Carbon-supported noble metal ordered alloy electrocatalyst capable of realizing mass production

Abstract

The invention relates to a carbon-supported noble metal ordered alloy electrocatalyst capable of realizing mass production. The electrocatalyst comprises a carbon carrier and small-size noble metal ordered alloy nanoparticles loaded on the carrier, the loading capacity of the alloy is 20 to 90 weight percent; the average particle size of the precious metal ordered alloy nanoparticles is 1-10 nm; the noble metal ordered alloy comprises an alloy consisting of a noble metal and at least one different transition metal M; wherein the noble metal is platinum, palladium, iridium, rhodium or ruthenium. The method is used for solving the problem that the size of catalyst particles becomes large in the high-temperature ordering process, high metal loading capacity is achieved, the feed ratio is increased to 60 times, successful synthesis of the catalyst can be achieved on the gram scale level, and the method can be popularized to actual production to achieve large-scale production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of materials and catalysts, and relates to the synthesis and preparation method of an electrocatalyst, and particularly proposes a high-loading carbon-supported noble metal ordered alloy electrocatalyst and a preparation method thereof. BACKGROUND

[0002] Fuel cells are an important alternative energy technology that can replace the current fossil fuel system. Among them, proton exchange membrane fuel cells are widely studied and used as a power source for fuel cell vehicles. However, due to the scarcity of platinum, we need to find a cathode electrocatalyst with high activity and low cost to promote the commercialization process of fuel cell vehicles.

[0003] Introducing transition metals to form alloyed nanoparticle catalysts is a simple and effective method, which is studied due to its enhanced electrocatalytic activity and reduced Pt loading. However, the degree of alloying is usually low at low temperatures, while high temperatures can lead to an increase in particle size. This makes it easy for transition metals to dissolve and lose in alloy catalysts in practical applications, and larger sizes reduce the exposure of active sites, thereby reducing the durability and stability of the catalyst.

[0004] Many researchers are also working on the synthesis of noble metal-based alloy catalysts for fuel cell applications, but traditional alloy catalysts are usually high-temperature synthesized nanoparticle catalysts, leading to particle agglomeration and growth, and the loading of the catalyst is not more than 40%, which results in lower effective catalytic performance of the catalyst in application, and there are problems such as noble metal particle agglomeration and uneven particle distribution, and the structure of the monodisperse metal nanoparticle catalyst synthesized at high temperature has serious disadvantages, such as easy agglomeration and shedding of nanoparticles, and lower electrochemical active surface area and higher mass transfer resistance. In the current production of catalysts, many of the existing catalyst preparation methods do not have the synthesis conditions that can be realized in actual mass production.

[0005] In the prior art, CN201910617257.4 "Carbon nanosheet supported noble metal nanoparticle catalyst and its preparation method and application" provides a commercial carbon source, and loads a noble metal nanoparticle catalyst on the commercial carbon precursor. The size of the noble metal nanoparticle catalyst obtained is 2nm-50nm, and the content of the noble metal is 0.5wt%-10wt%. However, it still has the problems of uneven particle size and low noble metal loading, which limits the further improvement of the catalyst activity and stability.

[0006] CN202210845558.4, "A Pt-based Intermetallic Ordered Alloy, Preparation Method and Application," describes a process where a heteroatom-rich coating layer is constructed on a support, followed by loading disordered alloy particles or a mixed Pt alloy precursor and then subjecting it to high-temperature pyrolysis. This effectively prevents further agglomeration of Pt particles. Although small-particle-size, highly dispersed PtM intermetallic ordered alloy particles are obtained, significantly reducing the pyrolysis time and temperature of the alloy catalyst, the process remains complex, with low Pt loading (27.7 wt%) and low Pt utilization. CN202311354567.4, "A High-Loading Pt / C Catalyst for Fuel Cells and Its Preparation Method," provides a high-loading Pt / C catalyst for fuel cells and its preparation method. It uses a special reducing agent (ethylene glycol, N-methylpyrrolidone) and pretreated carbon black as a support, which shortens the catalyst preparation time and produces catalyst particles with uniformity, good dispersion, and high loading. However, due to its complex preparation process, which requires the addition of reducing agents and alkaline solutions for pH adjustment, it is not conducive to the actual quantitative production of catalysts. Furthermore, pure platinum catalysts are expensive, and there is significant room for improvement in both their activity and stability.

[0007] Therefore, designing a high-load, high-activity, and high-stability noble metal ordered alloy nanoparticle catalyst that can be mass-produced remains a huge challenge. Summary of the Invention

[0008] The purpose of this invention is to address the shortcomings of existing technologies by providing a mass-producible carbon-supported noble metal ordered alloy electrocatalyst and its preparation method. This electrocatalyst comprises a carbon support and small-sized noble metal alloy nanoparticles supported on the support; the metal loading is 20wt%–90wt%. The preparation method combines pressure-assisted regulation with traditional high-temperature annealing, thereby achieving the goal of limiting particle size growth and homogenizing particles under high-temperature annealing conditions while maintaining the traditional high-temperature ordering of nanoparticles. Furthermore, a one-step direct synthesis of the catalyst replaces the current steps of "① precursor mixing + ② thermal annealing," simplifying the complex subsequent steps of loading nanoparticles onto conductive carbon powder using secondary loading. This results in a high-loading noble metal ordered alloy catalyst that can be easily synthesized at the gram scale. This invention solves the problem of catalyst particle size enlargement during high-temperature ordering and achieves high metal loading. Simultaneously, this invention increases the feed ratio by 10 times compared to previous methods, enabling successful catalyst synthesis at the gram scale and facilitating large-scale production.

[0009] The technical solution of this invention is as follows:

[0010] A mass-producible carbon-supported noble metal ordered alloy electrocatalyst, comprising a carbon support and small-sized noble metal ordered alloy nanoparticles supported on the support; the alloy loading is 20wt% to 90wt%; the average particle size of the noble metal ordered alloy nanoparticles is 1 to 10 nm.

[0011] The ordered noble metal alloy comprises an alloy consisting of a noble metal and at least one different transition metal M;

[0012] The precious metal is platinum, palladium, iridium, rhodium, or ruthenium;

[0013] The transition metal M is one or more of the following: iron, cobalt, nickel, copper, manganese, zinc, gallium, platinum, palladium, iridium, rhodium, and ruthenium.

[0014] In ordered alloys, noble metal atoms are arranged in a periodic order, and transition metal atoms inserted into the array of noble metal atoms also exhibit a periodic order.

[0015] The method for preparing the mass-producible carbon-supported noble metal ordered alloy electrocatalyst includes the following steps:

[0016] (1) The organic noble metal salt precursor, the transition metal M salt precursor and the carbon support are added to the mixed solvent and mixed. The mixture is ultrasonically stirred for 20 to 40 minutes, dried and ground to obtain a powder sample for later use.

[0017] The mixed solvent consists of anhydrous ethanol / deionized water; each 10 ml of the mixed solvent contains 0.01 mmol to 0.05 mmol of organic noble metal salt precursor, 0.001 mmol to 0.5 mmol of transition metal M salt precursor, and 1 mg to 10 mg of carbon support.

[0018] The mass ratio of the organic noble metal salt precursor to the carbon support is 1:1 to 40:1; the molar ratio of the organic noble metal salt precursor to the transition metal M salt precursor is 1:10 to 10:1.

[0019] (2) The powder sample above is transferred to a high-pressure furnace, heated to 500℃~1500℃, annealed in an inert atmosphere for 0.5h~48h, and after cooling to room temperature, the high loading of noble metal ordered alloy electrocatalysts of different components can be obtained.

[0020] The pressure of the inert atmosphere is 0.1 MPa to 50 MPa higher than the standard atmospheric pressure and the standard atmospheric pressure in a confined space;

[0021] As the pressure of the inert gas increases, the alloy particle size of the catalyst tends to decrease.

[0022] The precursor of the organic noble metal salt is acetylacetone salt.

[0023] The precursor of the transition metal M salt is an acetylacetone salt, nitrate, or chloride salt.

[0024] The carbon support is one of carbon black (acetylene black, Vulcan XC-72R and Ketjen black), carbon nanotubes, mesoporous carbon, carbon aerogel, and graphene, preferably Ketjen black.

[0025] The volume ratio of anhydrous ethanol to deionized water in the mixed solvent is 1:1.

[0026] The method for drying the mixed solution in step one is rotary evaporation solvent drying or forced-air oven drying. After drying, the solid powder is ground for 5 to 10 minutes.

[0027] The heat treatment annealing temperature is preferably 600℃~800℃, and the heat treatment inert atmosphere pressure is preferably 0.1MPa~10MPa higher than standard atmospheric pressure and the standard atmospheric pressure in a confined space.

[0028] The inert gas is argon or nitrogen.

[0029] In step (2), the heating rate is 1℃ / min to 50℃ / min, and the annealing time is preferably 1h to 24h.

[0030] The catalyst described herein can be used, but is not limited to, in proton exchange membrane fuel cells as an electrocatalyst for membrane electrodes. Due to its ability to be mass-produced with high loading of noble metal ordered alloy electrocatalysts, it can solve the problems of complex processes, catalyst costs, and activity and durability during application in the actual production of high loading of noble metal ordered alloy catalysts.

[0031] The essential features of this invention are:

[0032] This invention provides a mass-producible carbon-supported noble metal ordered alloy electrocatalyst with a small particle size and a high metal loading. The catalyst preparation method primarily uses carbon as a support and organic noble metal salts and transition metal salts M as precursors. Through thermal decomposition and reduction, noble metal-M-based alloy clusters loaded on the carbon support are initially obtained. These alloy clusters are then subjected to high-temperature calcination under pressure in an inert atmosphere for a period of time to achieve the preparation of a high-loading, ultra-small noble metal ordered alloy. This preparation method is simple, widely applicable, and can easily achieve large-scale mass production of high-loading ordered alloy catalysts. Furthermore, the presence of pressure effectively inhibits the sintering and growth of noble metal-M nanoparticles during the high-temperature ordering process, enabling the preparation of noble metal-M-based ordered alloys with a size smaller than 10 nm. This has significant scientific and engineering implications for improving catalyst stability.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] (1) The pressure-assisted synthesis method combines pressure with high-temperature thermal annealing. Under the action of pressure, the high-temperature annealing ensures that the noble metal-M-based alloy is ordered while limiting the size of the nanoparticles, making the nanoparticles more uniform. In the existing synthesis methods, some auxiliary reagents or template materials are usually added, and some relatively cumbersome steps are required to achieve similar effects. Furthermore, by applying appropriate pressure and high temperature to synthesize small-sized noble metal ordered alloy catalysts, the activity and stability of the catalyst can be significantly improved.

[0035] (2) The organic matter in the reduced metal salt precursor is used as a carbon matrix to load ordered alloy nanoparticles with carbon black, resulting in a catalyst with a high metal loading. This leads to lower mass transfer resistance in the membrane electrode assembly (MEA) of fuel cells and significantly improves the utilization rate of precious metals, resulting in higher effective catalytic performance with a half-wave potential as high as 0.9356 V and a mass activity as high as 0.58 A mg. Pt -1 After 30,000 cycles of stability testing, the mass activity decreased by only 8%.

[0036] (3) This preparation method can directly synthesize carbon-supported high-loading noble metal ordered alloy catalysts in one step, requiring only relatively low pressure and temperature. It can easily achieve a pressure 0.1 MPa above standard atmospheric pressure and standard atmospheric pressure in a closed space, and can easily prepare ordered alloys at a low temperature of 650℃. This is the first time a pressure-assisted method has been used in the prior art. Furthermore, compared to other methods that achieve ordering at around 1000℃, this invention is more practical and has greater potential for large-scale production considering energy conservation and emission reduction. In summary, the method of this invention has advantages such as simple preparation process, universality, and no complex pretreatment processes or the addition of other chemical substances, making it suitable for large-scale production and giving it broader application prospects and engineering significance in commercial production. Attached Figure Description

[0037] Figure 1 This is a low-magnification transmission electron microscope image of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1.

[0038] Figure 2 This is a high-magnification transmission electron microscope image of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1.

[0039] Figure 3 This is a particle size distribution chart of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1.

[0040] Figure 4 This is an HRTEM image of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1.

[0041] Figure 5 This is an atomic intensity distribution diagram of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1;

[0042] Figure 6 This is the XRD pattern of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1.

[0043] Figure 7 EDS energy spectrum of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1;

[0044] Figure 8 LSV curve of the mass-producible carbon-supported PtCo ordered alloy catalyst obtained in Example 1;

[0045] Figure 9 Example diagram of gram-scale production of the carbon-supported PtCo ordered alloy catalyst obtained in Example 1. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and should not be construed as limiting the invention.

[0047] First, the present invention provides a mass-producible carbon-supported noble metal ordered alloy electrocatalyst, which includes a carbon support and small-sized noble metal ordered alloy nanoparticles supported on the support. The noble metal ordered alloy contains a noble metal and at least one different transition metal M. The average particle size of the noble metal alloy nanoparticles is no greater than 10 nm, and the metal loading is 20% to 90%.

[0048] Wherein, the precious metal is one of platinum, palladium, iridium, rhodium, and ruthenium, the transition metal M is at least one of iron, cobalt, nickel, copper, manganese, zinc, gallium, platinum, palladium, iridium, rhodium, and ruthenium, and the ordered precious metal alloy is at least a binary ordered precious metal alloy, which can be understood as a binary, ternary, quaternary, pentagonal, or even a multi-element ordered precious metal alloy.

[0049] Specifically, taking Pt as a noble metal and Co as a transition metal as an example, Figure 1 The low-magnification transmission morphology of the mass-producible PtCo / C catalyst prepared according to this invention is shown. Figure 1As can be seen, PtCo nanoparticles are uniformly distributed and assembled on the surface of the carbon support, without exhibiting segregation or agglomeration. Figure 2 Its high-magnification transmission morphology image is composed of Figure 2 It can be seen that the PtCo / C catalyst has a relatively high metal loading; and it can obtain, for example Figure 3 The particle size distribution chart shows PtCo nanoparticles with an average particle size of 3.2 nm. Figure 4 Its high-resolution transmission image reveals the lattice fringes of the ordered alloy of PtCo nanoparticles. Figure 5 The image shows the atomic intensity distribution, illustrating the ordered arrangement of Pt and Co atoms; similarly, through... Figure 6 The XRD pattern confirmed the synthesis of an ordered PtCo alloy, exhibiting superlattice diffraction peaks at 22° and 32°; through... Figure 7 Energy-dispersive X-ray spectroscopy revealed that the catalyst had a high metal loading and Pt loading; further tests were conducted on its performance. Figure 8 The synthesized mass-produced catalyst exhibits excellent cathodic oxygen reduction performance; and through Figure 9 As we can see, we can successfully synthesize gram-scale catalysts in the laboratory stage.

[0050] On the other hand, the present invention further provides a method for preparing the above-mentioned mass-producible carbon-supported noble metal ordered alloy electrocatalyst, taking PtCo alloy as an example, including the following steps: Step 1, dissolve the Pt metal salt precursor and the transition metal Co metal salt precursor in a mixed solvent of anhydrous ethanol / deionized water, add the carbon support and mix thoroughly, ultrasonically stir for 20-40 minutes to completely dissolve the metal salt precursor, and obtain a mixed solution of metal salt precursor and carbon support. Dry the mixed solution by rotary evaporation and grind thoroughly to ensure that the metal salt precursor and carbon support are well integrated. The carrier is uniformly mixed and coated onto the carrier; in step two, the powder sample after being fully ground is transferred to a high-pressure furnace for uniform annealing, and ordered and annealed under an inert atmosphere at a specific temperature and pressure (wherein, the purpose of treating the nanoparticles in an inert gas is to act as a protective atmosphere to allow the nanoparticles to grow uniformly, and annealing is carried out at high temperature and pressure. Under the condition that conventional high temperature is used to order the particles, pressure is added to limit the particle size growth under high temperature annealing and to make them uniform). After cooling to room temperature, the mass-producible PtCo ordered alloy catalyst can be obtained.

[0051] Example 1

[0052] A method for preparing a mass-producible carbon-supported PtCo ordered alloy electrocatalyst, comprising the following steps:

[0053] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0254 mmol (6.6 mg) cobalt acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve the metal salt precursor, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0054] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C for 5 hours in a nitrogen atmosphere at a pressure 0.1 MPa higher than the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0055] Figure 1 The image shown is a low-magnification transmission electron microscope image of a mass-producible PtCo ordered alloy catalyst. It shows that the overall morphology of the catalyst consists of nanoparticles supported on a carbon support. The nanoparticles are uniformly loaded onto the carbon support without obvious agglomeration. It also shows that its high loading capacity can greatly improve the utilization rate of Pt metal and enable the catalyst to have higher effective catalytic performance in applications.

[0056] Figure 2 The image shown is a high-magnification transmission electron microscope (TEM) image of a mass-producible PtCo alloy catalyst, demonstrating that the catalyst as a whole consists of uniformly sized nanoparticles supported on carbon powder, and is combined with... Figure 3 The particle size distribution chart shows that the average particle size of the nanoparticles is 3.20 nm. Such a small particle size allows the catalyst to have a larger electrochemical active surface area, which greatly increases the exposure of active sites and is conducive to demonstrating its high activity.

[0057] Figure 4 The image shown is an HRTEM image of a mass-producible PtCo ordered alloy catalyst, which shows that the individual nanoparticles have ordered lattice stripes, indicating that the catalyst is composed of ordered alloy nanoparticles and has the characteristics of ordered alloys. This makes the nanoparticles have a more stable structure, which is beneficial to the catalyst having better stability.

[0058] Figure 5 The figure shows the atomic intensity distribution of the mass-producible PtCo ordered alloy catalyst. The figure shows the ordered arrangement of Pt and Co atoms, which further proves that the present invention can successfully synthesize PtCo intermetallic compounds with ordered phase structure.

[0059] Figure 6The XRD pattern of the mass-producible PtCo ordered alloy catalyst is shown. Its main peak matches the standard XRD card of PtCo alloy, and there are superlattice peaks near 25° and 33°, which proves that the preparation method successfully synthesized ordered PtCo alloy and further proves the feasibility of this method.

[0060] Figure 7 The image shows the energy-dispersive X-ray spectrum of a mass-producible PtCo ordered alloy catalyst. It can be seen that the Pt and Co element content ratio is the same as the feed ratio, and the catalyst has a high metal loading and Pt loading, proving that the PtCo alloy catalyst was successfully synthesized by a combination of high temperature and pressure.

[0061] Under the same conditions, mass production of large quantities of materials yields products of the same quality:

[0062] (1) Mix 1.5 mmol (600.0 mg) platinum acetylacetonate, 1.5 mmol (396.0 mg) cobalt acetylacetonate and 300.0 mg Ketjen black, add 300 ml anhydrous ethanol and 300 ml deionized water to dissolve the metal salt precursor, sonicate for 120 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0063] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C in a nitrogen atmosphere at a pressure 0.1 MPa higher than the standard atmospheric pressure. The temperature was maintained for 5 hours at a rate of 10°C / min. After that, it was naturally cooled to room temperature to obtain about 1.8 g of black product, which is the sample obtained.

[0064] Figure 8 The figure shows the polarization curves of a mass-producible PtCo ordered alloy catalyst and a commercial Pt / C catalyst. The figures display the polarization curves of the PtCo ordered alloy catalyst after 30,000 cycles of initial and accelerated degradation testing, and the polarization curves of 60% commercial Pt / C after 10,000 cycles of initial and accelerated degradation testing, respectively. All electrochemical experiments were conducted on a CHI 760E electrochemical workstation (Shanghai Chenhua) using a conventional three-electrode system at room temperature. A glassy carbon electrode (GCE, 5 mm diameter, 0.196 cm²) was used. 2 The working electrode was α, Ag / AgCl was the reference electrode, a platinum sheet was the counter electrode, and 0.1M HClO4 was the electrolyte. The catalyst was prepared to a concentration of 2 mg / mL. -1 The uniform ink droplet loading on the platinum-carbon electrode was 12.75 μg cm⁻¹. -2The performance of the PtCo ordered alloy catalyst, used as a catalyst for the oxygen reduction reaction at the cathode of a fuel cell, was tested. The kinetic current was calculated using the limiting diffusion current and the current corresponding to 0.9 V, from which the mass activity was obtained. The mass activity of the PtCo ordered alloy catalyst was 0.58 A mg Pt. -1 60% commercial Pt / C is 0.16 mg Pt -1 Furthermore, by calculating the half-wave potential loss before and after the accelerated degradation test (as shown in the figure), it can be seen that the PtCo ordered alloy catalyst has good stability compared with commercial Pt / C. The mass-produced PtCo ordered alloy catalyst only lost 8.7% of its mass activity after 30,000 cycles of stability testing, while 60% of commercial Pt / C lost 46.3% after only 10,000 cycles.

[0065] Figure 9 The image shown is a physical photograph of a mass-producible PtCo ordered alloy catalyst, demonstrating that the present invention can achieve mass production and meet the catalyst needs of actual social production.

[0066] Example 2

[0067] A method for preparing a mass-producible carbon-supported PtNi ordered alloy electrocatalyst, comprising the following steps:

[0068] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0254 mmol (6.6 mg) nickel acetylacetonate and 5.0 mg Vulcan XC-72R, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve the metal salt precursor, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0069] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C for 12 hours in a nitrogen atmosphere at a pressure 0.1 MPa higher than the standard atmospheric pressure. The temperature was increased at a rate of 10°C / min. The temperature was then maintained at that temperature for 12 hours. After that, the temperature was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0070] Example 3

[0071] A method for preparing a mass-producible carbon-supported PtFe ordered alloy electrocatalyst, comprising the following steps:

[0072] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0254 mmol (9.0 mg) iron acetylacetonate and 5.0 mg acetylene black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve the metal salt precursor, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0073] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 850°C for 2 hours in a nitrogen atmosphere at a pressure 0.5 MPa higher than the standard atmospheric pressure. Then the temperature was lowered to 650°C for 5 hours at a cooling rate of 10°C / min. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0074] Example 4

[0075] A mass-producible carbon-supported PtCo 0.8 Mn 0.2 The preparation method of ordered alloy electrocatalysts includes the following steps:

[0076] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.02 mmol (5.3 mg) cobalt acetylacetonate, 0.005 mmol (1.3 mg) cobalt acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve the metal salt precursor, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0077] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 700°C for 2 hours in a nitrogen atmosphere at a pressure 0.1 MPa higher than the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0078] Example 5

[0079] A method for preparing a mass-producible carbon-supported Pt2CoNi ordered alloy electrocatalyst, comprising the following steps:

[0080] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.013 mmol (3.3 mg) cobalt acetylacetonate, 0.013 mmol (3.3 mg) cobalt acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve the metal salt precursor, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0081] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C in a nitrogen atmosphere at a rate of 10°C / min above the standard atmospheric pressure for 5 hours. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0082] Example 6

[0083] A method for preparing a mass-producible carbon-supported PtZn ordered alloy electrocatalyst, comprising the following steps:

[0084] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0254 mmol (6.6 mg) zinc acetylacetonate and 5.0 mg carbon nanotubes, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0085] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C for 1 hour in an argon atmosphere at a pressure 1 MPa higher than the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0086] Example 7

[0087] A method for preparing a mass-producible carbon-supported PtCu ordered alloy electrocatalyst, comprising the following steps:

[0088] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0254 mmol (6.5 mg) copper acetylacetonate and 5.0 mg mesoporous carbon, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0089] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 700°C for 1 hour in an argon atmosphere at a pressure 1 MPa higher than the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0090] Example 8

[0091] A method for preparing a mass-producible carbon-supported PtMn ordered alloy electrocatalyst, comprising the following steps:

[0092] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0254 mmol (6.6 mg) manganese acetylacetonate and 5.0 mg graphene, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0093] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 700°C for 1 hour in an argon atmosphere at a rate of 10°C / min above the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0094] Example 9

[0095] A method for preparing a mass-producible carbon-supported IrCo alloy electrocatalyst, comprising the following steps:

[0096] (1) Mix 0.0254 mmol (10.0 mg) iridium acetylacetone, 0.0254 mmol (6.7 mg) nickel acetylacetone and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0097] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C for 5 hours in an argon atmosphere at a rate of 10°C / min above the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0098] Example 10

[0099] A method for preparing a mass-producible carbon-supported RhCo ordered alloy electrocatalyst, comprising the following steps:

[0100] (1) Mix 0.0254 mmol (10.0 mg) rhodium acetylacetone, 0.0254 mmol (6.7 mg) nickel acetylacetone and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0101] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 1500℃ in an argon atmosphere at a rate of 10℃ / min above the standard atmospheric pressure. The temperature was held for 1 hour and then naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0102] Example 11

[0103] A method for preparing a mass-producible carbon-supported PdCo ordered alloy electrocatalyst, comprising the following steps:

[0104] (1) Mix 0.0254 mmol (8.9 mg) palladium acetylacetone, 0.0254 mmol (6.7 mg) nickel acetylacetone and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0105] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 500°C for 2 hours in an argon atmosphere at a rate of 10°C / min above the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0106] Example 12

[0107] A method for preparing a mass-producible carbon-supported Pt2RuCo ordered alloy electrocatalyst, comprising the following steps:

[0108] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0127 mmol (5.0 mg) ruthenium acetylacetonate, 0.0127 mmol (3.3 mg) cobalt acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0109] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 750°C for 3 hours in an argon atmosphere at a rate of 10°C / min above the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0110] Example 13

[0111] A method for preparing a mass-producible carbon-supported Pt3NiCoFe ordered alloy electrocatalyst, comprising the following steps:

[0112] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0085 mmol (2.3 mg) nickel acetylacetonate, 0.0085 mmol (2.2 mg) cobalt acetylacetonate, 0.0085 mmol (3.0 mg) iron acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0113] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 700°C in an argon atmosphere at a rate of 10°C / min above the standard atmospheric pressure. The temperature was held for 5 hours and then naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0114] Example 14

[0115] A method for preparing a mass-producible carbon-supported Pt4NiCoFeZn alloy electrocatalyst, comprising the following steps:

[0116] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0064 mmol (1.7 mg) nickel acetylacetonate, 0.0064 mmol (1.7 mg) cobalt acetylacetonate, 0.0064 mmol (2.3 mg) iron acetylacetonate, 0.0064 mmol (1.7 mg) zinc acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0117] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C for 5 hours in a nitrogen atmosphere at a pressure 10 MPa higher than the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0118] Example 15

[0119] A method for preparing a mass-producible carbon-supported Pt4NiCoFeCu alloy electrocatalyst, comprising the following steps:

[0120] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0064 mmol (1.7 mg) nickel acetylacetonate, 0.0064 mmol (1.7 mg) cobalt acetylacetonate, 0.0064 mmol (2.3 mg) iron acetylacetonate, 0.0064 mmol (1.7 mg) copper acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0121] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 700°C for 5 hours in an argon atmosphere at a rate of 10°C / min above the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0122] Example 16

[0123] A method for preparing a mass-producible carbon-supported Pt5NiCoFeZnCu alloy electrocatalyst, comprising the following steps:

[0124] (1) Mix 0.0254 mmol (10.0 mg) platinum acetylacetonate, 0.0051 mmol (1.4 mg) nickel acetylacetonate, 0.0051 mmol (1.3 mg) cobalt acetylacetonate, 0.0051 mmol (1.8 mg) iron acetylacetonate, 0.0051 mmol (1.3 mg) zinc acetylacetonate, 0.0051 mmol (1.3 mg) copper acetylacetonate and 5.0 mg Ketjen black, add 5 ml anhydrous ethanol and 5 ml deionized water to dissolve, sonicate for 30 min, mix and dissolve thoroughly, dry with a rotary evaporator, scrape the solid sample from the eggplant flask and grind it thoroughly for 10 minutes to mix the metal salt precursor with the carbon support, put it in a porcelain boat and wrap it with copper foil for later use;

[0125] (2) Then the ceramic boat was placed in a high-pressure furnace and heated to 650°C for 5 hours at a heating rate of 10°C / min in an argon atmosphere 1 MPa higher than the standard atmospheric pressure. After that, it was naturally cooled to room temperature to obtain a black product. The sample was then dried at room temperature.

[0126] As can be seen from the above embodiments, the present invention further improves the preparation method by combining pressure-assisted regulation with traditional high-temperature annealing. This achieves the goal of adding pressure to limit particle size growth and homogenize the particles under the condition of traditional high temperature to make them ordered, allowing pressure assistance and high-temperature annealing to work together. This provides a very simple and quick way to prepare mass-producible carbon-supported noble metal ordered alloy electrocatalysts, thereby further reducing their cost, improving the activity and stability of the catalyst, and enabling its application in actual large-scale production.

[0127] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

[0128] Matters not covered in this invention are common knowledge.

Claims

1. A mass-producible carbon-supported noble metal ordered alloy electrocatalyst, characterized in that... The electrocatalyst comprises a carbon support and small-sized noble metal ordered alloy nanoparticles supported on the support; the alloy loading is 20wt% to 90wt%; the average particle size of the noble metal ordered alloy nanoparticles is 1 to 10 nm. The ordered noble metal alloy comprises an alloy consisting of a noble metal and at least one different transition metal M; The precious metal is platinum, palladium, iridium, rhodium, or ruthenium; The transition metal M is one or more of iron, cobalt, nickel, copper, manganese, zinc, gallium, platinum, palladium, iridium, rhodium, and ruthenium; the carbon support is one of carbon black (acetylene black, Vulcan XC-72R, or Ketjen black), carbon nanotubes, mesoporous carbon, carbon aerogel, and graphene.

2. The mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 1, characterized in that the noble metal atoms in the ordered alloy are arranged in a periodic order, and the transition metal atoms inserted into the noble metal atom array also exhibit a periodic order.

3. The method for preparing the mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 1. Its characteristic is that the method includes the following steps: (1) The organic noble metal salt precursor, the transition metal M salt precursor and the carbon support are added to the mixed solvent and mixed. The mixture is ultrasonically stirred for 20 to 40 minutes, dried and ground to obtain a powder sample for later use. in, The mixed solvent consists of anhydrous ethanol / deionized water; each 10 ml of mixed solvent contains 0.01 mmol to 0.05 mmol of organic noble metal salt precursor, 0.001 mmol to 0.5 mmol of transition metal M salt precursor, and 1 mg to 10 mg of carbon support. The mass ratio of the organic noble metal salt precursor to the carbon support is 1:1 to 40:1; the molar ratio of the organic noble metal salt precursor to the transition metal M salt precursor is 1:10 to 10:

1. (2) The powder sample was transferred to a high-pressure furnace and heated to 500℃~1500℃. It was annealed in an inert atmosphere for 0.5h~48h. After cooling to room temperature, the noble metal ordered alloy electrocatalyst was obtained. The pressure of the inert atmosphere is 0.1 MPa to 50 MPa higher than the standard atmospheric pressure and the standard atmospheric pressure in a confined space.

4. The method for preparing the mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 3, characterized in that the alloy particle size of the catalyst decreases as the pressure of the inert gas increases.

5. The method for preparing the mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 3, characterized in that the organic noble metal salt precursor is acetylacetone salt; the transition metal M metal salt precursor is acetylacetone salt, nitrate or chloride salt; and the inert gas is argon or nitrogen.

6. The method for preparing the mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 3, characterized in that the volume ratio of anhydrous ethanol to deionized water in the mixed solvent is 1:1; The method for drying the mixed solution in step one is rotary evaporation solvent drying or forced-air oven drying. After drying, the solid powder is ground for 5 to 10 minutes.

7. The method for preparing the mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 3, characterized in that the heat treatment annealing temperature is preferably 600℃~800℃, and the heat treatment inert atmosphere pressure is preferably 0.1MPa~10MPa higher than the standard atmospheric pressure; In step (2), the heating rate is 1℃ / min to 50℃ / min, and the annealing time is preferably 1h to 24h.

8. The application of the mass-producible carbon-supported noble metal ordered alloy electrocatalyst as described in claim 1, characterized in that it is used as an electrocatalyst for the membrane electrode in a proton exchange membrane fuel cell.

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