Preparation method and application of a xanthium-like mesoporous carbon supported platinum alloy catalyst

Abstract

The present application belongs to the technical field of metal nanometer catalytic material, and particularly relates to a preparation method of a xanthium-like mesoporous carbon loaded platinum alloy catalyst and application thereof. The method for preparing the platinum-based alloy catalyst comprises the following steps: firstly, preparing a nano-carrier; then, using active hydrogen generated by photocatalysis to reduce and prepare platinum nanoparticles, and loading the platinum nanoparticles on the nano-carrier; and finally, preparing the platinum-based alloy catalyst through evaporation and calcination. The preparation method has the advantages of cheap reactants, simple preparation process, low energy consumption, and less pollutant emission. The platinum-based alloy catalyst prepared by the method has the advantages of good catalytic performance, good stability, long service life, and the like, has the potential for large-scale production and application, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metal nanocatalytic materials, and particularly relates to a preparation method of a Xanthium-like mesoporous carbon supported platinum alloy catalyst. BACKGROUND

[0002] As one of fuel cells, proton exchange membrane fuel cell (PEMFC) can efficiently convert chemical energy in hydrogen into electrical energy, and its product is only water, which has the advantages of being clean, efficient, and pollution-free. However, the slow kinetics process seriously limits its commercialization process. In the proton exchange membrane fuel cell, platinum-based catalyst is widely used as electrode catalyst due to its excellent electrocatalytic performance, which is mainly composed of a carrier and platinum-based nanoparticles supported on the surface of the carrier. Therefore, the catalytic performance of the platinum-based catalyst is affected by the synergistic effect of the catalytic activity of the platinum-based particles and the carrier.

[0003] At present, in order to improve the catalytic performance of the catalyst, the following several ways are mainly used to achieve the purpose, the first way is to alloy platinum with other metals to improve the catalytic performance of the platinum-based catalyst, the second way is to optimize the morphology of the catalyst, such as adopting core-shell structure, hollow structure, nanowire and nanosheet to improve the catalytic performance of the platinum-based catalyst, the third way is to introduce non-metallic elements as dopants to change the electronic structure and adsorption properties of platinum to improve the catalytic performance of the platinum-based catalyst, the fourth way is to improve the utilization rate and stability of platinum by selecting suitable carrier materials to improve the catalytic performance of the platinum-based catalyst, and the fifth way is to improve the atomic utilization rate and construct a continuous network to improve the catalytic performance of the platinum-based catalyst.

[0004] However, in the practical application of the platinum-based catalyst, under the corrosion of the acidic environment of the proton exchange membrane fuel cell, the platinum-based catalyst is delaminated, which leads to the attenuation of the catalytic performance; the ionomer occupies the position on the surface of the platinum-based particles, which leads to the poisoning of the catalyst; and the migration of the catalyst particles on the surface of the carrier leads to the agglomeration of the nanoparticles, all of which will seriously affect the catalytic performance of the catalyst and eventually lead to the rapid attenuation of the performance of the fuel cell. In addition, in the preparation process of the platinum-based catalyst at present, there are problems such as high energy consumption, serious environmental pollution, long preparation process, etc. The traditional synthesis strategy uses high-priced solvents, which causes high cost and environmental pollution; the reaction needs to be heated to high temperature, which has high energy consumption; and the catalyst synthesis process is long, which causes solvent waste and environmental pollution.

[0005] Therefore, it is urgent to develop a platinum-based catalyst with good catalytic performance, good stability, simple synthesis process, low energy consumption, less environmental pollution, and large-scale production and application potential. SUMMARY

[0006] The present application aims to at least partly solve at least one of the technical problems existing in the prior art. To this end, the present application provides a preparation method of a xanthium-like mesoporous carbon supported platinum alloy catalyst and an application thereof. The preparation method of the platinum-based alloy catalyst has the advantages of cheap reactants, simple preparation process, low energy consumption, and less pollutant emission. The platinum-based alloy catalyst prepared by the method has the advantages of good catalytic performance, good stability, long service life, and the like, and has the potential for large-scale production and application, and wide application prospect.

[0007] In a first aspect of the present application, a preparation method of a platinum-based alloy catalyst is provided. According to an embodiment of the present application, the method comprises: S1: contacting a nitrogen source and / or a sulfur source, an activator, and a nano-carrier, and performing carbonization treatment to obtain a carbonized polymer; S2: removing excess nickel from the carbonized polymer to obtain mesoporous carbon; S3: fixing platinum nanoparticle colloid to the mesoporous carbon to obtain a composite; S4: depositing a plating layer material on the surface of the composite to obtain a plating layer material-composite; S5: performing alloying treatment on the plating layer material-composite to obtain a plating layer material-alloy composite; and S6: removing excess plating layer material from the plating layer material-alloy composite to obtain a platinum-based alloy catalyst. The preparation method according to the embodiment of the present application has the advantages of cheap reactants, simple preparation process, low energy consumption, and less pollutant emission. The platinum-based alloy catalyst prepared by the method has the advantages of good catalytic performance, good stability, long service life, and the like, and has the potential for large-scale production and application, and wide application prospect.

[0008] According to an embodiment of the present application, the above-mentioned preparation method of a platinum-based alloy catalyst can further have the following additional technical features:

[0009] According to an embodiment of the present application, the nano-carrier is prepared by contacting polyacrylic acid, a nickel salt, and a surfactant to obtain a nano-carrier; wherein the contacting is performed in a reaction medium with pH=2-8.

[0010] According to an embodiment of the present application, the polyacrylic acid has a molecular weight of 8000-12000.

[0011] According to an embodiment of the present application, the nickel salt comprises one or more of nickel nitrate, nickel chloride, nickel acetate, and nickel sulfate.

[0012] According to an embodiment of the present application, the surfactant comprises polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and / or cetyltrimethylammonium bromide.

[0013] According to an embodiment of the present application, the weight ratio of the polyacrylic acid, the nickel salt, and the surfactant is 1:(2-6):(1-3).

[0014] According to an embodiment of the present application, the reaction medium is water and / or an aqueous alcohol solution.

[0015] According to an embodiment of the present application, the reagent for adjusting the pH of the reaction medium is a basic solution.

[0016] According to an embodiment of the present application, the nanoparticle has a pore size of 2-50 nm, a specific surface area of ≥800 m 2 g -1 .

[0017] According to an embodiment of the present application, the platinum nanoparticle colloid is prepared by contacting a platinum source, a surfactant and a photocatalyst to obtain a platinum nanoparticle colloid; wherein the contacting is performed under a light source.

[0018] According to an embodiment of the present application, the platinum source includes one or more of chloroplatinic acid, potassium chloroplatinate and ammonium chloroplatinate.

[0019] According to an embodiment of the present application, the surfactant is one or more of sodium glycolate, cetyltrimethylammonium bromide, sodium cetyl sulfonate and cetyltrimethylammonium chloride.

[0020] According to an embodiment of the present application, the photocatalyst includes one or more of titanium dioxide, cadmium sulfide, zinc oxide and cadmium selenide.

[0021] According to an embodiment of the present application, the weight ratio of the platinum source, the reducing agent and the photocatalyst is 1:(2-10):(5-20).

[0022] According to an embodiment of the present application, the contacting is performed in a reaction medium.

[0023] According to an embodiment of the present application, the reaction medium is an alcohol solvent and / or water.

[0024] According to an embodiment of the present application, the alcohol solvent includes one or more of methanol, ethanol and isopropyl alcohol.

[0025] According to an embodiment of the present application, the activating agent is an alkali metal hydroxide.

[0026] According to an embodiment of the present application, the activating agent includes one or more of potassium hydroxide, sodium hydroxide and potassium nitrate.

[0027] According to an embodiment of the present application, the nitrogen source includes one or more of urea, melamine, dicyandiamide and amino acid.

[0028] According to an embodiment of the present application, the sulfur source includes one or more of thiourea, thioacetamide, cysteine and sulfur powder.

[0029] According to an embodiment of the present application, the carbonization treatment comprises a first-stage carbonization treatment and a second-stage carbonization treatment.

[0030] According to an embodiment of the present application, in the first-stage carbonization treatment, the calcination temperature is 200-400℃, the temperature rising rate is 4-6℃ / min, and the holding time is 2-3h.

[0031] According to an embodiment of the present application, in the alloying treatment, the calcination temperature is 800-900℃, the temperature rising rate is 4-6℃ / min, and the holding time is 2-3h.

[0032] According to an embodiment of the present application, the weight ratio of the nanocarrier and the nitrogen source and / or the sulfur source is 1:(0.5-3).

[0033] According to an embodiment of the present application, the weight ratio of the mesoporous carbon and the platinum nanoparticles is 1:(0.3-3).

[0034] According to an embodiment of the present application, the plating material is a base metal material.

[0035] According to an embodiment of the present application, the plating material comprises one or more of iron, nickel, cobalt, copper, zinc and manganese.

[0036] According to an embodiment of the present application, the weight ratio of the composite and the plating material in the composite-plating material is 1:(0.3-10).

[0037] According to an embodiment of the present application, in the alloying treatment, the calcination temperature is 600-800℃, the temperature rising rate is 4-6℃ / min, and the holding time is 2-3h.

[0038] According to an embodiment of the present application, the alloying treatment is carried out under a mixed gas of inert gas and hydrogen, and the proportion of hydrogen in the mixed gas is 5-20%.

[0039] According to an embodiment of the present application, the mass proportion of platinum in the platinum-based alloy catalyst is 10-70%.

[0040] In the second aspect of the present application, a platinum-based alloy catalyst is provided. According to an embodiment of the present application, the platinum-based alloy catalyst is prepared by the method of the first aspect. The platinum-based alloy catalyst according to an embodiment of the present application has the advantages of good catalytic performance, good stability, etc., and has a wide application prospect.

[0041] In the third aspect of the present application, a method for preparing a nanocarrier is provided. According to an embodiment of the present application, the method comprises: contacting polyacrylic acid, a nickel salt and a surfactant to obtain a nanocarrier; wherein the contacting is carried out in a reaction medium with pH=2-8.

[0042] According to the embodiment of the present application, the method for preparing the nanocarrier can further have the following additional technical features:

[0043] According to the embodiment of the present application, the polyacrylic acid has a molecular weight of 8000-12000.

[0044] According to the embodiment of the present application, the nickel salt includes one or more of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate.

[0045] According to the embodiment of the present application, the surfactant includes polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and / or cetyltrimethylammonium bromide.

[0046] According to the embodiment of the present application, the weight ratio of the polyacrylic acid, the nickel salt and the surfactant is 1:(2-6):(1-3).

[0047] According to the embodiment of the present application, the reaction medium is water and / or aqueous alcohol solution.

[0048] According to the embodiment of the present application, the reagent for adjusting the pH of the reaction medium is alkaline solution.

[0049] In the fourth aspect of the present application, the present application provides a nanocarrier. According to the embodiment of the present application, the nanocarrier is prepared by the method for preparing the nanocarrier of the first aspect. According to the embodiment of the present application, by controlling the reaction of the polyacrylic acid, the nickel salt and the surfactant at a specific pH value, the nickel polyacrylic acid nanocarrier with Xanthium structure is prepared with the help of the surfactant. The nanocarrier prepared by the method has Xanthium structure, can be used for loading catalyst and other substances, has the advantages of large specific surface area, high stability, good loading effect, etc., and has a wide application prospect.

[0050] According to the embodiment of the present application, the nanocarrier can further have the following additional technical features:

[0051] According to the embodiment of the present application, the nanocarrier has a pore size of 2-50 nm and a specific surface area of ≥800 m 2 g -1 .

[0052] In the fifth aspect of the present application, the present application provides a fuel cell. According to the embodiment of the present application, the fuel cell includes the platinum-based alloy catalyst of the fourth aspect. The fuel cell according to the embodiment of the present application has the advantages of good catalytic performance, good stability, long service life, low cost, easy preparation, etc., and has a wide application prospect.

[0053] In a sixth aspect, the present application provides the use of the platinum-based alloy catalyst according to the fifth aspect in a fuel cell. According to embodiments of the present application, the platinum-based alloy catalyst is used to improve the overall performance of the fuel cell.

[0054] It will be appreciated by a person skilled in the art that the features and advantages described above for the platinum-based alloy catalyst, the nanocarrier and the fuel cell also apply to this use, which will not be described again here.

[0055] According to embodiments of the present application, the use described above can further have the following additional technical features:

[0056] According to embodiments of the present application, the fuel cell comprises one or more of a proton exchange membrane fuel cell, a direct methanol fuel cell and a high-temperature fuel cell. BRIEF DESCRIPTION OF DRAWINGS

[0057] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description, including the appended drawings, wherein:

[0058] Figure 1 Figure for the reactor for preparing the colloidal platinum nanoparticles in Example 1 of the present application;

[0059] Figure 2 Figure for the BET curve results of the supported xanthan mesoporous carbon-platinum-based alloy catalyst I in Example 2 of the present application;

[0060] Figure 3 Figure for the SEM results of the supported xanthan mesoporous carbon-platinum-based alloy catalyst I in Example 2 of the present application;

[0061] Figure 4 Figure for the XRD detection results of the supported xanthan mesoporous carbon-platinum-based alloy catalyst I in Example 2 of the present application;

[0062] Figure 5 Figure for the LSV curve results of the supported xanthan mesoporous carbon-platinum-based alloy catalyst I in Example 2 of the present application;

[0063] Figure 6 Figure for the LSV curve results of the supported xanthan mesoporous carbon-platinum-based alloy catalyst I, the comparative catalyst II, the comparative catalyst III and the 50% TKK-Pt / C commercial catalyst in Example 2 of the present application. DETAILED DESCRIPTION

[0064] Embodiments of the present application are described in detail below. The embodiments described below are exemplary only, and are not to be construed as limiting the present application.

[0065] It should be noted that the terms "first", "second" are used only for descriptive purpose, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. Further, in the description of the present application, unless otherwise specified, the meaning of "plurality" is two or more.

[0066] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be roughly about the ranges or values. For ranges, the endpoints are included as well as intervening points which are included in the ranges. For values, the values are included as well as intervening values which are included in the values.

[0067] In the present text, the terms "comprising" or "including" are open-ended terms, i.e. they include the stated features but not excluding other features.

[0068] In the present text, the terms "optionally", "optional" or "option" generally mean that the event or circumstance subsequently described can or can not occur, and the description includes instances where the event or circumstance occurs and instances where it does not.

[0069] In the present text, "Pluronic F-127 surfactant" is a non-ionic high molecular surfactant, which belongs to the polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymer family.

[0070] In the present text, "Xanthan mesoporous carbon supported platinum-based alloy catalyst" is synonymous with "Nitrogen-doped mesoporous carbon supported platinum-copper alloy catalyst", "Supported xanthan mesoporous carbon-platinum-based alloy catalyst".

[0071] Method for preparing platinum-based alloy catalyst

[0072] The present application provides a method for preparing a platinum-based alloy catalyst. According to an embodiment of the present application, the method comprises: S1: contacting a nitrogen source and / or a sulfur source, an activator, and a nanocarrier, and performing carbonization treatment to obtain a carbonized polymer; S2: removing excess nickel from the carbonized polymer to obtain mesoporous carbon; S3: fixing a platinum nanoparticle colloid to the mesoporous carbon to obtain a composite; S4: depositing a plating layer material onto the surface of the composite to obtain a plating layer material-composite; S5: performing alloying treatment on the plating layer material-composite to obtain a plating layer material-alloy composite; and S6: removing excess plating layer material from the plating layer material-alloy composite to obtain a platinum-based alloy catalyst.

[0073] The inventors first mix the nano-carrier with a nitrogen / sulfur source and an activator, and then perform a programmed calcination to carbonize the polyacrylic acid and achieve nitrogen / sulfur doping, thereby obtaining a carbonized polymer; then the excess nickel in the carbonized polymer is removed through etching treatment and the like to construct a mesoporous structure, thereby obtaining mesoporous carbon; then platinum nanoparticle colloid is prepared using a photocatalytic reactor, and then the platinum nanoparticle colloid is uniformly dispersed on the mesoporous carbon; then the composite is vacuumed to deposit a base metal plating layer material on the surface of the composite, thereby obtaining a plating layer material-composite; then the plating layer material-alloy composite is obtained through high-temperature calcination in a reducing atmosphere to achieve alloying of platinum and the base metal plating layer material; finally, the excess base metal plating layer material is removed through etching treatment and the like, and the surface is dealloyed to form a platinum-rich surface, thereby obtaining a platinum-based alloy catalyst. The preparation method according to the embodiments of the present application has the advantages of low cost of reactants, simple preparation process, low energy consumption, and low emission of pollutants, and has great potential for large-scale production and application. The platinum-based alloy catalyst prepared by the method has the advantages of good catalytic performance, good stability, long service life, and the like, and has great potential for large-scale production and application, and has a wide application prospect.

[0074] According to the embodiments of the present application, the nano-carrier is prepared by contacting polyacrylic acid, a nickel salt and a surfactant to obtain a nickel polyacrylic acid nano-carrier; wherein the contacting is performed in a reaction medium with pH = 2-8. According to the preparation method of the embodiments of the present application, by controlling the reaction of polyacrylic acid, a nickel salt and a surfactant at a specific pH value, the nickel polyacrylic acid nano-carrier with a Xanthium-like structure can be prepared as soon as a white-green precipitate is generated with the assistance of the surfactant. The method for preparing the nano-carrier has the advantage of simple preparation method. The nano-carrier prepared by the method has the advantages of Xanthium-like structure, large specific surface area, high stability, good loading effect, and the like, and has a wide application prospect.

[0075] According to the embodiments of the present application, the molecular weight of the polyacrylic acid is 8000-12000. In this way, the physical and chemical properties of the prepared nano-carrier are controlled, thereby optimizing its performance as a catalyst carrier.

[0076] According to the embodiments of the present application, the nickel salt includes one or more of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate. In this way, it is suitable for various nickel salts, so that the most suitable nickel source can be selected according to the specific catalytic demand and cost-effectiveness, and the performance of the nano-carrier is optimized.

[0077] According to an embodiment of the present application, the surfactant comprises polyoxyethylene-polyoxypropylene-polyoxyethylene tri-block copolymer and / or cetyl trimethyl ammonium bromide. In this way, by adding the surfactant, the surface properties of the nanocarrier are adjusted, and the dispersibility and adhesion of the platinum-based alloy catalyst prepared are improved.

[0078] According to an embodiment of the present application, the weight ratio of the polyacrylic acid, the nickel salt and the surfactant is 1:(2-6):(1-3). In this way, by adjusting and optimizing the weight ratio of the polyacrylic acid, the nickel salt and the surfactant, the consistency and repeatability of the nanocarrier prepared are ensured, which is conducive to commercial mass production in the later stage. Illustratively, the weight ratio of the polyacrylic acid, the nickel salt and the surfactant is 1:2:1, 1:3:1, 1:4:1, 1:5:1, 1:6:1, 1:2:2, 1:3:2, 1:4:2, 1:5:2, 1:6:2, 1:2:3, 1:3:3, 1:4:3, 1:5:3, 1:6:3, preferably 1:(3.2-5.0):(1.5-2.5), more preferably 1:(3.8-4.2):(1.8-2.3).

[0079] According to an embodiment of the present application, the reaction medium is water and / or an aqueous alcohol solution. Illustratively, the reaction medium can be one or more of water, methanol aqueous solution, ethanol aqueous solution, ethylene glycol aqueous solution and isopropyl alcohol aqueous solution. In this way, the polyacrylic acid, the nickel salt and the surfactant are fully contacted, and the preparation time of the nanocarrier is shortened.

[0080] According to an embodiment of the present application, the weight ratio of the polyacrylic acid, the nickel salt, the surfactant and the reaction medium is 1:(2-6):(1-3):(10-50). In this way, by adjusting and optimizing the weight ratio of the polyacrylic acid, the nickel salt, the surfactant and the reaction medium, the consistency and repeatability of the nanocarrier prepared are ensured, which is conducive to commercial mass production in the later stage. Illustratively, the weight ratio of the polyacrylic acid, the nickel salt, the surfactant and the reaction medium is 1:2:1:10, 1:3:1:10, 1:4:1:10, 1:5:1:10, 1:6:1:10, 1:2:2:30, 1:3:2:30, 1:4:2:30, 1:5:2:30, 1:6:2:30, 1:2:3:50, 1:3:3:50, 1:4:3:50, 1:5:3:50, 1:6:3:50, preferably 1:(3.2-5.0):(1.5-2.5):(20-45), more preferably 1:(3.8-4.2):(1.8-2.3):(30-40).

[0081] According to an embodiment of the present application, the reagent for adjusting the pH of the reaction medium is an alkaline solution. Illustratively, the alkaline solution includes potassium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, and the like and aqueous solutions thereof; thereby, by adjusting the pH value with the alkaline solution, the size, morphology, and properties of the nanocarriers prepared are controlled.

[0082] According to an embodiment of the present application, the nanocarriers have a pore size of 2-50 nm and a specific surface area of ≥800 m 2 g -1 . Thus, the nanocarriers prepared have good carrier performance, which is important for maintaining the activity and stability of the load.

[0083] Illustratively, the nanocarriers have a pore size of 2 nm, 3 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, preferably 2-10 nm, and more preferably 3-5 nm; thereby, the nanocarriers prepared have good carrier performance, and at the same time, the pore size is uniform, further improving their utilization and selectivity, so that the carriers exhibit more excellent performance and stability in specific applications.

[0084] According to an embodiment of the present application, the platinum nanoparticle colloid is prepared by contacting a platinum source, a surfactant, and a photocatalyst to obtain a platinum nanoparticle colloid; wherein the contacting is performed under a light source. Thus, by reacting the platinum source, the surfactant, and the photocatalyst under a light source, the platinum nanoparticle colloid is efficiently, cleanly, and low-energy prepared, providing a basic condition for the catalyst part of the subsequent preparation of the platinum-based alloy catalyst.

[0085] According to an embodiment of the present application, the platinum source includes one or more of chloroplatinic acid, potassium chloroplatinate, and ammonium chloroplatinate. Thus, it is suitable for various platinum sources, so that the most suitable platinum source can be selected according to the specific catalytic needs and cost-effectiveness, and the performance of the platinum nanoparticle colloid is optimized.

[0086] According to an embodiment of the present application, the surfactant is one or more of sodium glycolate, cetyltrimethylammonium bromide, sodium cetyl sulfonate, and cetyltrimethylammonium chloride. Thus, under the photocatalytic conditions, active hydrogen is produced to help reduce the platinum in the chloroplatinum source, thereby preparing the platinum nanoparticle colloid, which provides a basic condition for the catalyst part of the subsequent preparation of the platinum-based alloy catalyst; and by controlling the concentration of the surfactant and the intensity of the light source, the generation rate and particle size of the platinum nanoparticle colloid are jointly controlled. Illustratively, the photocatalytic water splitting produces active hydrogen as a reducing agent, which reduces the platinum source to platinum nanoparticles, while the surfactant sodium glycolate can act as a stabilizer to prevent the aggregation of platinum nanoparticles.

[0087] According to an embodiment of the present application, the photocatalyst comprises one or more of titanium dioxide, cadmium sulfide, zinc oxide and cadmium selenide. Thus, a variety of photocatalysts are suitable, enabling the selection of the most suitable photocatalyst according to the specific catalytic requirements and cost effectiveness, and optimizing the performance of the platinum nanoparticle colloid. Illustratively, in an embodiment of the present application, titanium dioxide is utilized to generate platinum nanoparticles from the active hydrogen reducing platinum source under light, and further obtain the platinum nanoparticle colloid.

[0088] According to an embodiment of the present application, the intensity of the light source is 100-500 W. Thus, by controlling the intensity of the light source and the concentration of the surfactant, the generation rate and particle size of the platinum nanoparticle colloid are jointly controlled, further optimizing the performance of the platinum-based alloy catalyst subsequently prepared.

[0089] According to an embodiment of the present application, the weight ratio of the platinum source, the surfactant and the photocatalyst is 1:(2-10):(5-20). Thus, by precisely controlling the weight ratio of the platinum source, the reducing agent and the photocatalyst, the preparation process of the platinum nanoparticle colloid is further optimized.

[0090] Illustratively, the weight ratio of the platinum source, the surfactant and the photocatalyst is 1:2:5, 1:2:10, 1:2:15, 1:2:20, 1:5:5, 1:5:10, 1:5:15, 1:5:20, 1:10:5, 1:10:10, 1:10:15, 1:10:20, and preferably 1:(5.0-8.0):(10.0-15.0).

[0091] According to an embodiment of the present application, the contacting is performed in a reaction medium. Thus, in the reaction medium, the platinum source, the surfactant and the photocatalyst are fully contacted, shortening the preparation time of the platinum nanoparticle colloid.

[0092] According to an embodiment of the present application, the reaction medium is an alcohol solvent and / or water. Thus, in the reaction medium, the alcohol solvent and / or water, the platinum source, the surfactant and the photocatalyst are fully contacted, shortening the preparation time of the platinum nanoparticle colloid.

[0093] According to an embodiment of the present application, the alcohol solvent comprises one or more of methanol, ethanol and isopropanol. Thus, in the reaction medium, the alcohol solvent, the platinum source, the surfactant and the photocatalyst are fully contacted, shortening the preparation time of the platinum nanoparticle colloid. Illustratively, in an embodiment of the present application, methanol is used as the reaction medium, which not only enables the platinum source, the surfactant and the photocatalyst to be fully contacted, but also contains active hydrogen, which can be activated under photocatalysis and participate in the reduction of platinum in the platinum source, shortening the preparation time of the platinum nanoparticle colloid.

[0094] According to an embodiment of the present application, the weight ratio of the platinum source, the surfactant, the photocatalyst, the water and the alcohol solvent is 1:(2-10):(5-20):(80-100):(10-30). In this way, by precisely controlling the weight ratio of the platinum source, the reducing agent, the photocatalyst, the water and the alcohol solvent, the preparation process of the platinum nanoparticle colloid is further optimized.

[0095] Illustratively, the weight ratio of the platinum source, the surfactant, the photocatalyst, the water and the alcohol solvent is 1:2:5:18:90, 1:2:10:18:90, 1:2:15:18:90, 1:2:20:18:90, 1:5:15:18:90, 1:10:15:18:90, preferably 1:(5.0-8.0):(10.0-15.0):(18-25):(88-95).

[0096] According to an embodiment of the present application, the activating agent is an alkali metal hydroxide. In this way, by using an alkali metal hydroxide as the activating agent, the carbonization process of the nanocarrier is promoted, so that the mesoporous carbon carrier with ideal pore structure is quickly obtained.

[0097] According to an embodiment of the present application, the activating agent includes one or more of potassium hydroxide, sodium hydroxide and potassium nitrate. In this way, by using potassium hydroxide or the like as the activating agent, the carbonization process of the nanocarrier is promoted, so that the mesoporous carbon carrier with ideal pore structure is quickly obtained.

[0098] According to an embodiment of the present application, the nitrogen source includes one or more of urea, melamine, dicyandiamide and amino acid. In this way, a variety of nitrogen source options are provided, the chemical composition of the nitrogen / sulfur-doped mesoporous carbon carrier is precisely controlled according to the actual application, and the electrocatalytic performance and durability of the platinum-based alloy catalyst prepared are further improved.

[0099] According to an embodiment of the present application, the sulfur source includes one or more of thiourea, thioacetamide, cysteine and sulfur powder. In this way, a variety of sulfur source options are provided, the chemical composition of the nitrogen / sulfur-doped mesoporous carbon carrier is precisely controlled according to the actual application, and the electrocatalytic performance and durability of the platinum-based alloy catalyst prepared are further improved.

[0100] According to an embodiment of the present application, the carbonization treatment includes a first-stage carbonization treatment and a second-stage carbonization treatment. In this way, by the first-stage carbonization treatment and the second-stage carbonization treatment, the carbonized polymer is obtained by sufficiently carbonizing it, providing a carrier basis for the subsequent preparation of the platinum-based alloy catalyst.

[0101] According to an embodiment of the present application, in the first stage carbonization treatment, the calcination temperature is 200-400℃, the heating rate is 4-6℃ / min, and the holding time is 2-3h. Thus, through the first stage carbonization treatment, the polymer is preliminarily carbonized, while avoiding the structure damage caused by polymer melting, and a foundation is provided for the subsequent preparation of the platinum-based alloy catalyst. Illustratively, in the first stage carbonization treatment, the calcination temperature is 200℃, 250℃, 300℃, 350℃, 400℃, preferably 250-380℃, more preferably 280-350℃; the heating rate is 4℃ / min, 5℃ / min, 6℃ / min, preferably 4.5-5.5℃ / min, more preferably 4.8-5.3℃ / min; and the holding time is 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, preferably 2.2-2.8h, more preferably 2.4-2.7h.

[0102] According to an embodiment of the present application, in the second stage carbonization treatment, the calcination temperature is 800-900℃, the heating rate is 4-6℃ / min, and the holding time is 2-3h. Thus, through the second stage carbonization treatment, the polymer is completely carbonized, and a carrier foundation is provided for the subsequent preparation of the platinum-based alloy catalyst. Illustratively, in the second stage carbonization treatment, the calcination temperature is 800℃, 820℃, 840℃, 860℃, 880℃, 900℃, preferably 820-880℃, more preferably 850-870; the heating rate is 4℃ / min, 5℃ / min, 6℃ / min, preferably 4.5-5.5℃ / min, more preferably 4.8-5.3℃ / min; and the holding time is 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, preferably 2.2-2.8h, more preferably 2.4-2.7h.

[0103] According to an embodiment of the present application, the weight ratio of the nanocarrier and the nitrogen source and / or the sulfur source is 1:(0.5-3). Thus, by controlling the weight ratio of the nitrogen source and the sulfur source, the chemical composition of the nitrogen / sulfur doped mesoporous carbon carrier is accurately controlled, and the electrocatalytic performance and durability of the prepared platinum-based alloy catalyst are further improved.

[0104] According to an embodiment of the present application, the weight ratio of the mesoporous carbon and the platinum nanoparticles is 1:(0.3-3). Thus, the dispersibility and loading amount of the platinum nanoparticles on the mesoporous carbon carrier are further optimized, and the electrocatalytic performance and durability of the prepared platinum-based alloy catalyst are further improved.

[0105] Illustratively, the weight ratio of the mesoporous carbon and the platinum source for preparing the platinum nanoparticle colloid is 1:0, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, preferably 1:(0.5-2), more preferably 1:(1-1.2).

[0106] According to an embodiment of the present application, the plating material is a base metal material. Thus, by using a base metal material as the plating material, a catalyst with a specific metal alloy structure is prepared, further improving the durability and anti-poisoning ability of the platinum-based alloy catalyst.

[0107] According to an embodiment of the present application, the plating material comprises one or more of iron, nickel, cobalt, copper, zinc and manganese. Thus, according to the actual application, by using a base metal material such as nickel as the plating material, a catalyst with a specific metal alloy structure is prepared, further improving the catalytic activity, durability and anti-poisoning ability of the platinum-based alloy catalyst.

[0108] According to an embodiment of the present application, the weight ratio of the composite and the plating material in the plating material-composite is 1:(0.3-10). Thus, by controlling the proportion of the plating material in the plating material-composite, the proportion of the base metal and platinum in the obtained platinum-based alloy catalyst is accurately adjusted, further improving the electrocatalytic performance and durability of the prepared platinum-based alloy catalyst.

[0109] According to an embodiment of the present application, the plating material deposition method comprises one or more of vacuum evaporation, chemical vapor deposition, electrochemical deposition and co-precipitation. Thus, the plating material is deposited on the surface of the composite to prepare the plating material-composite. According to an embodiment of the present application, the plating material deposition method is vacuum evaporation, which has the characteristics of cleanliness, high efficiency and environmental protection, further reducing energy consumption and pollution, and further improving the electrocatalytic performance and durability of the prepared platinum-based alloy catalyst.

[0110] According to an embodiment of the present application, in the alloying treatment, the calcination temperature is 600-800℃, the heating rate is 4-6℃ / min, and the holding time is 2-3h. Thus, by alloying treatment, the close combination between the plating material and the mesoporous carbon carrier is achieved to obtain a plating material-alloy composite, further improving the electrocatalytic performance and durability of the prepared platinum-based alloy catalyst. Exemplarily, in the alloying treatment, the calcination temperature is 600℃, 50℃, 700℃, 750℃, 800℃, preferably 620-780℃, more preferably 650-770; the heating rate is 4℃ / min, 5℃ / min, 6℃ / min, preferably 4.5-5.5℃ / min, more preferably 4.8-5.3℃ / min; and the holding time is 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, preferably 2.2-2.8h, more preferably 2.4-2.7h.

[0111] According to an embodiment of the present application, the alloying treatment is performed under a mixed gas of inert gas and hydrogen, and the hydrogen accounts for 5-20% in the mixed gas. In this way, the platinum nanoparticles are alloyed with the plating material to form the platinum-based alloy under high temperature.

[0112] According to an embodiment of the present application, the platinum accounts for 10-70% in the platinum-based alloy catalyst. In this way, by determining the proportion of platinum in the platinum-based alloy catalyst, the composition of the catalyst is precisely controlled, and the electrocatalytic performance and durability of the prepared platinum-based alloy catalyst are further ensured.

[0113] Platinum-based alloy catalyst

[0114] The present application provides a platinum-based alloy catalyst. According to an embodiment of the present application, the platinum-based alloy catalyst is prepared by the method described above. The platinum-based alloy catalyst according to the embodiment of the present application has the advantages of good catalytic performance and good stability, and has a wide application prospect.

[0115] Method for preparing nanocarrier

[0116] The present application provides a method for preparing a nanocarrier. According to an embodiment of the present application, the method comprises: contacting polyacrylic acid, a nickel salt and a surfactant to obtain a nickel polyacrylic acid nanocarrier; wherein the contacting is performed in a reaction medium with pH=2-8. According to the preparation method of the embodiment of the present application, by controlling the reaction of polyacrylic acid, a nickel salt and a surfactant at a specific pH value, under the assistance of the surfactant, a nickel polyacrylic acid nanocarrier with a Xanthium structure is prepared as soon as a white-green precipitate is generated. The method for preparing a nanocarrier has the advantage of simple preparation method. The nanocarrier prepared by the method has a Xanthium structure, can be used to load catalysts and other substances, has the advantages of large specific surface area, high stability, good loading effect, and has a wide application prospect.

[0117] According to an embodiment of the present application, the molecular weight of the polyacrylic acid is 8000-12000. In this way, the physical and chemical properties of the prepared nanocarrier are controlled, so as to optimize its performance as a catalyst carrier.

[0118] According to an embodiment of the present application, the nickel salt comprises one or more of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate. In this way, it is suitable for various nickel salts, so that the most suitable nickel source can be selected according to the specific catalytic demand and cost-effectiveness, and the performance of the nanocarrier is optimized.

[0119] According to an embodiment of the present application, the surfactant comprises polyoxyethylene-polyoxypropylene-polyoxyethylene tri-block copolymer and / or cetyl trimethyl ammonium bromide. In this way, by adding the surfactant, the surface properties of the nanocarrier are adjusted, and the dispersibility and adhesion of the platinum-based alloy catalyst prepared are improved.

[0120] According to an embodiment of the present application, the weight ratio of the polyacrylic acid, the nickel salt and the surfactant is 1:(2-6):(1-3). In this way, by adjusting and optimizing the weight ratio of the polyacrylic acid, the nickel salt and the surfactant, the consistency and repeatability of the nanocarrier prepared are ensured, which is conducive to commercial mass production in the later stage. Illustratively, the weight ratio of the polyacrylic acid, the nickel salt and the surfactant is 1:2:1, 1:3:1, 1:4:1, 1:5:1, 1:6:1, 1:2:2, 1:3:2, 1:4:2, 1:5:2, 1:6:2, 1:2:3, 1:3:3, 1:4:3, 1:5:3, 1:6:3, preferably 1:(3.2-5.0):(1.5-2.5), more preferably 1:(3.8-4.2):(1.8-2.3).

[0121] According to an embodiment of the present application, the reaction medium is water and / or an aqueous alcohol solution. Illustratively, the reaction medium can be one or more of water, methanol aqueous solution, ethanol aqueous solution, ethylene glycol aqueous solution and isopropyl alcohol aqueous solution. In this way, the polyacrylic acid, the nickel salt and the surfactant are fully contacted, and the preparation time of the nanocarrier is shortened.

[0122] According to an embodiment of the present application, the weight ratio of the polyacrylic acid, the nickel salt, the surfactant and the reaction medium is 1:(2-6):(1-3):(10-50). In this way, by adjusting and optimizing the weight ratio of the polyacrylic acid, the nickel salt, the surfactant and the reaction medium, the consistency and repeatability of the nanocarrier prepared are ensured, which is conducive to commercial mass production in the later stage. Illustratively, the weight ratio of the polyacrylic acid, the nickel salt, the surfactant and the reaction medium is 1:2:1:10, 1:3:1:10, 1:4:1:10, 1:5:1:10, 1:6:1:10, 1:2:2:30, 1:3:2:30, 1:4:2:30, 1:5:2:30, 1:6:2:30, 1:2:3:50, 1:3:3:50, 1:4:3:50, 1:5:3:50, 1:6:3:50, preferably 1:(3.2-5.0):(1.5-2.5):(20-45), more preferably 1:(3.8-4.2):(1.8-2.3):(30-40).

[0123] According to an embodiment of the present application, the reagent for adjusting the pH of the reaction medium is an alkaline solution. Exemplarily, the alkaline solution comprises potassium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, etc. and aqueous solutions thereof; thus, by adjusting the pH value with the alkaline solution, the size, morphology and properties of the nanocarrier prepared are controlled.

[0124] Nanocarrier

[0125] The present application provides a nanocarrier. According to an embodiment of the present application, the nanocarrier is prepared by the aforementioned method for preparing a nanocarrier. According to an embodiment of the present application, by controlling the reaction of polyacrylic acid, nickel salt and surfactant at a specific pH value, under the assistance of the surfactant, a nickel polyacrylate nanocarrier with a Xanthium structure is prepared as soon as a white-green precipitate is generated. The nanocarrier prepared by this method has a Xanthium structure, can be used to load catalysts and other substances, has the advantages of large specific surface area, high stability, good loading effect, etc. and has a wide application prospect.

[0126] According to an embodiment of the present application, the pore size of the nanocarrier is 2-50 nm, and the specific surface area is ≥800 m 2 g -1 . Thus, the nanocarrier prepared has good carrier performance, which is important for maintaining the activity and stability of the loaded substance.

[0127] Exemplarily, the pore size of the nanocarrier is 2 nm, 3 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, preferably 2-10 nm, and more preferably 3-5 nm; thus, the nanocarrier prepared has good carrier performance, and at the same time, its pore size is uniform, further improving its utilization rate and selectivity, so that the carrier exhibits more excellent performance and stability in specific applications.

[0128] Fuel cell

[0129] The present application provides a fuel cell. According to an embodiment of the present application, the fuel cell comprises the aforementioned platinum-based alloy catalyst. The fuel cell according to an embodiment of the present application has the advantages of good catalytic performance, good stability, long service life, low cost, easy preparation, etc. and has a wide application prospect.

[0130] Application

[0131] The present application provides the application of the aforementioned platinum-based alloy catalyst in a fuel cell. According to an embodiment of the present application, the platinum-based alloy catalyst is used to improve the electrocatalytic performance of the cell.

[0132] It can be understood by those skilled in the art that the features and advantages described above for the platinum-based alloy catalyst, nanocarrier and fuel cell also apply to the application, which will not be described here again.

[0133] According to embodiments of the present application, the fuel cell comprises one or more of a proton exchange membrane fuel cell, a direct methanol fuel cell, and a high temperature fuel cell. Thus, the platinum-based alloy catalyst is suitable for use in a variety of fuel cells, particularly proton exchange membrane fuel cells.

[0134] The schemes of the present application will be explained below with reference to examples. Those skilled in the art will understand that the examples below are only for illustration of the present application and should not be considered as limiting the scope of the present application. If a specific technique or condition is not specified in the examples, the technique or condition described in the literature in the art or according to the product manual is used. If the manufacturer of the reagent or instrument is not specified, it is a conventional product that can be obtained commercially.

[0135] Example 1: Preparation of a xanthan gum supported platinum-based alloy catalyst I

[0136] Step S1: Preparation of polyacrylic acid nickel nanospheres

[0137] Accurately weigh 18 g of Pluronic F-127 surfactant (purchased from Shanghai Aladdin Biochem Technology Co., Ltd.), 120 g of water, 10 g of nickel nitrate hexahydrate, and 4 g of polyacrylic acid with a molecular weight of 8000 to prepare a solution, and ultrasonic for 40 min; add 10 g of nickel nitrate hexahydrate, and stir for 10 min; drop 5 mol / L potassium hydroxide into the solution until the pH is 2.0-8.0, and continue to stir for 10 h, filter and dry to obtain polyacrylic acid nickel nanospheres.

[0138] Step S2: Preparation of nitrogen / sulfur doped mesoporous carbon

[0139] Accurately weigh 3 g of urea, 3 g of potassium hydroxide, and 2 g of polyacrylic acid nickel nanospheres prepared in step S1, mix and grind the three, and place them in a 99.99% nitrogen atmosphere, and heat to 300°C at a heating rate of 5°C / min, and heat for 2 h to preliminarily carbonize the polymers of the three to avoid the destruction of the structure caused by the melting of the polymers; then heat to 800°C at a heating rate of 5°C / min, and heat for 2 h to completely carbonize the polymers; cool to room temperature, and etch the nickel in the polymers with a 3 mol / L nitric acid solution for 10 h, and filter, wash with water, and dry to obtain nitrogen / sulfur doped mesoporous carbon.

[0140] Step S3: Preparation of platinum nanoparticle colloid

[0141] Take 3g chloroplatinic acid hydrate, 50g methanol, 20g sodium glycolate dissolved in 300mL water, under the condition of ultrasonic power 200W, ultrasonic frequency 40kHz, keep 40min, the whole process to ensure the temperature below 25℃, make it disperse uniformly, then arrange the titanium mesh covered with titanium dioxide layer in the solution, irradiate with 500W high pressure mercury lamp for 10h, then get glycolic acid stable platinum nanoparticles colloid.

[0142] The reactor for preparing platinum nanoparticles colloid is shown in Figure 1 .

[0143] Step S4: preparation of Pt / C composite

[0144] Mix 0.8g platinum nanoparticles colloid prepared in step S3 with 0.8g nitrogen / sulfur doped mesoporous carbon prepared in step S2, so that the Pt content is about 50%, ultrasonic for 40min (ultrasonic power 200W, ultrasonic frequency 40kHz), make it disperse uniformly, then add 3mol / L nitric acid solution dropwise to pH=2, after filtration, water washing, drying, get Pt / C composite.

[0145] Step S5: vacuum evaporation of Cu

[0146] Take 2g Pt / C composite prepared in step S4 and place it in the vacuum evaporation chamber, select Cu target (coating material) and ultrasonic stirring (ultrasonic power 80W, ultrasonic frequency 40kHz) for 2h, get Pt / C-Cu composite.

[0147] Step S6: calcination to form Pt-Cu alloy composite

[0148] Take 5g Pt / C-Cu composite prepared in step S5 and place it in 10% hydrogen-nitrogen mixed atmosphere (hydrogen volume ratio 10%, nitrogen volume ratio 90%), with a heating rate of 5℃ / min, rise to 700℃, keep for 2h, make Cu alloy with Pt, cool to room temperature, get Pt-Cu alloy composite.

[0149] Step S7: etching treatment

[0150] Take 5g Pt-Cu alloy composite prepared in step S6, place it in etching solution with nitric acid concentration of 1mol / L and ferric nitrate concentration of 0.5mol / L, heat to 60℃ and react for 2h, remove excess Cu and make the alloy surface dealloying to generate platinum-rich surface, then filter, wash with water and dry, get supported xanthic mesoporous carbon-platinum-based alloy catalyst I (nitrogen-doped mesoporous carbon supported platinum-copper alloy catalyst I).

[0151] Step S8: crushing

[0152] The supported Xanthan mesoporous carbon-Pt-based alloy catalyst prepared in step S6 was ground in a pulverizer for 30 s to obtain a supported Xanthan mesoporous carbon-Pt-based alloy catalyst powder I (nitrogen-doped mesoporous carbon-supported Pt-Cu alloy catalyst powder I).

[0153] Preparation of Comparative Catalyst II

[0154] Example 2 differs from Example 1 in that the steps of vacuum evaporation of Cu, calcination to form a Pt-Cu alloy composite, and etching treatment are absent, and the specific preparation method is as follows:

[0155] Step S1: Preparation of poly-nickel-acrylic acid nanospheres

[0156] This step is the same as step S1 of Example 1.

[0157] Step S2: Preparation of nitrogen / sulfur-doped mesoporous carbon

[0158] This step is the same as step S2 of Example 1.

[0159] Step S3: Preparation of platinum nanoparticle colloid

[0160] This step is the same as step S3 of Example 1.

[0161] Step S4: Preparation of Pt / C composite

[0162] This step is the same as step S4 of Example 1.

[0163] Step S5: Grinding

[0164] This step is the same as step S8 of Example 1, and a comparative catalyst II powder is obtained.

[0165] Preparation of Comparative Catalyst III

[0166] Example 3 differs from Example 1 in steps 2 and 4, and the specifics are as follows:

[0167] Step S1: Preparation of poly-nickel-acrylic acid nanospheres

[0168] This step is the same as step S1 of Example 1.

[0169] Step S2: Preparation of mesoporous carbon

[0170] This step differs from Example 1 in that 3 g of urea and 3 g of potassium hydroxide are not added, and the specifics of this step are as follows:

[0171] Take 2g of S1 nanometer microspheres, place them in a 99.99% nitrogen atmosphere, and raise the temperature to 300°C at a rate of 5°C / min. Keep the temperature at 300°C for 2h to preliminarily carbonize the polymer and avoid the destruction of the structure caused by the melting of the polymer. Raise the temperature to 800°C at a rate of 5°C / min, and keep the temperature at 800°C for 2h to completely carbonize the above reaction product. Cool to room temperature, and etch the nickel in the carbon with a 3mol / L nitric acid solution for 10h. After filtration, water washing, and drying, mesoporous carbon is obtained.

[0172] Step S3: Preparation of platinum nanoparticle colloid

[0173] This step is the same as step S3 of Example 1.

[0174] Step S4: Preparation of Pt / C composite

[0175] The difference between this step and Example 1 is that the nitrogen / sulfur-doped mesoporous carbon is replaced by mesoporous carbon. This step is as follows:

[0176] Mix 0.8g of the platinum nanoparticle colloid prepared in step S3 with 0.8g of the mesoporous carbon prepared in step S2 to make the Pt content about 50%. Keep the mixture under ultrasonic conditions at an ultrasonic power of 200W and an ultrasonic frequency of 40kHz for 40min, and make sure that the temperature is below 25°C during the whole process to make the mixture uniformly dispersed. Then, add a 3mol / L nitric acid solution dropwise until the pH is 2. After filtration, water washing, and drying, a Pt / C composite is obtained.

[0177] Step S5: Vacuum evaporation of Co

[0178] The difference between this step and Example 1 is that the plating material Cu is replaced by the plating material Co. This step is as follows:

[0179] Take 2g of the Pt / C composite prepared in step S4, place it in a vacuum evaporation chamber, and select a Co target (plating material) to vacuum evaporate for 2h under the action of ultrasonic stirring (ultrasonic power of 80W and ultrasonic frequency of 40kHz) to obtain a Pt / C-Co composite.

[0180] Step S6: Calcination to form Pt-Co alloy composite

[0181] This step is the same as step S6 of Example 1.

[0182] Step S7: Etching treatment

[0183] This step is the same as step S7 of Example 1 to obtain comparative catalyst III (mesoporous carbon-supported platinum-cobalt alloy catalyst III)

[0184] Step S8: Crushing

[0185] The step is the same as step S8 of Example 1 to obtain comparative catalyst III powder (mesoporous carbon supported platinum cobalt alloy catalyst III powder).

[0186] Example 2: Performance test of Xanthium mesoporous carbon supported platinum-based alloy catalyst I

[0187] The comparative catalysts II and III prepared from Comparative Example I and Comparative Example II and the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I prepared from Example 1 are subjected to relevant performance tests, as follows:

[0188] 1. Specific surface area and pore size detection

[0189] The specific surface area and pore size of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I prepared from Example 1 are detected.

[0190] The BET curve of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I is shown in Figure 2 .

[0191] The results show that the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I prepared from Example 1 has a porous structure, and the specific surface area of the material is as high as 1292.51 m 2 / g, and the pore size is mostly distributed in 3-5 nm, belonging to mesoporous carbon.

[0192] 2. Scanning electron microscope detection

[0193] The scanning electron microscope detection of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I prepared from Example 1 is performed.

[0194] The SEM results of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I are shown in Figure 3 .

[0195] The results show that the surface of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I prepared from Example 1 is rough, which can provide abundant active sites for the attachment of Pt particles and can also alleviate the migration and agglomeration of Pt particles.

[0196] 3. X-ray diffraction detection

[0197] The X-ray diffraction detection of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I prepared from Example 1 is performed.

[0198] The XRD detection results of the supported Xanthium mesoporous carbon-platinum-based alloy catalyst I are shown in Figure 4 .

[0199] The results show that the XRD image of the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I prepared in Example 1 is obviously different from the Pt standard image, and the diffraction peak shifts to a high angle, which is caused by the Cu and Pt alloying, indicating that the platinum copper alloy is successfully synthesized.

[0200] 4. Electrochemical stability test

[0201] The electrochemical stability test is performed on the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I prepared in Example 1.

[0202] The LSV curve results of the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I are shown in Table 4. Figure 5 .

[0203] The results show that the initial LSV curve and the LSV curve after 30000 cycles are basically consistent, indicating that the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I prepared in Example 1 has excellent stability, and can still retain a mass activity of up to 508 mA / mg after 30000 cycles, and the mass activity retention rate is as high as 90.6%, indicating that the catalyst has excellent stability.

[0204] 5. Electrochemical comparison test

[0205] The electrochemical comparison test is performed on the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I prepared in Examples 1-3, the comparative catalyst II, the comparative catalyst III, and the commercially available 50% TKK-Pt / C commercial catalyst (purchased from Tanaka Precious Metals Group Co., Ltd.).

[0206] The LSV curve results of the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I, the comparative catalyst II, the comparative catalyst III, and the 50% TKK-Pt / C commercial catalyst are shown in Table 5. Figure 6 .

[0207] The results show that the initial mass activity of the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I prepared in Example 1 at 0.9V is as high as 561 mA / mg, which is much higher than that of the commercially available 50% TKK-Pt / C commercial catalyst (161 mA / mg), the comparative catalyst II prepared in Example 2 (203 mA / mg), and the comparative catalyst III prepared in Example 3 (323 mA / mg), indicating that the supported Xanthan mesoporous carbon-platinum-based alloy catalyst I prepared in Example 1 has very excellent catalytic activity and has a strong application potential.

[0208] The test results 1-5 above show that the supported Xanthan mesoporous carbon-platinum-based alloy catalyst prepared by the method of the present application has more excellent catalytic activity and catalytic stability compared with the commercially available catalyst.

[0209] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are contained in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any suitable manner in any one or more embodiments or examples. In addition, the person skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of the different embodiments or examples without contradiction.

[0210] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. A method of preparing a platinum-based alloy catalyst, characterized by, The application relates to a preparation method of a platinum-based alloy catalyst. S1: contacting a nitrogen source and / or a sulfur source, an activator and a nano carrier, and performing carbonization treatment to obtain a carbonized polymer; S2: removing excess nickel from the carbonized polymer to obtain mesoporous carbon; S3: fixing a platinum nanoparticle colloid to the mesoporous carbon to obtain a composite; S4: depositing a plating layer material on the surface of the composite to obtain a plating layer material-composite; S5: performing alloying treatment on the plating layer material-composite to obtain a plating layer material-alloy composite; S6: removing excess plating layer material from the plating layer material-alloy composite to obtain a platinum-based alloy catalyst; The nano carrier is prepared by the following method: The first contact is performed in a first reaction medium with pH=2-8. The platinum nanoparticle colloid is prepared by the following method: The second contact is performed under a light source. The plating layer material is a base metal material. The molecular weight of the polyacrylic acid is 8000-12000. The nickel salt includes one or more of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate.

2. The method of claim 1, wherein, The surfactant includes polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and / or cetyltrimethylammonium bromide.

3. The method of claim 1, wherein, The weight ratio of the polyacrylic acid, the nickel salt and the surfactant is 1:(2-6):(1-3).

4. The method of claim 1, wherein, The first reaction medium is water and / or an alcohol aqueous solution.

5. The method of claim 1, wherein, The reagent for adjusting the pH of the first reaction medium is an alkaline solution.

6. The method of claim 1, wherein, The platinum source includes one or more of chloroplatinic acid, potassium chloroplatinate and ammonium chloroplatinate.

7. The method of claim 1, wherein, The surfactant is one or more of sodium glycolate, cetyltrimethylammonium bromide, sodium cetyl sulfonate and cetyltrimethylammonium chloride.

8. The method of claim 1, wherein, The nanoparticle has a pore size of 2-50 nm, a specific surface area of ≥800 m 2 g -1 .

9. The method of claim 1, wherein, The photocatalyst includes one or more of titanium dioxide, cadmium sulfide, zinc oxide and cadmium selenide.

10. The method of claim 1, wherein, The weight ratio of the platinum source, the surfactant and the photocatalyst is 1:(2-10):(5-20).

11. The method of claim 1, wherein, The second contact is performed in a second reaction medium.

12. The method of claim 1, wherein, The second reaction medium is an alcohol solvent and / or water.

13. The method of claim 1, wherein, The alcohol solvent includes one or more of methanol, ethanol and isopropanol.

14. The method of claim 13, wherein, The activator is an alkali metal hydroxide.

15. The method of claim 14, wherein, The activator includes one or more of potassium hydroxide, sodium hydroxide and potassium nitrate.

16. The method of claim 1, wherein, The nitrogen source includes one or more of urea, melamine, dicyandiamide and amino acid.

17. The method of claim 16, wherein, The sulfur source includes one or more of thiourea, thioacetamide, cysteine and sulfur powder.

18. The method of claim 1, wherein, The carbonization treatment includes first-stage carbonization treatment and second-stage carbonization treatment.

19. The method of claim 1, wherein, In the first-stage carbonization treatment, the calcination temperature is 200-400 DEG C, the temperature rising rate is 4-6 DEG C / min, and the holding time is 2-3 h.

20. The method of claim 1, wherein, In the second-stage carbonization treatment, the calcination temperature is 800-900 DEG C, the temperature rising rate is 4-6 DEG C / min, and the holding time is 2-3 h.

21. The method of claim 20, wherein, The weight ratio of the nano carrier and the nitrogen source and / or the sulfur source is 1:(0.5-3).

22. The method of claim 20, wherein, ​ 23. The method of claim 1, wherein, ​ 24. The method of claim 1, wherein, The weight ratio of the mesoporous carbon and the platinum nanoparticles is 1: (0.3-3).

25. The method of claim 1, wherein, The plating layer material comprises one or more of iron, nickel, cobalt, copper, zinc and manganese.

26. The method of claim 1, wherein, The weight ratio of the composite and the plating layer material in the plating layer material-composite is 1: (0.3-10).

27. The method of claim 1, wherein, In the alloying treatment, the calcination temperature is 600-800 ℃, the heating rate is 4-6 ℃ / min, and the holding time is 2-3 h.

28. The method of claim 1, wherein, The alloying treatment is carried out in a mixed gas of inert gas and hydrogen, and the proportion of hydrogen in the mixed gas is 5-20%.

29. The method of claim 1, wherein, The mass proportion of platinum in the platinum-based alloy catalyst is 10-70%.

30. A platinum-based alloy catalyst characterized by, The platinum-based alloy catalyst is prepared by the method of any one of claims 1-29.

31. A fuel cell, characterized by The platinum-based alloy catalyst of claim 30 is included.

32. Use of the platinum-based alloy catalyst of claim 30 in a fuel cell, wherein The platinum-based alloy catalyst is used to improve the comprehensive performance of a fuel cell.

33. The use according to claim 32, wherein The fuel cell comprises one or more of a proton exchange membrane fuel cell, a direct methanol fuel cell and a high-temperature fuel cell.

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