Carbon-supported platinum-cobalt ordered alloy catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of battery catalysts, and discloses a carbon-supported platinum-cobalt ordered alloy catalyst and a preparation method and application thereof. The carbon-loaded platinum-cobalt ordered alloy catalyst comprises a porous carbon carrier and an active component loaded on the porous carbon carrier, the active components comprise platinum and cobalt, and the platinum and the cobalt form a face-centered cubic structure with ordered atom arrangement. The carbon-supported platinum-cobalt ordered alloy catalyst has the advantages of better catalytic efficiency, stability and durability, and is beneficial to further improvement of the performance of the fuel cell.

Description

Technical Field

[0001] The present invention belongs to the technical field of battery catalysts, and particularly relates to a carbon-supported platinum-cobalt ordered alloy catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] Driven by the dual imperatives of energy transition and environmental protection, fuel cell technology has attracted much attention due to its high efficiency and cleanliness. As the core component of fuel cells, the performance of the catalyst directly affects the overall efficiency of the battery. Currently, although platinum-carbon catalysts are widely used, due to the high cost and scarce resources of platinum, seeking alternative or improved solutions has become a research hotspot. Platinum-cobalt alloy catalysts, with their relatively excellent catalytic activity and relatively low cost, have gradually become the focus of research. However, the platinum-cobalt alloy catalysts in the prior art still have problems that need to be further improved in terms of catalytic efficiency, stability, and durability. Solving these problems remains a challenge for the industry.

[0003] Therefore, there is an urgent need to provide a catalyst with better catalytic efficiency, stability, and durability. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above prior art. For this purpose, the present invention provides a carbon-supported platinum-cobalt ordered alloy catalyst, a preparation method thereof, and an application thereof. The carbon-supported platinum-cobalt ordered alloy catalyst of the present invention has the advantages of better catalytic efficiency, stability, and durability, which is beneficial to further improving the performance of fuel cells.

[0005] The preparation method of the present invention mainly uses nano-zinc oxide and cobalt salt to induce the self-assembly of dopamine hydrochloride in an alkaline buffer. After high-temperature carbonization, pickling, water washing, and drying, a porous carbon carrier is formed. Then, platinum salt is dispersed in the ethylene glycol / aqueous solution of the porous carbon carrier, and oil bath reduction and high-temperature annealing are carried out to finally obtain a platinum-cobalt ordered alloy catalyst with a unique structure in which platinum and cobalt form a face-centered cubic structure with an ordered atomic arrangement.

[0006] The first aspect of the present invention provides a carbon-supported platinum-cobalt ordered alloy catalyst.

[0007] A carbon-supported platinum-cobalt ordered alloy catalyst, comprising a porous carbon carrier and an active component supported on the porous carbon carrier; The active component includes platinum and cobalt, and the platinum and cobalt form a face-centered cubic structure with an ordered atomic arrangement.

[0008] Preferably, by mass percentage, the porous carbon carrier is 60 - 80%, platinum is 10% - 20%, and cobalt is 5% - 20%.

[0009] Preferably, the platinum and cobalt exist in the form of platinum-cobalt alloy particles and are uniformly distributed on the porous carbon carrier.

[0010] Preferably, the porous carbon support in the carbon-supported platinum-cobalt ordered alloy catalyst also contains nitrogen. The content of nitrogen accounts for 1-8% of the mass of the carbon-supported platinum-cobalt ordered alloy catalyst. For example, it is 7.3%.

[0011] Preferably, the particle size of the platinum-cobalt alloy particles is 1-8 nm, and more preferably 2-5 nm.

[0012] The second aspect of the present invention provides a method for preparing a carbon-supported platinum-cobalt ordered alloy catalyst.

[0013] A method for preparing a carbon-supported platinum-cobalt ordered alloy catalyst includes the following steps: (1) Dispersing zinc oxide in a solvent, adding a cobalt metal salt, a basic buffer, and dopamine hydrochloride and mixing to obtain self-assembled polydopamine nanospheres. After carbonizing the self-assembled polydopamine nanospheres, pickling and drying are performed to obtain a porous carbon support; (2) Dispersing the porous carbon support in an ethylene glycol / water solution, adding a platinum salt, and ultrasonically dispersing and mixing to obtain a mixed solution. Heating in an oil bath and performing solid-liquid separation to obtain a black powder; (3) Performing annealing treatment under a protective gas atmosphere to obtain the carbon-supported platinum-cobalt ordered alloy catalyst.

[0014] Preferably, in step (1), the mass ratio of zinc oxide, cobalt metal salt, and dopamine hydrochloride is 80-90:0.05-10:10-20, and more preferably 80-90:0.05-1:10-20.

[0015] Preferably, in step (1), the zinc oxide can also be nano-zinc oxide, for example, zinc oxide with a particle size of 50-200 nanometers.

[0016] Preferably, in step (1), the solvent is deionized water.

[0017] Preferably, in step (1), the cobalt metal salt is selected from at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.

[0018] Preferably, the cobalt metal salt and dopamine hydrochloride are added in the form of a solution.

[0019] Preferably, the concentration of the cobalt metal salt solution is 1-100 mg / mL, and more preferably 10-50 mg / mL.

[0020] Preferably, the concentration of the dopamine hydrochloride solution is 1-50 mg / mL, and more preferably 5-30 mg / mL.

[0021] Preferably, in step (1), zinc oxide is dispersed in a solvent, and the pH of the mixture formed by adding a cobalt metal salt, an alkaline buffer, and dopamine hydrochloride is 7-14. The dosage of the alkaline buffer is limited by the pH of 7-14.

[0022] Preferably, in step (1), the alkaline buffer is selected from at least one of ammonia water and tris(hydroxymethyl)aminomethane hydrochloride.

[0023] Preferably, in step (1), the mixing is carried out by stirring, and the mixing time is 3-24 h, further preferably 10-24 h.

[0024] The mixing is carried out by magnetic stirring, and the rotation speed at room temperature is 200-1000 revolutions per minute.

[0025] Preferably, in step (1), after the self-assembled polydopamine nanospheres are washed, filtered by suction, and freeze-dried, they are placed in a tube furnace and carbonized under the condition of a protective gas atmosphere (such as argon).

[0026] Preferably, in step (1), the temperature of the carbonization is 500-700 °C, and more preferably 600-650 °C.

[0027] Preferably, in step (1), the time of the carbonization is 1-3 hours, and more preferably 2-2.5 hours.

[0028] Preferably, in step (2), in the ethylene glycol / water solution, the volume ratio of water to ethylene glycol is 1:1-6, and more preferably 1:4.

[0029] Preferably, in step (2), the platinum salt includes chloroplatinic acid.

[0030] Preferably, in step (2), the ultrasonic time of the ultrasonic dispersion mixing is 1-5 hours.

[0031] Preferably, in step (2), the solid-liquid separation includes the processes of suction filtration and freeze-drying.

[0032] Preferably, in step (2), the temperature of heating in the oil bath is 200-230 °C, and more preferably 220-230 °C.

[0033] Preferably, in step (3), the temperature of the annealing is 500-900 °C, and more preferably 600-700 °C.

[0034] Preferably, after step (3), step (4) is further included. Step (4) includes pickling, suction filtration, and drying of the carbon-supported platinum-cobalt ordered alloy catalyst obtained by the annealing treatment to obtain a pure carbon-supported platinum-cobalt ordered alloy catalyst.

[0035] Preferably, the acidic cleaning solution used for pickling is selected from at least one of perchloric acid, hydrochloric acid, and sulfuric acid. For example, it is a 0.5-1 M perchloric acid solution.

[0036] The third aspect of the present invention provides an application of a carbon-supported platinum-cobalt ordered alloy catalyst.

[0037] A fuel cell includes an anode and a cathode, and the cathode includes the above-mentioned carbon-supported platinum-cobalt ordered alloy catalyst.

[0038] The application of the above-mentioned carbon-supported platinum-cobalt ordered alloy catalyst in the oxygen reduction reaction.

[0039] Preferably, the oxygen reduction reaction includes an acidic oxygen reduction reaction.

[0040] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The preparation method of the present invention uses less platinum raw materials, reducing the economic cost of the catalyst; at the same time, water and ethylene glycol system are used as reducing agents, and argon is used as a protective gas. The whole process is simple to operate, significantly reducing the synthesis cost of the catalyst; the present invention separates the reduction step and the ordering step of platinum metal, reduces it through ethylene glycol at low temperature, avoiding the use of high-temperature reduction atmosphere, making the synthesis process safer, and at the same time further reducing the particle size of platinum metal. While reducing the synthesis cost, relatively good electrochemical performance can be obtained.

[0041] (2) The platinum metal outer skin of the present invention protects platinum-cobalt inside, improving the stability of the catalyst in acidic electrolyte; at the same time, the cobalt-nitrogen-carbon sites anchor cobalt nanoparticles through strong metal-metal interactions to prevent their agglomeration, enabling the catalyst to work continuously and stably. This type of material provides certain reference value for the controllable synthesis of ordered alloys. Description of the Drawings

[0042] Figure 1 It is the linear voltammetric scanning curve of the catalysts prepared in Examples 1-2 and Comparative Examples 1-2 of the present invention; Figure 2 It is the linear voltammetric scanning curve of the catalyst in Example 1 of the present invention after accelerated durability test; Figure 3 It is the electrochemically stable mass activity diagram of the catalyst in Example 1 of the present invention; Figure 4 It is the XRD (X-ray diffraction) diagram of the catalysts in Examples 1-2 of the present invention; Figure 5 It is the SEM (scanning electron microscope) diagram of the catalyst in Example 1 of the present invention; Figure 6 It is the HR-TEM (high-resolution transmission electron microscopy) diagram of the catalyst in Example 1 of the present invention; Figure 7 This is the XPS (X-ray Photoelectron Spectroscopy) diagram of the catalyst in Example 1 of the present invention. Detailed implementation manners

[0043] To make the technical solutions of the present invention clearer and more understandable to those skilled in the art, the following examples are listed for illustration. It should be noted that the following examples do not limit the scope of protection required by the present invention.

[0044] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial channels or can be obtained by known existing methods.

[0045] The carbon-supported platinum-cobalt ordered alloy catalyst for the cathode of a fuel cell in the present invention is composed of a porous carbon support and active components. The active components are platinum and cobalt. By mass percentage, the porous carbon support is 60%-80%, platinum is 10%-20%, and cobalt is 5%-20%. The total mass of the carbon support, platinum, and cobalt is 100%. Platinum and cobalt have a face-centered cubic structure with an ordered atomic arrangement.

[0046] The preparation method of the carbon-supported platinum-cobalt ordered alloy catalyst of the present invention includes two major steps, that is, first, using the self-assembly of dopamine hydrochloride to synthesize porous carbon spheres by carbonization under an argon atmosphere; then using the obtained porous carbon support to load platinum onto the surface of the carbon spheres through ethylene glycol reduction and high-temperature annealing to obtain an alloy with an ordered platinum-cobalt structure, and preparing the carbon-supported platinum-cobalt ordered alloy catalyst (L10-PtCo / ZPDA).

[0047] Figure 1 This is the linear voltammetry scan curve of the catalysts prepared in Examples 1-2 and Comparative Examples 1-2 of the present invention; "Potential / V (vs. RHE)" represents the electrode potential with a reversible hydrogen electrode as the reference, and "Current density" represents the current density.

[0048] Figure 2 This is the linear voltammetry scan curve of the catalyst in Example 1 of the present invention after an accelerated durability test; "Potential / V (vs. RHE)" represents the electrode potential with a reversible hydrogen electrode as the reference, "Current density" represents the current density, and "Initial" represents the initial.

[0049] Figure 3 This is the electrochemical stability mass activity diagram of the catalyst in Example 1 of the present invention; "Initial" represents the initial, and "Mass Activity" represents the mass activity.

[0050] Figure 4XRD (X-ray diffraction) pattern of the catalyst in Examples 1-2 of the present invention; "Intensity" represents intensity, and "2Theta(degree)" represents diffraction angle 2θ (degree). "PDF#65-8969 CoPt" represents the PDF card of PtCo alloy numbered #65-8969, and "PDF#65-8968 CoPt" represents the PDF card of PtCo alloy numbered #65-8968.

[0051] Figure 5 SEM (scanning electron microscope) image of the catalyst in Example 1 of the present invention.

[0052] Figure 6 HR-TEM (high-resolution transmission electron microscopy) image of the catalyst in Example 1 of the present invention; "d" represents diameter Figure 7 XPS (X-ray photoelectron spectroscopy) image of the catalyst in Example 1 of the present invention. "Intensity" represents intensity, and "Binding Energy" represents binding energy. Example 1

[0053] A preparation method of a carbon-supported platinum-cobalt ordered alloy catalyst, comprising the following steps: (1) Weigh 100 mg of nano-zinc oxide powder into a flat-bottomed flask, add 200 mL of deionized water, and stir evenly to obtain a mixed solution; (2) Add 2.4 mL of tris(hydroxymethyl)aminomethane hydrochloride solution (1.5 M, pH = 8.5) and 200 μL of cobalt chloride hexahydrate solution (20 mg / mL) to the mixed solution in step (1), and stir for 10 minutes to mix evenly; (3) At room temperature, add 50 mL of hydrochloric acid dopamine solution (1 mg / mL, PDA) to the mixed solution obtained in step (2), stir for 24 hours, and fully react to obtain a mixed solution; (4) Filter, wash, and freeze-dry the mixed solution obtained in step (3) to obtain a blue-black solid powder; (5) Place the blue-black solid powder obtained in step (4) in a tube furnace, and calcine it at 700 °C (heating rate 8 °C / min) for 2 hours in an argon atmosphere to obtain a black powder; (6) At room temperature, disperse the black powder obtained in step (5) into 100 mL of 2 M sulfuric acid solution and stir for 4 hours to obtain a mixed suspension; (7) Filter, wash, and freeze-dry the mixed suspension obtained in step (6) to obtain a carbon support (ZPDA); (8) Weigh 20 mg of ZPDA and disperse it in 1 mL of chloroplatinic acid solution (10 mg / mL), add 1 mL of cobalt chloride hexahydrate solution (20 mg / mL), and add 16 mL of ethylene glycol (EG), then stir and mix evenly; (9) Ultrasonicate the mixed solution obtained in step (8) at 25 °C for 2 hours and stir for 18 hours; (10) Heat the mixed solution obtained in step (9) at 220 °C for 2 hours; (11) Filter, wash, and freeze-dry the product obtained in step (10) to obtain a black powder; (12) Place the black powder obtained in step (11) in a tube furnace under an argon protection atmosphere and calcine it at 700 °C for 1 hour (heating rate 5 °C / min); (13) Disperse the product obtained in step (12) in 100 mL of 1 M HClO4 solution and stir magnetically for 6 hours; (14) Filter, wash, and freeze-dry the product obtained in step (13) to obtain a carbon-supported platinum-cobalt ordered alloy catalyst (denoted as L10-PtCo / ZPDA).

[0054] The carbon-supported platinum-cobalt ordered alloy catalyst (referred to as the catalyst) prepared in Example 1 has excellent oxygen reduction performance. The half-wave potential of the linear voltammetry curve is 0.95 V vs. RHE and the limiting current density is 6 mA / cm 2 (as Figure 1 shown); after normalization, at 0.85 V, the mass activity of the catalyst is 7.41 A / mg Pt . The catalyst still maintains good catalytic ability after 70,000 accelerated durability tests, and its mass activity only decreases by 14.7%, showing excellent electrochemical stability (as Figure 2 and Figure 3 shown).

[0055] The scanning electron microscope results of the carbon-supported platinum-cobalt ordered alloy catalyst prepared in Example 1 (as Figure 5 shown) indicate that the carbon support is composed of porous nano-spheres with a particle size of 100 - 300 nm; the transmission electron microscope results of the carbon-supported platinum-cobalt ordered alloy catalyst prepared in Example 1 (as Figure 6 shown) indicate that the average particle size of the metal on the carbon support surface is 2.63 nm.

[0056] The XRD of the carbon-supported platinum-cobalt ordered alloy catalyst prepared in Example 1 (as Figure 4In the results (as shown), the diffraction peak position of platinum metal shifted positively, and characteristic peaks of structural ordering appeared, indicating that cobalt entered the face-centered cubic lattice of platinum, resulting in lattice contraction and forming a platinum-cobalt alloy phase. After high-temperature annealing, an ordering phase transformation occurred in the platinum-cobalt alloy.

[0057] The XPS results (as shown Figure 7 in) of the carbon-supported platinum-cobalt ordered alloy catalyst prepared in Example 1 showed that the platinum(IV) precursor was completely reduced to elemental Pt(0) or Pt 2+ . Example 2

[0058] A preparation method of a carbon-supported platinum-cobalt ordered alloy catalyst includes the following steps: (1) Weigh 100 mg of nano-zinc oxide powder into a flat-bottom flask, add 200 mL of deionized water, and stir evenly to obtain a mixed solution; (2) Add 2.4 mL of tris(hydroxymethyl)aminomethane hydrochloride solution (1.5 M, pH = 8.5) and 200 μL of cobalt(II) chloride hexahydrate solution (20 mg / mL) to the mixed solution in step (1), and stir for 10 minutes to mix evenly; (3) At room temperature, add 50 mL of hydrochloric acid dopamine solution (1 mg / mL) to the mixed solution obtained in step (2), and stir for 24 hours to fully react to obtain a mixed solution; (4) Filter, wash, and freeze-dry the mixed solution obtained in step (3) to obtain a blue-black solid powder; (5) Place the blue-black solid powder obtained in step (4) in a tube furnace, and calcine it at 700 °C (heating rate 8 °C / min) for 2 hours in an argon atmosphere to obtain a black powder; (6) At room temperature, disperse the black powder obtained in step (5) into 100 mL of 2 M sulfuric acid solution and stir for 4 hours to obtain a mixed suspension; (7) Filter, wash, and freeze-dry the mixed suspension obtained in step (6) to obtain a carbon support (ZPDA); (8) Weigh 20 mg of ZPDA and disperse it in 1 mL of chloroplatinic acid solution (10 mg / mL), add 1 mL of cobalt(II) chloride hexahydrate solution (20 mg / mL), and add 16 mL of ethylene glycol (EG) and stir to mix evenly; (9) Ultrasonic the mixed solution obtained in step (8) at 25 °C for 2 hours and stir for 18 hours; (10) Heat the mixed solution obtained in step (9) at 220 °C for 2 hours; (11) Filter, wash, and freeze-dry the product obtained in step (10) to obtain a black powder; (12) The black powder obtained in step (11) is calcined in a tubular furnace at 500 °C for 1 hour (heating rate: 5 °C / min) under an argon protection atmosphere; (13) The product obtained in step (12) is dispersed in 100 mL of 1 M HClO4 solution and magnetically stirred for 6 hours; (14) The product obtained in step (13) is filtered, washed, and freeze-dried to obtain a carbon-supported platinum-cobalt ordered alloy catalyst (denoted as L10-PtCo low / ZPDA).

[0059] The carbon-supported platinum-cobalt ordered alloy catalyst prepared in this Example 2 changes the ordered alloying annealing temperature, causing a metal phase change in the carbon-supported platinum-cobalt ordered alloy catalyst. From Figure 4 the XRD and Figure 1 results, it can be seen that the platinum-cobalt ordered alloy transforms from a high-temperature ordered phase to a low-temperature ordered phase. The alloy phase change has a great influence on the electrochemical performance of the catalyst; after the calcination temperature is lowered, the degree of order will decrease; a high degree of order results in good electrochemical performance. Comparative Example 1

[0060] A method for preparing a catalyst includes the following steps: (1) Weigh 20 mg of carbon powder (XC-72 carbon black) and disperse it in 1 mL of chloroplatinic acid solution (10 mg / mL), add 1 mL of cobalt chloride hexahydrate solution (20 mg / ml), add 16 mL of ethylene glycol (EG), and stir and mix evenly to obtain a mixed solution; (2) Ultrasonic the mixed solution obtained in step (1) at 25 °C for 2 hours and stir for 18 hours; (3) Heat the mixed solution obtained in step (2) at 220 °C for 2 hours; (4) Filter, wash, and freeze-dry the mixed solution obtained in step (3) to obtain a black powder; (5) Place the black powder obtained in step (4) in a tubular furnace at 550 °C for 2 hours under an argon protection atmosphere, and then calcine it at 800 °C for 1 hour (heating rate: 5 °C / min); (6) Disperse the product obtained in step (5) in 100 mL of 1 M HClO4 solution and magnetically stir for 6 hours; (7) Filter, wash, and freeze-dry the mixed solution obtained in step (6) to obtain L10-PtCo / C.

[0061] Comparative Example 2

[0062] A method for preparing a catalyst includes the following steps: (1)Weigh 100 mg of nano-zinc oxide powder into a flat-bottom flask, add 200 mL of deionized water, and stir evenly to obtain a mixed solution; (2)Add 2.4 mL of tris(hydroxymethyl)aminomethane hydrochloride solution (1.5 M, pH = 8.5) and 200 μL of cobalt(II) chloride hexahydrate solution (20 mg / mL) to the mixed solution in step (1), stir for 10 minutes, and mix evenly; (3)At room temperature, add 50 mL of dopamine hydrochloride solution (1 mg / mL) to the mixed solution obtained in step (2), stir for 24 hours, and react fully to obtain a mixed solution; (4)Filter, wash, and freeze-dry the mixed solution obtained in step (3) to obtain a blue-black solid powder; (5)Place the blue-black solid powder obtained in step (4) in a tube furnace, and calcine it at 900 °C (heating rate 3 °C / min) for 2 hours in an argon atmosphere to obtain a black powder; (6)At room temperature, disperse the black powder obtained in step (5) into 100 mL of 1 M sulfuric acid solution, and stir for 4 hours to obtain a mixed suspension; (7)Filter, wash, and freeze-dry the mixed suspension obtained in step (6) to obtain a carbon support (ZPDA); (8)Weigh 20 mg of ZPDA and disperse it in 1 mL of chloroplatinic acid solution (10 mg / mL), and add 1 mL of cobalt(II) chloride hexahydrate solution (20 mg / mL); (9)Ultrasonic the mixed solution obtained in step (8) at 25 °C for 2 hours and stir for 18 hours; (10)Dropwise add 20 mL of sodium borohydride solution (0.02 mol / L NaBH4) to the product obtained in step (9); (11)Filter, wash, and freeze-dry the product obtained in step (10) to obtain a black powder; (12)Place the black powder obtained in step (11) in a tube furnace under an argon protection atmosphere and calcine it at 900 °C for 1 hour (heating rate 5 °C / min); (13)Disperse the product obtained in step (12) in 100 mL of 1 M HClO4 solution and stir magnetically for 6 hours; (14)Filter, wash, and freeze-dry the product obtained in step (13) to obtain a carbon-supported platinum-cobalt ordered alloy catalyst (denoted as PtCo / ZPDA).

[0063] In Comparative Example 2, the particle size of the PtCo particles generated by sodium borohydride reduction increased significantly, resulting in a decrease in the electrocatalytic activity of the catalyst.

[0064] FromFigure 1 It can be seen that Comparative Example 1 changed the type of carbon carrier, and Comparative Example 2 changed the reduction conditions in step (10), resulting in significantly poorer electrochemical performance of the catalysts prepared in Comparative Examples 1-2 than that of Example 1.

Claims

1. A carbon-supported platinum-cobalt ordered alloy catalyst, characterized in that, It includes a porous carbon support and an active component supported on the porous carbon support; The active component includes platinum and cobalt, and the platinum and cobalt form a face-centered cubic structure with an ordered atomic arrangement.

2. The carbon-supported platinum-cobalt ordered alloy catalyst according to claim 1, wherein By mass percentage, the porous carbon support is 60 - 80%, platinum is 10% - 20%, and cobalt is 5% - 20%.

3. The carbon-supported platinum-cobalt ordered alloy catalyst according to claim 1, wherein The platinum and cobalt exist in the form of platinum-cobalt alloy particles.

4. The carbon-supported platinum-cobalt ordered alloy catalyst according to claim 1, wherein The particle size of the platinum-cobalt alloy particles is 1 - 8 nm.

5. The preparation method of the carbon-supported platinum-cobalt ordered alloy catalyst according to any one of claims 1-4, characterized in that, It includes the following steps: (1) Disperse zinc oxide in a solvent, add a cobalt metal salt, a basic buffer, and dopamine hydrochloride and mix to obtain self-assembled polydopamine nanospheres. After carbonizing the self-assembled polydopamine nanospheres, perform pickling and drying to obtain a porous carbon support; (2) Disperse the porous carbon support in an ethylene glycol / water solution, add a platinum salt, and perform ultrasonic dispersion and mixing to obtain a mixed solution. Heat it in an oil bath and perform solid-liquid separation to obtain a black powder; (3) Under the atmosphere of a protective gas, perform annealing treatment to obtain the carbon-supported platinum-cobalt ordered alloy catalyst.

6. The preparation method according to claim 5, wherein In step (1), the mass ratio of the zinc oxide, the cobalt metal salt, and the dopamine hydrochloride is 80 - 90:0.05 - 10:10 - 20; and / or, in step (1), the cobalt metal salt is selected from at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.

7. The preparation method according to claim 5, characterized in that, In step (1), the basic buffer is selected from at least one of ammonia water and tris(hydroxymethyl)aminomethane hydrochloride; and / or, in step (1), the temperature of the carbonization is 500 - 700 °C; and / or, in step (1), the time of the carbonization is 1 - 3 hours; and / or, in step (2), in the ethylene glycol / water solution, the volume ratio of water to ethylene glycol is 1:1 - 6; and / or, in step (2), the platinum salt includes chloroplatinic acid.

8. The preparation method according to claim 5, characterized in that, In step (2), the temperature of heating in the oil bath is 200 - 230 °C; and / or, in step (3), the temperature of the annealing is 500 - 900 °C.

9. A fuel cell, characterized in that, It includes an anode and a cathode, and the cathode includes the carbon-supported platinum-cobalt ordered alloy catalyst according to any one of claims 1 - 4.

10. Use of the carbon-supported platinum-cobalt ordered alloy catalyst according to any one of claims 1 - 4 in an oxygen reduction reaction.

Images