydrogen decomposition performance of the cathode electrolysis. Deionized water was added to the electrolysis chamber to carry out the water electrolysis reaction. The ozone produced by electrolysis was connected to the ozone detector through the anode outlet, and the hydrogen produced by electrolysis was connected to the hydrogen detector through the cathode outlet. The electrolysis voltage was set to 5.0 V and the current was set to 10.0 A. The volume and mass concentrations of the produced ozone and hydrogen changed with time, as shown in the figure. Figure 11 、 12 As shown. Figure 11 、 12 It can be seen that the ozone volume mass concentration detected by the ozone detector is stable at 182.32 g / m 3 The hydrogen gas concentration was detected by the hydrogen detector and was stable at 152.28 g / m 3 .

[0084] The boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst of Example 3 is used for the electrolysis of water to produce ozone:

[0085] In the process of preparing the electrode anode using the catalyst prepared in Example 3, the catalyst of Example 1 was replaced with the catalyst prepared in Example 3 of equal mass. The remaining operating conditions were the same as those in the experimental process of preparing ozone by electrolysis of water in Example 1. The relationship between the concentration of ozone generated by the electrolysis of water catalysis and the reaction time is shown in FIG. Figure 13 As shown, as the reaction proceeds, the ozone concentration gradually increases, and when the reaction time reaches 60 minutes, the ozone concentration is stabilized at 3000 ppm.

[0086] The boron nitrogen carbon nanotube-supported platinum palladium alloy bifunctional electrocatalyst of Example 3 is used for the electrolysis of water to produce hydrogen:

[0087] In the process of preparing the electrode anode, the catalyst prepared in Example 3 was used to replace the catalyst in Example 1 with the catalyst prepared in Example 3 of the same mass. The other operating conditions were the same as those in the experimental process of preparing hydrogen by electrolysis of water in Example 1. The hydrogen production produced by the electrolysis of water catalytic reaction was detected as shown in the figure below. Figure 14 As shown. Figure 14 It can be seen that as the reaction proceeds, the hydrogen production gradually increases. When the reaction time reaches 275 seconds, the hydrogen production can reach 10 mL, and the yield is stable at 2.2 mL·min -1 .

[0088] Example 4

[0089] Preparation of a boron-nitrogen-carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst, comprising the following steps:

[0090] 1) Add 3.9 mg of chloroplatinic acid, 3.1 mg of molybdenum acetylacetonate, and 20 mL of tetrahydrofuran to a 100 mL two-necked flask. Sodium carbonate is added to the solution while stirring to adjust the pH to 10. CO is then continuously introduced into the solution. Heat to 60°C under a CO atmosphere and react for 50 h to prepare a metal carbonyl complex solution A.

[0091] 2) 0.15 g of boric acid, 5 g of urea, 0.5 g of polyethylene glycol, and 1 g of melamine were dissolved in deionized water and stirred for 3 h to mix thoroughly. The resulting solution was dried in an oven at 180°C for 20 h to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture was evenly ground and placed in a tube furnace for calcination under high-purity nitrogen at 800°C for 6 h to produce BNC nanotubes.

[0092] 3) Ultrasonic dispersion of 40 mg of BNC nanotubes, 5.7 mg of sodium dodecyl sulfate, and 10 mL of tetrahydrofuran for 60 min to prepare solution B.

[0093] 4) pouring the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically dispersing for 30 minutes, and then hydrothermally heating at 160° C. for 24 hours to obtain the product;

[0094] 5) The product obtained in step 4) was filtered, washed with anhydrous ethanol and deionized water three times each, and vacuum dried at 60° C. for 24 h. After drying, the boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst was collected.

[0095] The SEM image of the boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst obtained in Example 4 at 3 μm is as follows: Figure 7 As shown in the figure, tubular BNC nanotubes were prepared, and the TEM image at 5 nm is shown in Figure 8 As shown in the figure, it can be seen that the platinum-molybdenum alloy nanoparticles have basically achieved good loading.

[0096] The boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst of Example 4 is used in SPE / electrolytic ozone and hydrogen generators:

[0097] The prepared boron nitrogen carbon nanotube-loaded platinum-molybdenum alloy bifunctional electrocatalyst was used as the cathode and anode catalysts of the SPE / electrolytic ozone and hydrogen generator. The proton exchange membrane (Nafion NRE211) was used as the membrane electrode substrate. The boron nitrogen carbon nanotube-loaded platinum-molybdenum alloy bifunctional electrocatalyst was coated on the anode and cathode surfaces of the proton exchange membrane to prepare the membrane electrode. The membrane electrode was assembled into an SPE / electrolytic ozone and hydrogen generator for testing the ozone production performance of the anode electrolysis and the hydrogen decomposition performance of the cathode electrolysis. Deionized water was added to the electrolysis chamber to carry out the water electrolysis reaction. The ozone produced by electrolysis was connected to the ozone detector through the anode outlet, and the hydrogen produced by electrolysis was connected to the hydrogen detector through the cathode outlet. The electrolysis voltage was set to 5.0 V and the current was set to 10.0 A. The volume and mass concentrations of the produced ozone and hydrogen changed with time, as shown in the figure. Figure 11 、 12 As shown. Figure 11 、 12 It can be seen that the ozone volume mass concentration detected by the ozone detector is stable at 127.22 g / m 3 The hydrogen gas concentration was detected by the hydrogen detector and was stable at 100 g / m 3 .

[0098] The boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst of Example 4 is used for the electrolysis of water to produce ozone:

[0099] In the process of preparing the electrode anode using the catalyst prepared in Example 4, the catalyst of Example 1 was replaced with the catalyst prepared in Example 4 of equal mass. The remaining operating conditions were the same as those in the experimental process of preparing ozone by electrolysis of water in Example 1. The relationship between the concentration of ozone generated by the electrolysis of water catalysis and the reaction time is shown in FIG. Figure 13 As shown, as the reaction proceeds, the ozone concentration gradually increases, and when the reaction time reaches 60 minutes, the ozone concentration is stabilized at 1500 ppm.

[0100] The boron nitrogen carbon nanotube-supported platinum-molybdenum alloy bifunctional electrocatalyst of Example 4 is used for the electrolysis of water to produce hydrogen:

[0101] In the process of preparing the electrode anode, the catalyst prepared in Example 4 was used to replace the catalyst in Example 1 with the catalyst prepared in Example 4 of the same mass. The other operating conditions were the same as those in the experimental process of preparing hydrogen by electrolysis of water in Example 1. The hydrogen production produced by the electrolysis of water catalytic reaction was detected as shown in the figure below. Figure 14 As shown. Figure 14 It can be seen that as the reaction proceeds, the hydrogen production gradually increases. When the reaction time reaches 345 seconds, the hydrogen production can reach 10 mL, and the yield is stable at 1.7 mL·min -1 .

[0102] Example 5

[0103] Preparation of a boron-nitrogen-carbon nanotube-supported platinum-iron alloy bifunctional electrocatalyst comprises the following steps:

[0104] 1) Add 3.9 mg of chloroplatinic acid, 2 mg of ferric acetylacetonate, and 20 mL of tetrahydrofuran to a 100 mL two-necked flask. Sodium carbonate is added to the solution while stirring to adjust the pH to 13. CO is then continuously introduced into the solution. Heat to 70°C under a CO atmosphere and react for 72 h to prepare a metal carbonyl complex solution A.

[0105] 2) 0.15 g of boric acid, 5 g of urea, 0.5 g of polyethylene glycol, and 1 g of melamine were dissolved in deionized water and stirred for 3 h to mix thoroughly. The resulting solution was dried in an oven at 200°C for 24 h to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture was evenly ground and placed in a tube furnace for calcination under high-purity nitrogen at 900°C for 8 h to produce BNC nanotubes.

[0106] 3) Ultrasonic dispersion of 40 mg of BNC nanotubes, 6.7 mg of sodium dodecylbenzenesulfonate, and 10 mL of tetrahydrofuran for 60 min to prepare solution B.

[0107] 4) pouring the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically dispersing for 30 minutes, and then hydrothermally heating at 200°C for 24 hours to obtain the product;

[0108] 5) The product obtained in step 4) was filtered, washed with anhydrous ethanol and deionized water 4 times each, and vacuum dried at 60° C. for 24 h. After drying, the boron nitrogen carbon nanotube-supported platinum iron alloy bifunctional electrocatalyst was collected.

[0109] The SEM image of the boron nitrogen carbon nanotube-supported platinum iron alloy bifunctional electrocatalyst obtained in Example 5 at 3 μm is as follows: Figure 9 As shown in the figure, tubular BNC nanotubes were prepared, and the TEM image at 5 nm is shown in Figure 10 As shown in the figure, it can be seen that the platinum-iron alloy nanoparticles have basically achieved good loading.

[0110] The boron nitrogen carbon nanotube-supported platinum iron alloy bifunctional electrocatalyst of Example 5 is used in SPE / electrolytic ozone and hydrogen generators:

[0111] The prepared boron nitrogen carbon nanotube-loaded platinum iron alloy bifunctional electrocatalyst was used as the anode and cathode catalyst of the SPE / electrolytic ozone and hydrogen generator. The proton exchange membrane (Nafion NRE212) was used as the membrane electrode substrate. The boron nitrogen carbon nanotube-loaded platinum iron alloy bifunctional electrocatalyst was coated on the anode and cathode surfaces of the proton exchange membrane to prepare the membrane electrode. The membrane electrode was assembled into an SPE / electrolytic ozone and hydrogen generator for testing the ozone production performance of the anode electrolysis and the hydrogen decomposition performance of the cathode electrolysis. Deionized water was added to the electrolysis chamber to carry out the water electrolysis reaction. The ozone produced by electrolysis was connected to the ozone detector through the anode outlet, and the hydrogen produced by electrolysis was connected to the hydrogen detector through the cathode outlet. The electrolysis voltage was set to 5.0 V and the current was set to 10.0 A. The volume and mass concentrations of the produced ozone and hydrogen changed with time, as shown in the figure. Figure 11 、 12 As shown. Figure 11 、 12 It can be seen that the ozone volume mass concentration detected by the ozone detector is stable at 87.76 g / m 3 The hydrogen volume mass concentration was detected by the hydrogen detector and was stable at 92.09 g / m 3 .

[0112] The boron-nitrogen-carbon nanotube-supported platinum-iron alloy bifunctional electrocatalyst of Example 5 is used for the electrolysis of water to produce ozone:

[0113] In the process of preparing the electrode anode using the catalyst prepared in Example 1, the catalyst of Example 1 was replaced with the catalyst prepared in Example 2 of equal mass. The remaining operating conditions were the same as those in the experimental process of preparing ozone by electrolysis of water in Example 1. The relationship between the concentration of ozone generated by the electrolysis of water catalysis and the reaction time is shown in FIG. Figure 13 As shown, as the reaction proceeds, the ozone concentration gradually increases, and when the reaction time reaches 60 minutes, the ozone concentration is stabilized at 5000 ppm.

[0114] The boron nitrogen carbon nanotube-supported platinum iron alloy bifunctional electrocatalyst of Example 5 is used for the electrolysis of water to produce hydrogen:

[0115] In the process of preparing the electrode anode, the catalyst prepared in Example 5 was used to replace the catalyst in Example 1 with the catalyst prepared in Example 5 of the same mass. The other operating conditions were the same as those in the experimental process of preparing hydrogen by electrolysis of water in Example 1. The hydrogen production produced by the electrolysis of water catalytic reaction was detected as shown in the figure below. Figure 14 As shown. Figure 14 It can be seen that as the reaction proceeds, the hydrogen production gradually increases. When the reaction time reaches 370 seconds, the hydrogen production can reach 10 mL, and the yield is stable at 1.6 mL·min -1 .

[0116] Example 6

[0117] PbO2 catalyst is used for ozone production at the anode, and 20wt% Pt / C catalyst is used for hydrogen evolution at the cathode.

[0118] The PbO2 catalyst and 20 wt% Pt / C catalyst of Comparative Example 6 were used in SPE / electrolytic ozone and hydrogen generators:

[0119] PbO2 catalyst (purchased from Aladdin Reagent Network) was used as the anode catalyst of the SPE / electrolytic ozone and hydrogen generator, 20wt% Pt / C catalyst (purchased from Aladdin Reagent Network) was used as the cathode catalyst of the SPE / electrolytic ozone and hydrogen generator, and proton exchange membrane (Nafion HP) was used as the membrane electrode substrate. PbO2 catalyst and 20wt% Pt / C catalyst were coated on the anode and cathode surfaces of the proton exchange membrane, respectively, to prepare the membrane electrode, which was assembled into an SPE / electrolytic ozone and hydrogen generator for testing the anode electrolysis ozone production performance and cathode electrolysis hydrogen decomposition performance. Deionized water was added to the electrolysis chamber to carry out the water electrolysis reaction. The ozone produced by electrolysis was connected to the ozone detector through the anode outlet, and the hydrogen produced by electrolysis was connected to the hydrogen detector through the cathode outlet. The electrolysis voltage was set to 5.0 V and the current was set to 10.0 A. The volume mass concentration of the produced ozone and hydrogen changed with time, as shown in the figure. Figure 11 、 12 As shown. Figure 11 、12 It can be seen that the ozone volume mass concentration detected by the ozone detector is stable at 110.78 g / m 3 The hydrogen gas concentration was detected by the hydrogen detector and was stable at 144.21 g / m 3 .

[0120] The PbO2 catalyst of Comparative Example 6 was used for the electrolysis of water to produce ozone:

[0121] Weigh 8 mg of commercial PbO2 catalyst (purchased from Aladdin Reagent Network) and mix it with 900 μL of ethanol and 100 μL of Nafion solution (Nafion solution concentration: 5%). Ultrasonicate for 0.5 hours to completely disperse the catalyst in the mixture of ethanol and Nafion solution, creating a uniform catalyst slurry. Cut a carbon cloth to approximately 2 cm × 2 cm in size, and evenly apply the dispersed catalyst slurry to the cloth. After drying, this serves as the working electrode (i.e., the PbO2 catalyst coated on the carbon cloth serves as the working electrode).

[0122] The voltage and current were controlled by a constant current meter, and an H-type electrolytic cell was used for the reaction. Water and air were kept unobstructed between the two electrode chambers. A saturated potassium sulfate aqueous solution was used as the electrolyte. A Pt / C catalyst was coated on a carbon cloth as the working electrode in the anode chamber, and a platinum sheet was used as the counter electrode in the cathode chamber. One end of the H-type electrolytic cell was connected to an ozone detector to monitor the production of ozone in real time. When electrocatalytically producing ozone, the reaction current was controlled at 200-300 mA, the cell voltage was controlled at 5-7 V, and the reaction time was 60 minutes. As the reaction proceeded, the real-time detection of the ozone concentration produced by the electrocatalytic reaction was as shown in the figure below. Figure 13 As shown. Figure 13 It can be seen that as the reaction proceeds, the ozone concentration gradually increases, and when the reaction time reaches 60 minutes, the ozone concentration stabilizes at 1000 ppb.

[0123] The 20 wt% Pt / C catalyst of Comparative Example 6 was used for the electrolysis of water to produce hydrogen:

[0124] 8 mg of the prepared commercial 20wt% Pt / C catalyst was weighed and mixed with 900 μL of ethanol and 100 μL of a 5% Nafion solution. Ultrasonication was performed for 0.5 hours to completely disperse the catalyst in the mixture of ethanol and Nafion solution, resulting in a uniform catalyst slurry. The carbon cloth was cut into approximately 2 cm × 2 cm pieces, and the dispersed catalyst slurry was evenly drop-coated on the carbon cloth. After drying, it served as the working electrode (i.e., the Pt / C catalyst was coated on the carbon cloth as the working electrode).

[0125] The voltage and current were controlled by a constant current meter, and an H-type electrolytic cell was used for the reaction. Water and air were kept unobstructed between the two electrode chambers. A 0.5M H2SO4 solution was used as the electrolyte. A Pt / C catalyst was coated on a carbon cloth as the working electrode in the anode chamber, an Ag / AgCl electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode in the cathode chamber. The reaction voltage was set to 0.4 V, and the reaction current was controlled between 100-200 mA. Electrocatalytic hydrogen production was carried out, and the hydrogen yield was calculated using the water displacement method. As the reaction proceeded, the hydrogen production produced by the electrocatalytic reaction was detected as shown in the figure below. Figure 14 As shown. Figure 14 It can be seen that as the reaction proceeds, the hydrogen production gradually increases. When the reaction time reaches 300 seconds, the hydrogen production can reach 10 mL, and the yield is stable at 1.9 mL·min -1 .

[0126] from Figure 11 、 13 It can be seen that when applied to the electrocatalytic production of ozone, the catalytic reaction rate and catalytic effect of the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst of the present invention are superior to those of the commercial PbO2 catalyst. Figure 12 、 14 It can be seen that when applied to the electrocatalytic hydrogen production reaction, the catalytic reaction rate and catalytic effect of the boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst of the present invention are partially superior to those of the commercial 20wt% Pt / C catalyst.

[0127] The contents described in this specification are merely an enumeration of implementation forms of the inventive concept, and the protection scope of the present invention should not be considered as being limited to the specific forms described in the embodiments.

Claims

1. A method for preparing a boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst, characterized in that: The following steps are involved: 1) A platinum source, a transition metal source, and a solvent are added to a two-necked flask. A base is added to the solution under stirring to adjust the pH to 6-13. CO is then continuously introduced into the solution. The solution is heated to 30-70° C. under a CO atmosphere and reacted for 12-72 h to prepare a metal carbonyl complex solution A, wherein the platinum source is one of potassium chloroplatinate, sodium chloroplatinate, platinum acetylacetonate, and chloroplatinic acid; the transition metal source is cobalt acetylacetonate, iron acetylacetonate, palladium acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate, or copper acetylacetonate; the solvent is one of ethanol, methanol, tetrahydrofuran, N,N-dimethylpyrrolidone, and toluene; and the base is one of NaOH, KOH, CH3COONa, NaCO3, and ammonia solution; 2) dissolving polyethylene glycol, urea, boric acid, and melamine in deionized water and stirring for 1-3 hours to mix uniformly. The resulting solution is dried in an oven at 80-200°C for 6-24 hours to completely evaporate the water in the solution to obtain a solid mixture. The resulting solid mixture is ground uniformly and placed in a tube furnace. The mixture is calcined in a high-purity nitrogen atmosphere at a temperature of 500-900°C for 2-8 hours to obtain BNC nanotubes. The mass ratio of polyethylene glycol, urea, boric acid, and melamine is 0.08-0.12: 0.8-1.2: 0.02-0.05: 0.16-0.

24. 3) ultrasonically dispersing the BNC nanotubes prepared in step 2), a surfactant, and a solvent for 30-60 min to prepare solution B, wherein the mass ratio of BNC nanotubes to surfactant is 6-10:1; 4) pouring the metal carbonyl complex solution A and solution B obtained in step 1) and step 3) into the lining of the reactor, ultrasonically dispersing for 10-30 minutes, and then hydrothermally heating at 100-200° C. for 6-24 hours to obtain the product; 5) filtering the product obtained in step 4), washing it with anhydrous ethanol and deionized water 3-5 times each, and vacuum drying it at 40-60° C. for 12-24 hours. After drying, collecting it to obtain a boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst; The total metal loading of platinum and transition metals was 5-50%.

2. The method for preparing the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst according to claim 1, characterized in that The molar ratio of the platinum source to the transition metal source in step 1) is 1-5:

1.

3. The method for preparing the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst according to claim 1, characterized in that The surfactant in step 3) is one of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecylsulfonate, sodium hexadecylbenzenesulfonate, polyvinyl pyrrolidone, polyvinyl alcohol, 1-methyl-2-pyrrolidone, citrate and sodium ethylenediaminetetraacetate.

4. The method for preparing the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst according to claim 1, characterized in that: The total metal loading of platinum and transition metals was 5%.

5. Use of the boron nitrogen carbon nanotube-supported platinum alloy bifunctional electrocatalyst according to claim 4 in electrocatalytic water decomposition to produce ozone and hydrogen, characterized in that Boron-nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst is coated on the anode and cathode sides of a proton exchange membrane to prepare a membrane electrode, which is assembled into an SPE / electrolytic ozone and hydrogen generator. Deionized water is added to the electrolysis chamber to carry out water electrolysis reaction. The electrolysis voltage is set to 5.0V and the current is set to 10.0A. Ozone is generated at the anode and hydrogen is generated at the cathode. The proton exchange membrane is Nafion N117, Nafion N115, Nafion D520, Nafion NRE211, Nafion NRE212 or Nafion HP.

6. Use of the boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst according to claim 4 in the production of ozone by electrolysis of water, characterized in that The voltage and current were controlled by a constant current meter, and an H-type electrolytic cell was used for the reaction. Water and air were kept unobstructed between the two electrode chambers. A saturated potassium sulfate solution was used as the electrolyte. A boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst was coated on a carbon cloth as the working electrode in the anode chamber, and a platinum sheet was used as the counter electrode in the cathode chamber. The reaction current was controlled at 200-300 mA, and the cell voltage was controlled at 5-7 V to electrocatalytically produce ozone.

7. Use of the boron-nitrogen-carbon nanotube-supported platinum alloy bifunctional electrocatalyst according to claim 4 in the electrolysis of water to produce hydrogen, characterized in that The voltage and current were controlled by a constant current meter, and an H-type electrolytic cell was used for the reaction. Water and gas were kept unobstructed between the two electrode chambers. A 0.5 M H2SO4 solution was used as the electrolyte. A boron nitrogen carbon nanotube-loaded platinum alloy bifunctional electrocatalyst was coated on a carbon cloth as the working electrode in the anode chamber, an Ag / AgCl electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode in the cathode chamber. The reaction voltage was set to 0.4 V, and the reaction current was controlled between 100-200 mA. Hydrogen was produced by electrocatalysis, and the hydrogen yield was calculated using the water displacement method.

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