CN115584529B - Boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst and preparation method and application thereof - Google Patents
Boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst and preparation method and application thereofInfo
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Abstract
本发明公开了一种硼氮碳纳米管负载铂合金双功能电催化剂及其制备方法和应用，包括如下步骤：将铂源、过渡金属源和溶剂搅拌混合调节pH，在CO气氛下加热升温制得金属羰基络合物溶液A；将聚乙二醇、尿素、硼酸和三聚氰胺溶于去离子水中，干燥得固态混合物，固态混合物研磨置于管式炉内，在高纯气体气氛下焙烧制得BNC纳米管；将BNC纳米管、表面活性剂和溶剂超声分散均匀制得溶液B；将金属羰基络合物溶液A与溶液B倒入反应釜内衬中，超声分散均匀后水热制得产物；过滤、洗涤、干燥得到硼氮碳纳米管负载铂合金双功能电催化剂。本发明的制备方法制备成本低，电催化产臭氧量高，制取氢气有较高的反应效率，电催化反应过程的操作条件温和、绿色无污染。
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
The invention belongs to the technical field of electrocatalysis, and particularly relates to a boron-nitrogen-carbon nanotube supported platinum alloy bifunctional electrocatalyst, and a preparation method and application thereof.
Background
Ozone has strong oxidizing property, is an oxidant stronger than oxygen, can perform oxidation reaction at lower temperature, is widely used for bacterial inactivation, fruit and vegetable disinfection, medical sanitation disinfection and the like, is reduced to oxygen in the use process, and cannot generate secondary pollution, so that the ozone is widely applied to the fields of water treatment, chemical industry, food, spice, pharmaceutical industry and the like, air disinfection, sterilization and the like, and is widely paid attention. However, the overpotential for the oxygen evolution reaction of the electrolyzed water anode is 1.23V, and the overpotential for the ozone production reaction is 1.51V, which means that more energy is needed for generating ozone to overcome the larger reaction energy barrier, and the reaction formulas of the anode and the cathode are as follows:
anode reaction:
3H2O = O3 + 6H+ + 6e- (E1 0 = 1.51 V)
2H2O = O2 + 4H+ + 4e- (E2 0 = 1.23 V)
cathode reaction:
2H+ + 2e- = H2 (E3 0 = 0.00 V)
thus, the dual-function catalyst for producing ozone and hydrogen by electrochemical water decomposition is more deficient.
At present, pt-based catalysts are commonly used electrocatalysts for ozone-generating reactions and hydrogen evolution reactions, have higher overpotential and unique electronic structures, but platinum is expensive and poor in stability, so that the practical application of the Pt-based catalysts is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst, and a preparation method and application thereof. According to the invention, another metal element M is added into the Pt-based catalyst, and the platinum alloy nano particles are loaded on the BNC nano tube carrier by a carbonyl complex method, so that the cost is reduced, meanwhile, the BNC nano tube has good stability and reactivity, and the tubular structure of the BNC nano tube has a larger specific surface area, so that the electrolytic reaction efficiency is increased. The catalyst can be used as a positive catalyst and a negative catalyst of an SPE/electrolytic ozone and hydrogen generator to generate high-purity ozone and hydrogen.
The preparation method of the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst comprises the following steps:
1) Adding a platinum source, a transition metal source and a solvent into a two-neck flask, adding an inorganic base into the solution under stirring to adjust the pH to 6-13, continuously introducing CO into the solution, heating to 30-70 ℃ under the CO atmosphere to react for 12-72 h ℃ to obtain 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 one of cobalt acetylacetonate, iron acetylacetonate, palladium acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate or copper acetylacetonate, the solvent is one of ethanol, methanol, tetrahydrofuran, N-dimethyl pyrrolidone and toluene, and the inorganic base is one of NaOH, KOH, CH 3COONa、NaCO3 and ammonia water;
2) Dissolving polyethylene glycol, urea, boric acid and melamine in deionized water, stirring 1-3 h, mixing uniformly, placing the formed solution in an oven, drying 6-24 h at 80-200 ℃ to completely evaporate water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, roasting in a high-purity nitrogen atmosphere at 500-900 ℃ for 2-8 h, and obtaining BNC nanotubes, wherein 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 nano tube prepared in the step 2), a surfactant and a solvent for 30-60 min to prepare a solution B, wherein the mass ratio of the BNC nano tube to the surfactant is 6-10:1;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion for 10-30 min, and performing hydrothermal treatment at 100-200 ℃ for 6-24: 24 h to obtain a product;
5) Filtering the product obtained in the step 4), washing with absolute ethyl alcohol and deionized water for 3-5 times respectively, vacuum drying at 40-60 ℃ for 12-24 h, and collecting after drying to obtain the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst.
Further, the molar ratio of the platinum source to the transition metal source in step 1) is 1-5:1, preferably 1:1.
Further, the surfactant in the step 3) is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, 1-methyl-2-pyrrolidone, citrate and sodium ethylenediamine tetraacetate.
Further, the total metal loading of platinum and transition metal is 5-50%, preferably 5%.
The application of the boron nitrogen carbon nano tube supported platinum alloy dual-function electrocatalyst in preparing ozone and hydrogen by performing electrocatalytic decomposition on water is that the boron nitrogen carbon nano tube supported platinum alloy dual-function electrocatalyst is coated on the anode side and the cathode side of a proton exchange membrane to prepare membrane electrodes, the membrane electrodes are assembled into an SPE/electrolytic ozone and hydrogen generator, deionized water is added into an electrolytic chamber to perform electrolytic water reaction, the electrolytic voltage is set to be 5.0V, the current is set to be 10.0A, ozone is generated by the anode, and hydrogen is generated by the cathode, wherein the proton exchange membrane is Nafion N117, nafion N115, nafion D520, nafion NRE211, nafion NRE212 or Nafion HP.
The application of the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst in preparing ozone by electrolyzing water is characterized in that a constant current meter is used for controlling voltage and current, an H-shaped electrolytic tank is used for reaction, water and gas are kept smooth between two electrode chambers, a saturated potassium sulfate solution is used as electrolyte, the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst is coated on carbon cloth and used as a working electrode in an anode chamber, a platinum sheet is used as a counter electrode in a cathode chamber, the reaction current is controlled to be 200-300 mA, the tank voltage is controlled to be 5-7V, and the ozone is prepared by electrocatalytic.
The application of the boron nitrogen carbon nano tube supported platinum alloy dual-function electrocatalyst in preparing hydrogen by electrolyzing water is characterized in that a constant current meter is used for controlling voltage and current, an H-type electrolytic tank is used for carrying out reaction, water and gas are kept smooth between two electrode chambers, 0.5M H 2SO4 solution is used as electrolyte, the boron nitrogen carbon nano tube supported platinum alloy dual-function electrocatalyst is coated on carbon cloth to be used as a working electrode in an anode chamber, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode in a cathode chamber, the reaction voltage is set to be 0.4V, the reaction current is controlled to be 100-200mA, the hydrogen is prepared by electrocatalytic, and the hydrogen yield is calculated by adopting a drainage method.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) The hollow carbon nanotube structure of the BNC nanotube in the boron-nitrogen-carbon nanotube supported platinum alloy dual-functional electrocatalyst is beneficial to mass transfer diffusion of reaction raw materials and reaction products, and the tubular structure has good conductivity and large specific surface area, so that the electrolytic reaction efficiency is improved;
2) The active component of the platinum alloy nano particles prepared by the carbonyl complex method in the preparation method of the boron nitrogen carbon nano tube supported platinum alloy dual-functional electrocatalyst is supported on the BNC nano tube carrier, compared with the traditional active component supported on the carrier, the active component has small particle size and narrow particle size distribution, is not easy to agglomerate in the reaction, has good stability and reactivity, and provides advantages for the large-scale production of the alloy nano particles;
3) The preparation cost of the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst is low, the catalyst has higher reaction efficiency when being used for preparing hydrogen through electrocatalytic reaction, the generated ozone amount is higher, and the operation condition of the electrocatalytic reaction process is mild, green and pollution-free.
Drawings
FIG. 1 is a view of a transmission electron microscope of a dual-function platinum nickel alloy electrocatalyst supported by boron nitrogen carbon nanotubes prepared in example 1 at 3 μm;
FIG. 2 is a view of a transmission electron microscope under 5nm of a dual-function platinum nickel alloy electrocatalyst supported by boron nitrogen carbon nanotubes prepared in example 1;
FIG. 3 is a view of a transmission electron microscope of a dual-function electrocatalyst of platinum-cobalt alloy supported by boron-nitrogen-carbon nanotubes prepared in example 2 at 3 μm;
FIG. 4 is a view of a transmission electron microscope under 5nm of a dual-function electrocatalyst of boron-nitrogen-carbon nanotube supported platinum-cobalt alloy prepared in example 2;
FIG. 5 is a transmission electron microscope view of the dual-function platinum-palladium alloy electrocatalyst with boron nitrogen carbon nanotubes prepared in example 3 at 3 μm;
FIG. 6 is a transmission electron microscope view of the dual-function platinum-palladium alloy electrocatalyst with boron nitrogen carbon nanotubes prepared in example 3 under 5 nm;
FIG. 7 is a view of a transmission electron microscope of a dual-function electrocatalyst of a platinum-molybdenum alloy supported by boron-nitrogen-carbon nanotubes prepared in example 4 at 3 μm;
FIG. 8 is a view of a transmission electron microscope of a dual-function electrocatalyst of boron nitrogen carbon nanotube-supported platinum molybdenum alloy prepared in example 4 under 5 nm;
FIG. 9 is a view of a transmission electron microscope of a dual-function electrocatalyst of a boron nitrogen carbon nanotube-supported platinum-iron alloy prepared in example 5 at 3 μm;
FIG. 10 is a view of a transmission electron microscope of a dual-function electrocatalyst of boron nitrogen carbon nanotubes supported platinum iron alloy prepared in example 5 under 5 nm;
FIG. 11 is a graph of time versus concentration for the boron nitrogen carbon nanotube supported platinum alloy dual function electrocatalyst prepared in examples 1-5 and the commercial PbO 2 catalyst of example 6 to generate ozone at the SPE/electrolyze ozone, hydrogen generator anode;
FIG. 12 is a graph of time versus concentration for the boron nitrogen carbon nanotube supported platinum alloy dual function electrocatalysts prepared in examples 1-5 and the commercial Pt/C catalyst of example 6 to produce hydrogen at the SPE/electrolyze ozone, hydrogen generator cathode;
FIG. 13 is a graph showing a comparison of the real-time detection of ozone concentration produced by the use of the dual-function electrocatalyst comprising a platinum alloy supported on boron nitrogen carbon nanotubes prepared in examples 1-5 and the commercial PbO 2 catalyst of example 6 in the electrocatalytic production of ozone;
FIG. 14 is a graph comparing data of hydrogen evolution rates of the boron nitrogen carbon nanotube supported platinum alloy dual-function electrocatalysts prepared in examples 1-5 and the commercial Pt/C catalyst of example 6 for electrocatalytic production of hydrogen.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
The preparation method of the boron-nitrogen-carbon nanotube supported platinum-nickel alloy bifunctional electrocatalyst comprises the following steps:
1) Adding 4mg potassium chloroplatinate, 2.18 mg nickel acetylacetonate and 20mL methanol into a two-neck flask with a 100 mL mouth, adding sodium acetate into the solution under stirring to adjust the pH to 7, continuously introducing CO into the solution, heating to 30 ℃ under the CO atmosphere, and reacting 12 h to obtain a metal carbonyl complex solution A;
2) Dissolving 0.15 g boric acid, 5g urea, 0.5 g polyethylene glycol and 1g melamine in deionized water, stirring for 1h, uniformly mixing, placing the formed solution in an oven, drying at 80 ℃ for 6h, completely evaporating water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, and roasting at 500 ℃ for 2h ℃ under high-purity nitrogen to obtain BNC nanotubes;
3) Ultrasonically dispersing 40 mg BNC nano tubes, 4 mg polyvinylpyrrolidone and 10 mL methanol for 30 min to prepare a solution B;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion for 10 min, and performing hydrothermal treatment at 100 ℃ for 6: 6h to obtain a product;
5) Filtering the product obtained in the step 4), washing with absolute ethyl alcohol and deionized water for 3 times respectively, vacuum drying at 40 ℃ for 12 h, and collecting the boron-nitrogen-carbon nanotube supported platinum-nickel alloy dual-function electrocatalyst after drying.
The SEM image of the boron nitrogen carbon nanotube supported platinum nickel alloy dual-function electrocatalyst obtained in example 1 at 3 μm is shown in fig. 1, from which it can be seen that the BNC nanotubes with tubular structure were prepared, and the TEM image at 5 nm is shown in fig. 2, from which it can be seen that the platinum nickel alloy nanoparticles have achieved substantially good loading.
The boron nitrogen carbon nanotube supported platinum nickel alloy dual-function electrocatalyst of example 1 was used in SPE/electrolytic ozone, hydrogen generator:
The prepared boron nitrogen carbon nanotube supported platinum nickel alloy dual-function electrocatalyst is used as an SPE/electrolytic ozone and a positive electrode catalyst and a negative electrode catalyst of a hydrogen generator, a proton exchange membrane (Nafion N117) is used as a membrane electrode substrate, the boron nitrogen carbon nanotube supported platinum nickel alloy dual-function electrocatalyst is coated on the positive electrode surface and the negative electrode surface of the proton exchange membrane to prepare a membrane electrode, and the membrane electrode is assembled to form the SPE/electrolytic ozone and the hydrogen generator, and is used for testing the ozone production performance of anode electrolysis and the hydrogen evolution performance of cathode electrolysis, deionized water is added into an electrolysis chamber to carry out electrolytic water reaction. The ozone generated by electrolysis is connected with an ozone detector through an anode gas outlet, the hydrogen generated by electrolysis is connected with a hydrogen detector through a cathode gas outlet, the voltage of electrolysis is set to 5.0V, the current is set to 10.0A, and the volume mass concentration of the generated ozone and hydrogen changes with time, as shown in figures 11 and 12. As can be seen from fig. 11 and 12, the ozone volume mass concentration detected by the ozone detector was stable at 241.32 g/m 3, and the hydrogen volume mass concentration detected by the hydrogen detector was stable at 207.38 g/m 3.
The boron nitrogen carbon nanotube supported platinum nickel alloy dual-function electrocatalyst of example 1 was used for the water electrolysis to prepare ozone reaction:
The boron nitrogen carbon nano tube supported platinum nickel alloy dual-function electrocatalyst powder prepared by 8 mg is weighed and mixed with 900 mu L of ethanol and 100 mu L of Nafion solution (the mass concentration of the Nafion solution is 5%), and the catalyst is fully dispersed in the mixed solution of the ethanol and the Nafion solution for 0.5 hour by ultrasonic treatment, so that uniform catalyst slurry is obtained. Cutting carbon cloth to a size of about 2 cm multiplied by 2 cm, uniformly dripping all the dispersed catalyst slurry on the carbon cloth, and drying to obtain the working electrode (namely, the boron nitrogen carbon nano tube supported platinum nickel alloy bifunctional electrocatalyst is coated on the carbon cloth to serve as the working electrode).
The voltage and current are controlled by a constant current meter, an H-shaped electrolytic tank is adopted for reaction, water and gas are kept smooth between two electrode chambers, a saturated potassium sulfate aqueous solution is used as electrolyte, a boron nitrogen carbon nanotube loaded platinum nickel alloy dual-function electrocatalyst is coated on carbon cloth to be used as a working electrode in an anode chamber, a platinum sheet is used as a counter electrode in a cathode chamber, one end of the H-shaped electrolytic tank is connected with an ozone detector, and the generation condition of ozone is detected in real time. The reaction current is controlled at 200-300 mA, the tank voltage is controlled at 5-7V, and the electro-catalysis is carried out to prepare ozone, and the reaction time is 60 minutes. The graph of the real-time detection of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeds is shown in FIG. 13. As can be seen from fig. 13, the ozone concentration gradually increased as the reaction proceeded, and the ozone concentration stabilized at 6000ppm as the reaction time reached 60 minutes.
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 after 1 reaction was left for 24 hours, and then repeated electrocatalytic preparation ozone reaction experiments were performed (the anode chamber working electrode was left for one day after each use, and then used again). In experiment 1 of the anode chamber working electrode recycling reaction, the ozone concentration was stabilized at 6000ppm after the reaction reached 60 minutes. In experiment 2 of the repeated reaction of the working electrode of the anode chamber, the ozone concentration after the reaction reaches 60 minutes is stabilized at 6000ppm. In experiment 3 of the anode chamber working electrode recycling reaction, the ozone concentration was stabilized at 5800ppm after the reaction reached 60 minutes. The fact that the electrocatalytic effect is not weakened basically in the recycling process of the working electrode of the anode chamber can be seen, and the boron-nitrogen-carbon nanotube supported platinum-nickel alloy bifunctional electrocatalyst prepared in the embodiment 1 has good stability.
The boron nitrogen carbon nanotube supported platinum nickel alloy dual-function electrocatalyst of example 1 was used for the electrolysis of water to produce hydrogen:
The boron nitrogen carbon nano tube supported platinum nickel alloy dual-function electrocatalyst powder prepared by 8 mg is weighed and mixed with 900 mu L of ethanol and 100 mu L of Nafion solution (the mass concentration of the Nafion solution is 5%), and the catalyst is fully dispersed in the mixed solution of the ethanol and the Nafion solution for 0.5 hour by ultrasonic treatment, so that uniform catalyst slurry is obtained. Cutting carbon cloth to a size of about 2 cm multiplied by 2 cm, uniformly dripping all the dispersed catalyst slurry on the carbon cloth, and drying to obtain the working electrode (namely, the boron nitrogen carbon nano tube supported platinum nickel alloy bifunctional electrocatalyst is coated on the carbon cloth to serve as the working electrode).
The method comprises the steps of controlling voltage and current by a constant current meter, performing reaction by an H-type electrolytic tank, keeping water and gas smooth between two electrode chambers, using 0.5M H 2SO4 solution as electrolyte, coating a boron-nitrogen-carbon nanotube supported platinum-nickel alloy dual-function electrocatalyst on carbon cloth as a working electrode in an anode chamber, using an Ag/AgCl electrode as a reference electrode, using a platinum sheet as a counter electrode in a cathode chamber, setting the reaction voltage to be 0.4V, controlling the reaction current to be 100-200mA, performing electrocatalytic preparation of hydrogen, and calculating the hydrogen yield by a drainage method. As the reaction proceeds, a graph of the hydrogen production produced by the electrocatalytic reaction is shown in FIG. 14. As shown in FIG. 14, as the reaction proceeds, the hydrogen yield gradually increases, the hydrogen yield for the reaction time of 250 seconds reaches 10mL, and the yield is stabilized at 2.3 mL.min -1.
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 after 1 time of the above reaction was left for 24 hours, and then a repeated electrocatalytic hydrogen preparation reaction experiment was performed (the anode chamber working electrode was left for one day after each use, and then used again). In experiment 1 of the anode chamber working electrode recycling reaction, the hydrogen yield was stabilized at 2.3 mL.min -1. In experiment 2 of the anode chamber working electrode recycling reaction, the hydrogen yield was stabilized at 2.3 mL.min -1. In experiment 3 of the anode chamber working electrode recycling reaction, the hydrogen yield was stabilized at 2.3 mL min -1. The fact that the electrocatalytic effect is not weakened basically in the recycling process of the working electrode of the anode chamber can be seen, and the boron-nitrogen-carbon nanotube supported platinum-nickel alloy bifunctional electrocatalyst prepared in the embodiment 1 has good stability.
Example 2
The preparation method of the boron-nitrogen-carbon nanotube supported platinum-cobalt alloy dual-function electrocatalyst comprises the following steps:
1) Adding 4.2 mg sodium chloroplatinate, 2.2 mg cobalt acetylacetonate and 20 mL ethanol into a 100 mL two-neck flask, adding sodium hydroxide into the solution under stirring to adjust the pH to 8, continuously introducing CO into the solution, heating and heating to 40 ℃ under the CO atmosphere to react 18 h to prepare a metal carbonyl complex solution A;
2) Dissolving 0.15g boric acid, 5g urea, 0.5 g polyethylene glycol and 1g melamine in deionized water, stirring for 2 hours, mixing uniformly, placing the formed solution in an oven, drying at 100 ℃ for 10 h, completely evaporating water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, and roasting at a roasting temperature of 600 ℃ and a roasting time of 3h to obtain BNC nanotubes;
3) Ultrasonically dispersing 40 mg BNC nano tubes, 4.5 mg hexadecyl sodium sulfonate and 10 mL ethanol for 40 min to prepare a solution B;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion on the solution A and the solution B for 20min, and performing hydrothermal treatment at 120 ℃ for 12h to obtain a product;
5) Filtering the product obtained in the step 4), washing the product with absolute ethyl alcohol and deionized water for 4 times, vacuum drying the product at 50 ℃ for 18 h, and collecting the product after drying to obtain the boron-nitrogen-carbon nanotube supported platinum-cobalt alloy dual-function electrocatalyst.
The SEM image of the boron nitrogen carbon nanotube supported platinum cobalt alloy dual-function electrocatalyst obtained in example 2 at 3 μm is shown in fig. 3, from which it is known that BNC nanotubes with tubular structures are prepared, and the TEM image at 5 nm is shown in fig. 4, from which it is known that the platinum cobalt alloy nanoparticles have achieved substantially good loading.
The boron nitrogen carbon nanotube supported platinum cobalt alloy dual-function electrocatalyst of example 2 was used in SPE/electrolytic ozone, hydrogen generator:
The prepared boron nitrogen carbon nanotube supported platinum cobalt alloy dual-function electrocatalyst is used as an anode catalyst and a cathode catalyst of an SPE/electrolytic ozone and hydrogen generator, a proton exchange membrane (Nafion N115) is used as a membrane electrode substrate, the boron nitrogen carbon nanotube supported platinum cobalt alloy dual-function electrocatalyst is coated on the anode surface and the cathode surface of the proton exchange membrane to prepare a membrane electrode, and the membrane electrode is assembled to form the SPE/electrolytic ozone and hydrogen generator, and is used for testing the ozone production performance of anode electrolysis and the hydrogen evolution performance of cathode electrolysis, deionized water is added into an electrolysis chamber to carry out electrolytic water reaction. The ozone generated by electrolysis is connected with an ozone detector through an anode gas outlet, the hydrogen generated by electrolysis is connected with a hydrogen detector through a cathode gas outlet, the voltage of electrolysis is set to 5.0V, the current is set to 10.0A, and the volume mass concentration of the generated ozone and hydrogen changes with time, as shown in figures 11 and 12. As can be seen from fig. 11 and 12, the ozone volume mass concentration detected by the ozone detector was stable at 220.02 g/m 3, and the hydrogen volume mass concentration detected by the hydrogen detector was stable at 185.84 g/m 3.
The boron nitrogen carbon nanotube supported platinum cobalt alloy dual-function electrocatalyst of example 2 was used for the water electrolysis to prepare ozone reaction:
In the process of preparing the electrode anode by using the catalyst prepared in the example 2, the catalyst of the example 1 is replaced by the catalyst prepared in the example 2 with the same quality, other operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, the change relation of the concentration of the ozone generated by the catalytic reaction of the electrolyzed water along with the reaction time is shown in figure 13, the concentration of the ozone is gradually increased along with the progress of the reaction, and the concentration of the ozone is stabilized at 3000ppm when the reaction time reaches 60 minutes.
The boron nitrogen carbon nanotube supported platinum cobalt alloy dual-function electrocatalyst of example 2 was used for the water electrolysis reaction to prepare hydrogen:
In the process of preparing the electrode anode by using the catalyst prepared in the example 2, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 2 with the same quality, and the rest of the operation conditions are the same as those in the experimental process of preparing the hydrogen by using the electrolyzed water in the example 1, and a hydrogen yield detection chart prepared by using the electrolyzed water for catalytic reaction is shown in fig. 14. As is clear from FIG. 14, as the reaction proceeds, the hydrogen yield gradually increases, and the hydrogen yield for 380 seconds reaches 10 mL, and the yield is stabilized at 1.6 mL.min -1.
Example 3
The preparation method of the boron nitrogen carbon nanotube supported platinum-palladium alloy bifunctional electrocatalyst comprises the following steps:
1) Adding 3.5 mg platinum acetylacetonate, 3.9 mg palladium acetylacetonate and 20 mLN N-dimethyl pyrrolidone into a two-neck flask of 100 mL, adding potassium hydroxide into the solution under stirring to adjust the pH to 9, continuously introducing CO into the solution, heating to 50 ℃ under the CO atmosphere, and reacting 24 h to obtain a metal carbonyl complex solution A;
2) Dissolving 0.15g boric acid, 5g urea, 0.5 g polyethylene glycol and 1g melamine in deionized water, stirring for 3 hours, mixing uniformly, placing the formed solution in an oven, drying at 150 ℃ for 15 h, completely evaporating water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, roasting at a roasting temperature of 700 ℃ and a roasting time of 5h, and obtaining BNC nanotubes;
3) Ultrasonically dispersing 40 mg BNC nano tubes, 5mg hexadecyl sodium benzenesulfonate and 10 mL N, N-dimethyl pyrrolidone for 50 min to prepare a solution B;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion for 30 min, and performing hydrothermal treatment at 140 ℃ for 18: 18 h to obtain a product;
5) Filtering the product obtained in the step 4), washing with absolute ethyl alcohol and deionized water for 5 times respectively, vacuum drying at 60 ℃ for 24 h, and collecting the boron-nitrogen-carbon nanotube supported platinum-palladium alloy dual-function electrocatalyst after drying.
An SEM image of the boron nitrogen carbon nanotube supported platinum palladium alloy bifunctional electrocatalyst obtained in example 3 at 3 μm is shown in fig. 5, from which it is known that BNC nanotubes with tubular structures are prepared, and a TEM image at 5 nm is shown in fig. 6, from which it is known that the platinum palladium alloy nanoparticles have achieved substantially good loading.
The boron nitrogen carbon nanotube supported platinum palladium alloy dual-function electrocatalyst of example 3 was used in SPE/electrolytic ozone, hydrogen generator:
The prepared boron nitrogen carbon nanotube supported platinum-palladium alloy dual-function electrocatalyst is used as an anode catalyst and a cathode catalyst of an SPE/electrolytic ozone and hydrogen generator, a proton exchange membrane (Nafion D520) is used as a membrane electrode substrate, the boron nitrogen carbon nanotube supported platinum-palladium alloy dual-function electrocatalyst is coated on the anode surface and the cathode surface of the proton exchange membrane to prepare a membrane electrode, and the membrane electrode is assembled to form the SPE/electrolytic ozone and hydrogen generator, and is used for testing the ozone generating performance of anode electrolysis and the hydrogen generating performance of cathode electrolysis, deionized water is added into an electrolysis chamber to perform electrolytic water reaction. The ozone generated by electrolysis is connected with an ozone detector through an anode gas outlet, the hydrogen generated by electrolysis is connected with a hydrogen detector through a cathode gas outlet, the voltage of electrolysis is set to 5.0V, the current is set to 10.0A, and the volume mass concentration of the generated ozone and hydrogen changes with time, as shown in figures 11 and 12. As can be seen from fig. 11 and 12, the ozone volume mass concentration detected by the ozone detector was stable at 182.32 g/m 3, and the hydrogen volume mass concentration detected by the hydrogen detector was stable at 152.28 g/m 3.
The boron nitrogen carbon nanotube supported platinum-palladium alloy dual-function electrocatalyst of example 3 was used for the water electrolysis to produce ozone:
In the process of preparing the electrode anode by using the catalyst prepared in the example 3, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 3 with the same quality, other operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, the change relation of the concentration of the ozone generated by the catalytic reaction of the electrolyzed water along with the reaction time is shown in figure 13, the concentration of the ozone is gradually increased along with the progress of the reaction, and the concentration of the ozone is stabilized at 3000ppm when the reaction time reaches 60 minutes.
The boron nitrogen carbon nanotube supported platinum-palladium alloy dual-function electrocatalyst of example 3 was used for the electrolysis of water to produce hydrogen:
In the process of preparing the electrode anode by using the catalyst prepared in the example 3, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 3 with the same quality, and the rest of the operation conditions are the same as those in the experimental process of preparing the hydrogen by using the electrolyzed water in the example 1, and a hydrogen yield detection chart prepared by using the electrolyzed water for catalytic reaction is shown in fig. 14. As shown in FIG. 14, as the reaction proceeds, the hydrogen yield gradually increases, the hydrogen yield for 275 seconds reaches 10 mL, and the yield is stabilized at 2.2 mL. Min -1.
Example 4
The preparation method of the boron-nitrogen-carbon nanotube supported platinum-molybdenum alloy dual-function electrocatalyst comprises the following steps:
1) Adding 3.9 mg chloroplatinic acid, 3.1 mg molybdenum acetylacetonate and 20 mL tetrahydrofuran into a 100 mL two-neck flask, adding sodium carbonate into the solution under stirring to adjust the pH to 10, continuously introducing CO into the solution, heating to 60 ℃ under the CO atmosphere, and reacting 50 h to obtain a metal carbonyl complex solution A;
2) Dissolving 0.15g boric acid, 5g urea, 0.5 g polyethylene glycol and 1g melamine in deionized water, stirring for 3 hours, mixing uniformly, placing the formed solution in an oven, drying at 180 ℃ for 20h, completely evaporating water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, and roasting at 800 ℃ for 6h ℃ under high-purity nitrogen to obtain BNC nanotubes;
3) Ultrasonically dispersing 40 mg BNC nano tubes, 5.7 mg sodium dodecyl sulfate and 10mL tetrahydrofuran for 60 min to prepare a solution B;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion for 30 min, and performing hydrothermal treatment at 160 ℃ for 24: 24 h to obtain a product;
5) Filtering the product obtained in the step 4), washing with absolute ethyl alcohol and deionized water for 3 times respectively, vacuum drying at 60 ℃ for 24 h, and collecting the boron-nitrogen-carbon nanotube supported platinum-molybdenum alloy dual-function electrocatalyst after drying.
The SEM image of the boron nitrogen carbon nanotube supported platinum molybdenum alloy dual-function electrocatalyst obtained in example 4 at 3 μm is shown in fig. 7, from which it is known that BNC nanotubes with tubular structures are prepared, and the TEM image at 5 nm is shown in fig. 8, from which it is known that the platinum molybdenum alloy nanoparticles have achieved substantially good loading.
The boron nitrogen carbon nanotube supported platinum molybdenum alloy dual-function electrocatalyst of example 4 was used in SPE/electrolytic ozone, hydrogen generator:
The prepared boron nitrogen carbon nano tube supported platinum molybdenum alloy dual-function electrocatalyst is used as an SPE/electrolytic ozone and an anode catalyst of a hydrogen generator, a proton exchange membrane (Nafion NRE 211) is used as a membrane electrode substrate, the boron nitrogen carbon nano tube supported platinum molybdenum alloy dual-function electrocatalyst is coated on the anode surface and the cathode surface of the proton exchange membrane to prepare a membrane electrode, and the membrane electrode is assembled into the SPE/electrolytic ozone and the hydrogen generator, and is used for testing the ozone generating performance of anode electrolysis and the hydrogen generating performance of cathode electrolysis, deionized water is added into an electrolysis chamber to carry out electrolytic water reaction. The ozone generated by electrolysis is connected with an ozone detector through an anode gas outlet, the hydrogen generated by electrolysis is connected with a hydrogen detector through a cathode gas outlet, the voltage of electrolysis is set to 5.0V, the current is set to 10.0A, and the volume mass concentration of the generated ozone and hydrogen changes with time, as shown in figures 11 and 12. As can be seen from fig. 11 and 12, the ozone volume mass concentration detected by the ozone detector was stable at 127.22 g/m 3, and the hydrogen volume mass concentration detected by the hydrogen detector was stable at 100 g/m 3.
The boron nitrogen carbon nanotube supported platinum molybdenum alloy dual-function electrocatalyst of example 4 was used for the water electrolysis to produce ozone:
In the process of preparing the electrode anode by using the catalyst prepared in the example 4, the catalyst of the example 1 is replaced by the catalyst prepared in the example 4 with the same quality, other operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, the change relation of the concentration of the ozone generated by the catalytic reaction of the electrolyzed water along with the reaction time is shown in figure 13, the concentration of the ozone is gradually increased along with the progress of the reaction, and the concentration of the ozone is stabilized at 1500ppm when the reaction time reaches 60 minutes.
The boron nitrogen carbon nanotube supported platinum molybdenum alloy dual-function electrocatalyst of example 4 was used for the electrolysis of water to produce hydrogen:
In the process of preparing the electrode anode by using the catalyst prepared in the example 4, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 4 with the same quality, and the rest of the operation conditions are the same as those in the experimental process of preparing the hydrogen by using the electrolyzed water in the example 1, and a hydrogen yield detection chart prepared by using the electrolyzed water for catalytic reaction is shown in fig. 14. As shown in FIG. 14, as the reaction proceeds, the hydrogen yield gradually increases, the hydrogen yield for 345 seconds reaches 10 mL, and the yield is stabilized at 1.7 mL.min -1.
Example 5
The preparation method of the boron-nitrogen-carbon nanotube-supported platinum-iron alloy dual-function electrocatalyst comprises the following steps:
1) Adding 3.9 mg chloroplatinic acid, 2 mg ferric acetylacetonate and 20 mL tetrahydrofuran into a two-neck flask with 100mL, adding sodium carbonate into the solution under stirring to adjust the pH to 13, continuously introducing CO into the solution, heating to 70 ℃ under the CO atmosphere, and reacting 72 h to obtain a metal carbonyl complex solution A;
2) Dissolving 0.15g boric acid, 5g urea, 0.5 g polyethylene glycol and 1g melamine in deionized water, stirring for 3 hours, mixing uniformly, placing the formed solution in an oven, drying at 200 ℃ for 24h, completely evaporating water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, roasting at 900 ℃ under high-purity nitrogen, and roasting for 8h to obtain BNC nanotubes;
3) Ultrasonically dispersing 40 mg BNC nano tubes, 6.7 mg sodium dodecyl benzene sulfonate and 10mL tetrahydrofuran for 60 min to prepare a solution B;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion for 30 min, and performing hydrothermal treatment at 200 ℃ for 24: 24 h to obtain a product;
5) Filtering the product obtained in the step 4), washing the product with absolute ethyl alcohol and deionized water for 4 times, vacuum drying the product at 60 ℃ for 24 h, and collecting the product after drying to obtain the boron-nitrogen-carbon nanotube supported platinum-iron alloy dual-function electrocatalyst.
The SEM image of the boron nitrogen carbon nanotube supported platinum iron alloy dual-function electrocatalyst obtained in example 5 at 3 μm is shown in fig. 9, from which it is known that the tube-like structure BNC nanotubes were prepared, and the TEM image at 5 nm is shown in fig. 10, from which it is known that the platinum iron alloy nanoparticles have substantially achieved good loading.
The boron nitrogen carbon nanotube supported platinum iron alloy dual-function electrocatalyst of example 5 was used in SPE/electrolytic ozone, hydrogen generator:
The prepared boron nitrogen carbon nanotube supported platinum iron alloy dual-function electrocatalyst is used as an anode catalyst and a cathode catalyst of an SPE/electrolytic ozone and hydrogen generator, a proton exchange membrane (Nafion NRE 212) is used as a membrane electrode substrate, the boron nitrogen carbon nanotube supported platinum iron alloy dual-function electrocatalyst is coated on the anode surface and the cathode surface of the proton exchange membrane to prepare a membrane electrode, and the membrane electrode is assembled into the SPE/electrolytic ozone and hydrogen generator for testing the ozone generating performance and the hydrogen generating performance of the cathode electrolysis, and deionized water is added into an electrolysis chamber to perform the water electrolysis reaction. The ozone generated by electrolysis is connected with an ozone detector through an anode gas outlet, the hydrogen generated by electrolysis is connected with a hydrogen detector through a cathode gas outlet, the voltage of electrolysis is set to 5.0V, the current is set to 10.0A, and the volume mass concentration of the generated ozone and hydrogen changes with time, as shown in figures 11 and 12. As can be seen from fig. 11 and 12, the ozone volume mass concentration detected by the ozone detector was stabilized at 87.76 g/m 3, and the hydrogen volume mass concentration detected by the hydrogen detector was stabilized at 92.09 g/m 3.
The boron nitrogen carbon nanotube supported platinum iron alloy dual-function electrocatalyst of example 5 was used for the water electrolysis to produce ozone:
In the process of preparing the electrode anode by using the catalyst prepared in the example 1, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 2 with the same quality, other operation conditions are the same as those in the experimental process of preparing the ozone by using the electrolyzed water in the example 1, the change relation of the concentration of the ozone generated by the catalytic reaction of the electrolyzed water along with the reaction time is shown in figure 13, the concentration of the ozone is gradually increased along with the progress of the reaction, and the concentration of the ozone is stabilized at 5000ppm when the reaction time reaches 60 minutes.
The boron nitrogen carbon nanotube supported platinum iron alloy dual-function electrocatalyst of example 5 was used for the electrolysis of water to produce hydrogen:
In the process of preparing the electrode anode by using the catalyst prepared in the example 5, the catalyst prepared in the example 1 is replaced by the catalyst prepared in the example 5 with the same quality, and the rest of the operation conditions are the same as those in the experimental process of preparing the hydrogen by using the electrolyzed water in the example 1, and a hydrogen yield detection chart prepared by using the electrolyzed water for catalytic reaction is shown in fig. 14. As shown in FIG. 14, as the reaction proceeds, the hydrogen yield gradually increases, and the hydrogen yield for the reaction time of 370 seconds reaches 10 mL, and the yield is stabilized at 1.6 mL.min -1.
Example 6
PbO 2 catalyst for anode ozone-producing reaction and 20wt% Pt/C catalyst for cathode hydrogen evolution reaction
The PbO 2 catalyst of comparative example 6 and 20wt% Pt/C catalyst were used in SPE/electrolytic ozone, hydrogen generator:
PbO 2 catalyst (purchased from Ama Ding Shiji mesh) is used as an anode catalyst of an SPE/electrolytic ozone and hydrogen generator, 20wt% of Pt/C catalyst (purchased from Ama Ding Shiji mesh) is used as a cathode catalyst of the SPE/electrolytic ozone and hydrogen generator, a proton exchange membrane (Nafion HP) is used as a membrane electrode substrate, the PbO 2 catalyst and 20wt% of Pt/C catalyst are respectively coated on the anode surface and the cathode surface of the proton exchange membrane to prepare membrane electrodes, the SPE/electrolytic ozone and hydrogen generator is assembled and used for testing the ozone production performance and the hydrogen production performance of the cathode electrolysis, deionized water is added into an electrolysis chamber, and the electrolytic water reaction is carried out. The ozone generated by electrolysis is connected with an ozone detector through an anode gas outlet, the hydrogen generated by electrolysis is connected with a hydrogen detector through a cathode gas outlet, the voltage of electrolysis is set to 5.0V, the current is set to 10.0A, and the volume mass concentration of the generated ozone and hydrogen changes with time, as shown in figures 11 and 12. As can be seen from fig. 11 and 12, the ozone volume mass concentration detected by the ozone detector was stable at 110.78 g/m 3, and the hydrogen volume mass concentration detected by the hydrogen detector was stable at 144.21 g/m 3.
The PbO 2 catalyst of comparative example 6 was used for the electrolytic water preparation ozone reaction:
8 mg commercial PbO 2 catalyst (purchased from Aba Ding Shiji net) was weighed, mixed with 900. Mu.L of ethanol and 100. Mu.L of Nafion solution (Nafion solution mass concentration 5%) and sonicated for 0.5 hours to completely disperse the catalyst in the mixture of ethanol and Nafion solution to give a uniform catalyst slurry. Cutting carbon cloth to a size of about 2 cm multiplied by 2 cm, uniformly dripping all the dispersed catalyst slurry on the carbon cloth, and drying to obtain a working electrode (namely, a material coated on the carbon cloth by a PbO 2 catalyst is used as the working electrode).
The constant current instrument is used for controlling voltage and current, the H-shaped electrolytic tank is used for carrying out reaction, water and gas are kept smooth between the two electrode chambers, saturated potassium sulfate aqueous solution is used as electrolyte, pt/C catalyst is coated on carbon cloth to be used as a working electrode in the anode chamber, a platinum sheet is used as a counter electrode in the cathode chamber, and one end of the H-shaped electrolytic tank is connected with the ozone detector for detecting the generation condition of ozone in real time. When the electrocatalytic ozone is prepared, the reaction current is controlled to be 200-300 mA, the tank voltage is controlled to be 5-7V, and the reaction time is 60 minutes. The graph of the real-time detection of the concentration of ozone produced by the electrocatalytic reaction as the reaction proceeds is shown in FIG. 13. As is clear from fig. 13, the ozone concentration gradually increased as the reaction proceeded, and the ozone concentration was stabilized at 1000ppb for a reaction time of 60 minutes.
Comparative example 6 20wt% Pt/C catalyst was used for the electrolysis of water to produce hydrogen:
The commercial 20wt% Pt/C catalyst prepared by 8 mg was weighed, mixed with 900. Mu.L of ethanol and 100. Mu.L of Nafion solution (Nafion solution mass concentration 5%) and sonicated for 0.5 hours to completely disperse the catalyst in the mixture of ethanol and Nafion solution to give a uniform catalyst slurry. Cutting the carbon cloth to a size of about 2 cm multiplied by 2 cm, uniformly dripping all the dispersed catalyst slurry on the carbon cloth, and drying to obtain the working electrode (namely, coating the Pt/C catalyst on the carbon cloth to serve as the working electrode).
The method comprises the steps of controlling voltage and current by a constant current meter, performing reaction by an H-type electrolytic tank, keeping water and gas smooth between two electrode chambers, using 0.5M H 2SO4 solution as electrolyte, coating Pt/C catalyst on carbon cloth as a working electrode in an anode chamber, using Ag/AgCl electrode as a reference electrode, using a platinum sheet as a counter electrode in a cathode chamber, setting the reaction voltage to be 0.4V, controlling the reaction current to be 100-200mA, performing electrocatalytic preparation of hydrogen, and calculating the hydrogen yield by a drainage method. As the reaction proceeds, a graph of the hydrogen production produced by the electrocatalytic reaction is shown in FIG. 14. As is clear from FIG. 14, as the reaction proceeds, the hydrogen yield gradually increases, the hydrogen yield for 300 seconds reaches 10mL, and the yield is stabilized at 1.9 mL.min -1.
As can be seen from fig. 11 and 13, when the catalyst is applied to the electrocatalytic reaction for preparing ozone, the catalyst reaction rate and the catalytic effect of the dual-function catalyst of the boron-nitrogen-carbon nanotube supported platinum alloy are partially better than those of the commercial PbO 2 catalyst. As can be seen from fig. 12 and 14, when the catalyst is applied to the electrocatalytic reaction for preparing hydrogen, the catalytic reaction rate and the catalytic effect of the dual-function catalyst of the boron-nitrogen-carbon nanotube supported platinum alloy of the invention are partially better than those of a commercial 20wt% Pt/C catalyst.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (7)
1. The preparation method of the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst is characterized by comprising the following steps of:
1) Adding a platinum source, a transition metal source and a solvent into a two-neck flask, adding alkali into the solution under stirring to adjust the pH to 6-13, continuously introducing CO into the solution, heating to 30-70 ℃ under the CO atmosphere to react 12-72 h to obtain 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 one of cobalt acetylacetonate, iron acetylacetonate, palladium acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate or copper acetylacetonate, the solvent is one of ethanol, methanol, tetrahydrofuran, N-dimethyl pyrrolidone and toluene, and the alkali is one of NaOH, KOH, CH 3COONa、NaCO3 and ammonia water;
2) Dissolving polyethylene glycol, urea, boric acid and melamine in deionized water, stirring 1-3 h, mixing uniformly, placing the formed solution in an oven, drying 6-24 h at 80-200 ℃ to completely evaporate water in the solution to obtain a solid mixture, grinding the obtained solid mixture uniformly, placing the solid mixture in a tube furnace, roasting in a high-purity nitrogen atmosphere at 500-900 ℃ for 2-8 h, and obtaining BNC nanotubes, wherein 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 nano tube prepared in the step 2), a surfactant and a solvent for 30-60 min to prepare a solution B, wherein the mass ratio of the BNC nano tube to the surfactant is 6-10:1;
4) Pouring the metal carbonyl complex solution A and the metal carbonyl complex solution B obtained in the step 1) and the step 3) into a liner of a reaction kettle, performing ultrasonic dispersion for 10-30 min, and performing hydrothermal treatment at 100-200 ℃ for 6-24: 24 h to obtain a product;
5) Filtering the product obtained in the step 4), washing with absolute ethyl alcohol and deionized water for 3-5 times respectively, vacuum drying at 40-60 ℃ for 12-24 h, and collecting after drying to obtain the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst;
the total metal loading of platinum and transition metal is 5-50%.
2. The method for preparing the boron nitrogen carbon nanotube supported platinum alloy dual-function electrocatalyst according to claim 1, wherein the feeding molar ratio of the platinum source to the transition metal source in step 1) is 1-5:1.
3. The preparation method of the boron nitrogen carbon nanotube supported platinum alloy dual-function electrocatalyst according to claim 1, wherein the surfactant in step 3) is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, 1-methyl-2-pyrrolidone, citrate and sodium ethylenediamine tetraacetate.
4. The method for preparing the boron nitrogen carbon nanotube supported platinum alloy dual-function electrocatalyst according to claim 1, wherein the total metal loading of platinum and transition metal is 5%.
5. The application of the boron nitrogen carbon nano tube supported platinum alloy dual-function electrocatalyst in preparing ozone and hydrogen by electrocatalytic decomposition of water is characterized in that the boron nitrogen carbon nano tube supported platinum alloy dual-function electrocatalyst is coated on the anode side and the cathode side of a proton exchange membrane to prepare membrane electrodes, SPE/electrolytic ozone and a hydrogen generator are assembled, deionized water is added into an electrolytic chamber to carry out electrolytic water reaction, the electrolytic voltage is set to be 5.0V, the current is set to be 10.0A, ozone is generated at an anode, and hydrogen is generated at a cathode, and the proton exchange membrane is Nafion N117, nafion N115, nafion D520, nafion NRE211, nafion NRE212 or Nafion HP.
6. The application of the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst in preparing ozone by electrolyzing water, which is characterized in that a constant current meter is used for controlling voltage and current, an H-type electrolytic tank is used for reaction, water and gas are kept smooth between two electrode chambers, a saturated potassium sulfate solution is used as electrolyte, the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst is coated on carbon cloth as a working electrode in an anode chamber, a platinum sheet is used as a counter electrode in a cathode chamber, the reaction current is controlled to be 200-300 mA, the tank voltage is controlled to be 5-7V, and the electro-catalysis is carried out to prepare ozone.
7. The application of the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst in preparing hydrogen by electrolyzing water, which is characterized in that a constant current meter is used for controlling voltage and current, an H-type electrolytic tank is used for reaction, water and gas are kept smooth between two electrode chambers, 0.5M H 2SO4 solution is used as electrolyte, the boron-nitrogen-carbon nanotube supported platinum alloy dual-function electrocatalyst is coated on carbon cloth as a working electrode in an anode chamber, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode in a cathode chamber, the reaction voltage is set to be 0.4V, the reaction current is controlled to be 100-200mA, the electrocatalytic hydrogen is prepared, and the hydrogen yield is calculated by adopting a drainage method.
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