A non-precious metal M-doped carbon-supported PtM alloy catalyst and its preparation method and application

Abstract

A non-precious metal M-doped carbon-supported PtM alloy catalyst, its preparation method, and application, relates to a PtM alloy catalyst, its preparation method, and application. The catalyst aims to address the technical issues of poor catalytic activity and insufficient adaptability of existing PtM alloy catalysts. The catalyst of the present invention comprises PtM alloy nanoparticles uniformly supported on a non-precious metal M-doped carbon support, wherein M is Co, Fe, Zn, Ni, or Ce. The preparation method involves using M-doped carbon as a support, loading Pt by microwave reduction, and then alloying at high temperature to obtain a non-precious metal M-doped carbon-supported PtM alloy catalyst. The mass activities of PtCo / Co-NC@C and Pt / Fe-NC@C are 0.381 mA / μg, respectively. Pt and 0.285A / mg Pt , which is about 3.4 times and 2.5 times that of 20% Pt / C, and can be used in the field of proton exchange membrane fuel cells.

Description

Technical Field

[0001] The present invention belongs to the field of new energy materials, and specifically relates to a preparation method and application of a PtM alloy catalyst supported by carbon doped with non-precious metal M (M = Co, Fe, Zn, Ni, Ce, etc.). Background Art

[0002] Pt / C materials are widely used as cathode catalysts in proton exchange membrane fuel cells (PEMFCs) due to their excellent catalytic performance for the oxygen reduction reaction (ORR). However, commercial Pt / C suffers from issues such as insufficient activity and durability during long-term operation under harsh reaction conditions.

[0003] PtM / C (M = Co, Fe, Zn, Ni, etc.) catalysts have shown good performance in the field of oxygen reduction catalysis. At present, PtM ​​alloy catalysts are mostly prepared by co-impregnation and high-temperature reduction using ordinary commercial carbon as a carrier, or by using MOF-derived M-NC as a carrier and providing an M source, and then performing high-temperature alloying. However, in the co-impregnation method, due to the weak interaction between the carbon carrier and the PtM alloy particles, it is easy to agglomerate and sinter during the high-temperature reduction process, resulting in a decrease in its catalytic performance; although the PtM alloy catalyst prepared with MOF-derived M-NC as a carrier has achieved good catalytic performance, the MOF-based M-NC carrier has not yet been mass-produced, which limits the widespread application of this catalyst. Therefore, it is imperative to modify the commercial carbon carrier while retaining its good applicability to fuel cells to prepare a PtM alloy catalyst with good performance. Summary of the Invention

[0004] The present invention aims to address the technical issues of poor catalytic activity and insufficient adaptability of existing PtM alloy catalysts by providing a non-precious metal M-doped carbon-supported PtM alloy catalyst, its preparation method, and application. The present invention utilizes non-precious metal M (M = Co, Fe, Zn, Ni, Ce)-doped carbon (M-NC@C) as a carrier, loads Pt via microwave reduction, and then alloys the catalyst at high temperature to produce a non-precious metal M-doped carbon-supported PtM alloy catalyst (PtM / M-NC@C). The catalyst exhibits significantly higher activity and stability than a 20% Pt / C catalyst. Furthermore, the M-NC@C derived from a traditional carbon carrier possesses the applicability of traditional carbon carriers in fuel cell applications.

[0005] The non-precious metal M-doped carbon-supported PtM alloy catalyst of the present invention comprises PtM alloy nanoparticles uniformly supported on a non-precious metal M-doped carbon support. The non-precious metal M-doped carbon support is represented by M-NC@C, wherein M exists in an atomically dispersed form and M is Co, Fe, Zn, Ni or Ce. The mass percentage of M in the non-precious metal M-doped carbon-supported PtM alloy catalyst is 5% to 15%, and the mass percentage of Pt is 5% to 30%.

[0006] The preparation method of the above-mentioned non-noble metal M-doped carbon-supported PtM alloy catalyst is carried out according to the following steps:

[0007] 1. Preparation of non-precious metal M-doped carbon support (M-NC@C): adding carbon powder to methanol and ultrasonically stirring until the carbon powder is evenly dispersed to obtain a mixed solution A; then, an anhydrous methanol solution of a non-precious metal M salt and an anhydrous methanol solution of a ligand are sequentially added dropwise to the mixed solution A to obtain a mixed solution B after the addition is complete; the mixed solution B is stirred at room temperature for 1 to 2 hours to allow a complex of the M salt and the ligand to self-grow on the carbon; then, the mixed solution B is evaporated to dryness in a water bath to obtain a precursor; the precursor is ground evenly, placed in a high-temperature furnace in an inert atmosphere at a temperature of 700 to 1100°C for 1 to 4 hours for carbonization treatment, and after natural cooling, ground evenly to obtain a non-precious metal M-doped carbon support, represented by M-NC@C; wherein the anhydrous methanol solution of the ligand is prepared by dissolving o-phenanthroline, o-bipyridine or dimethylimidazole in anhydrous methanol;

[0008] 2. Microwave reduction of Pt: A non-precious metal M-doped carbon support is added to a dispersion and uniformly dispersed, followed by addition of a chloroplatinic acid solution and ultrasonic stirring to uniformize the slurry to obtain a mixed solution C; the pH of the mixed solution C is adjusted to alkaline and an inert gas is introduced to expel oxygen from the solution; microwave reduction is performed, and after natural cooling, the pH of the mixed solution is adjusted to acidic and stirred for 8 to 20 hours. After filtration and cleaning, the mixed solution is vacuum dried and ground uniformly to obtain a Pt-loaded non-precious metal M-doped carbon support, denoted as Pt / M-NC@C;

[0009] 3. Preparation of PtM / M-NC@C by high-temperature annealing: The non-precious metal M-doped carbon support loaded with Pt is placed in a high-temperature furnace with a reducing atmosphere, annealed at a temperature of 700-1000°C for 0.5-3h, cooled to room temperature, and ground evenly to obtain a non-precious metal M-doped carbon-supported PtM alloy catalyst, recorded as PtM / M-NC@C.

[0010] Furthermore, the carbon powder in step 1 is XC-72C, Ecp-600jd, Ec-300 or BP-2000;

[0011] Furthermore, the anhydrous methanol solution of the non-noble metal M salt described in step 1 is prepared by dissolving cobalt chloride, cobalt nitrate, cobalt sulfate, ferrous sulfate, ferric chloride, ferric nitrate, nickel nitrate, zinc nitrate, cerium nitrate or cerium chloride in anhydrous methanol;

[0012] Furthermore, in the mixed solution B described in step 1, the concentration of carbon powder is 0.3-2 g / L, the concentration of the non-noble metal M salt is 0.01-0.05 mol / L, and the concentration of the ligand is 0.01-0.3 mol / L.

[0013] Furthermore, the inert atmosphere in step 1 is Ar or N2.

[0014] Furthermore, the dispersion in step 2 is a mixed solution of ethylene glycol and isopropyl alcohol in a volume ratio of (2-6):1;

[0015] Furthermore, the pH of the mixed solution C is adjusted to be alkaline in step 2, and the pH value is adjusted to 11-13.

[0016] Furthermore, the pH of the mixed solution is adjusted to be acidic in step 2, which is to adjust the pH value to 2-3.

[0017] Furthermore, the reducing atmosphere in step 3 is a mixture of H2 and Ar, wherein the volume percentage of H2 is 5% to 10%;

[0018] The application of the above-mentioned non-noble metal M-doped carbon-supported PtM alloy catalyst is the application of the catalyst in the cathode oxygen reduction reaction (ORR) of fuel cells.

[0019] The beneficial effects of the present invention compared to the prior art are:

[0020] (1) The present invention can combine a traditional carbon carrier with a non-precious metal M-NC to obtain an M-NC@C carrier, and load Pt onto the M-NC@C carrier by microwave reduction to obtain Pt / M-NC@C. The atomically dispersed M and Pt in the M-NC@C are converted into a PtM alloy by high-temperature annealing under a reducing atmosphere, thereby obtaining the alloy catalyst PtM / M-NC@C.

[0021] (2) Using o-phenanthroline, o-bipyridine or dimethylimidazole as ligands, the complex of M salt and ligand grows on the carbon surface. By controlling the carbonization conditions of the precursor, the M in the prepared non-noble metal M-doped carbon support M-NC@C is at the atomic level MN xThe form of M is enriched on the surface of carbon, which greatly enhances the interaction between the support and the metal, thereby improving the activity and stability of the catalyst. In addition, the M in the atomically dispersed form in the support can be reduced by H2 during the annealing process and alloyed with Pt to form a PtM alloy structure. When Pt forms a PtM alloy with the 3d transition metal M, Pt(5d)-M(3d) orbital coupling will occur, changing the Pt 5d band vacancies, Pt-Pt atomic distance and Pt coordination number, causing the Pt-d band center to move downward, thereby changing the electronic structure of Pt, weakening the binding energy between Pt surface atoms and oxygen-containing species, and improving the activity and stability of the catalyst. The mass activity (MA) of PtCo / Co-NC@C is 0.381mA / μg Pt , which is about 3.4 times that of 20% Pt / C; the mass activity (MA) of PtFe / Fe-NC is 0.285A / mg Pt , which is about 2.5 times that of 20% Pt / C. The peak power density of PtCo / Co-NC@C is 2.4W / cm 2 The peak power density of Pt / Fe-NC@C is 1.9 W / cm 2 , which are higher than the peak power density of 1.8W / cm of 20% Pt / C. 2 .

[0022] (3) The carbon carrier of the present invention is a conventional carbon powder doped with a non-precious metal M, which has good fuel cell applicability, so that the alloy catalyst PtM / M-NC@C also has excellent performance in fuel cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a TEM image of PtCo / Co-NC prepared in Example 1;

[0024] Figure 2 is the XRD spectrum of PtCo / Co-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1;

[0025] Figure 3 ORR polarization diagrams of PtCo / Co-NC, PtFe / Fe-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1;

[0026] Figure 4 is a graph of mass specific activity of PtCo / Co-NC, PtFe / Fe-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1;

[0027] Figure 5 ORR polarization diagrams of PtCo / Co-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1 before and after aging;

[0028] Figure 6 is a mass specific activity diagram of PtCo / Co-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1 before and after aging;

[0029] Figure 7 1 is a fuel cell polarization diagram of PtCo / Co-NC and PtFe / Fe-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1. DETAILED DESCRIPTION

[0030] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention that does not depart from the spirit and scope of the technical solution of the present invention should be included in the scope of protection of the present invention.

[0031] Example 1: The preparation method of the non-noble metal Co-doped carbon-supported PtM alloy catalyst of this embodiment is carried out according to the following steps:

[0032] 1. Preparation of non-precious metal Co-doped carbon support (Co-NC@C): 120 mg of carbon powder Ecp-600jd was added to 40 mL of methanol, ultrasonically dispersed for 1 h, and stirred for 12 h to uniformly disperse the carbon powder to obtain a mixed solution A; 58 mg of cobalt nitrate was dissolved in 10 mL of methanol to obtain a cobalt nitrate solution; 108 mg of o-phenanthroline was added to 10 mL of methanol and ultrasonically treated for 0.5 h, and then stirred to fully dissolve it to obtain an o-phenanthroline solution; then the cobalt nitrate solution and the o-phenanthroline solution were mixed. The precursors were then added dropwise to the mixed solution A to obtain a mixed solution B. The mixed solution B was stirred at 25°C for 1 hour to allow the complex of the cobalt salt and the ligand o-phenanthroline to grow on the carbon. The mixed solution B was then evaporated to dryness in a water bath at 60°C to obtain a precursor. The precursor was ground evenly and placed in a high-temperature furnace in an Ar atmosphere at 850°C for 2 hours for carbonization treatment. After natural cooling, the precursor was ground evenly to obtain a non-precious metal Co-doped carbon support, represented by Co-NC@C.

[0033] 2. Microwave reduction of Pt: 40 mg of non-precious metal Co-doped carbon support Co-NC@C was added to 60 ml of ethylene glycol-isopropanol mixed solution with ultrasonic stirring for 120 min for dispersion, wherein the volume ratio of ethylene glycol to isopropanol in the ethylene glycol-isopropanol mixed solution was 4:1, and then 0.950 ml of 0.0485 mol / L chloroplatinic acid-ethylene glycol solution was added and ultrasonic stirring was performed to make the slurry uniform to obtain mixed solution C; 1 mol L -1The pH of the mixed solution C was adjusted to 12 using a NaOH-ethylene glycol solution, and nitrogen was introduced to expel dissolved air from the solution to protect the solution. The mixed solution was then placed in a microwave and heated for 100 seconds. After natural cooling, the pH of the mixed solution was adjusted to 2 using a nitric acid-ethylene glycol solution and stirred for 8 hours. After being filtered and washed three times, the mixed solution was vacuum-dried at 80°C for 8 hours and ground uniformly to obtain a Pt-loaded non-precious metal Co-doped carbon support, represented by Pt / Co-NC@C.

[0034] 3. Preparation of PtCo / Co-NC@C by high-temperature annealing: The non-precious metal Co-doped carbon support loaded with Pt was placed in a high-temperature furnace with a H2-Ar reducing atmosphere, annealed at 750°C for 1 hour, cooled to room temperature, and ground evenly to obtain a non-precious metal Co-doped carbon-supported PtM alloy catalyst, recorded as PtCo / Co-NC@C.

[0035] TEM images of the PtCo / Co-NC@C catalyst prepared in this example are as follows: Figure 1 As shown by Figure 1 It can be seen that PtCo particles are evenly distributed on the surface of Co-NC@C with a particle size of 3 to 4 nm.

[0036] Example 2: The preparation method of the non-precious metal Fe-doped carbon-supported PtM alloy catalyst of this embodiment is carried out according to the following steps:

[0037] 1. Preparation of non-precious metal Fe-doped carbon support (Fe-NC@C): 120 mg of carbon powder Ecp-600jd was added to 40 mL of methanol, ultrasonically dispersed for 1 h, and stirred for 12 h to uniformly disperse the carbon powder to obtain a mixed solution A; 56 mg of ferrous sulfate was dissolved in 10 mL of methanol to obtain a ferrous sulfate solution; 108 mg of o-phenanthroline was added to 10 mL of methanol and ultrasonically treated for 0.5 h, and then stirred to fully dissolve it to obtain an o-phenanthroline solution; then the ferrous sulfate solution and the o-phenanthroline solution were mixed. The first step is to add the first phase of the carbonization reaction to the carbonization reaction mixture A, and then add the first phase of the carbonization reaction mixture A to obtain the carbonization reaction mixture B. The first phase of the carbonization reaction mixture B is stirred at 25 ° C for 1 hour to allow the complex of the cobalt salt and the ligand o-phenanthroline to grow on the carbon. The second phase of the carbonization reaction mixture B is evaporated to dryness in a water bath at 60 ° C to obtain a precursor. The precursor is ground evenly and placed in a high-temperature furnace in an Ar atmosphere at a temperature of 850 ° C for 2 hours for carbonization treatment. After natural cooling, the precursor is ground evenly to obtain a non-precious metal Fe-doped carbon support, represented by Fe-NC@C.

[0038] 2. Microwave reduction of Pt: 40 mg of Fe-NC@C, a non-precious metal Fe-doped carbon support, was added to 60 ml of ethylene glycol-isopropanol mixed solution with ultrasonic stirring for 120 min for dispersion, wherein the volume ratio of ethylene glycol to isopropanol in the ethylene glycol-isopropanol mixed solution was 4:1. Then, 0.950 ml of 0.0485 mol / L chloroplatinic acid-ethylene glycol solution was added and ultrasonic stirring was performed to make the slurry uniform to obtain mixed solution C; 1 mol L -1 The pH value of the mixed solution C was adjusted to 12 using a NaOH-ethylene glycol solution, and nitrogen was introduced to expel dissolved air from the solution to protect the solution. The mixed solution was then placed in a microwave and heated for 100 seconds. After natural cooling, the mixed solution was adjusted to a pH of 2 using a nitric acid-ethylene glycol solution and stirred for 8 hours. After being filtered and washed three times, the mixed solution was vacuum-dried at 80°C for 8 hours and ground uniformly to obtain a Pt-loaded non-precious metal Fe-doped carbon support, represented by Pt / Fe-NC@C.

[0039] 3. Preparation of PtFe / Fe-NC@C by high-temperature annealing: The non-precious metal Fe-doped carbon support loaded with Pt was placed in a high-temperature furnace with a H2-Ar reducing atmosphere, annealed at 800°C for 1 hour, cooled to room temperature, and ground evenly to obtain a non-precious metal Fe-doped carbon-supported PtM alloy catalyst, recorded as PtFe / Fe-NC@C.

[0040] Comparative Example 1: In this comparative example, XC-72 was directly reduced to Pt nanoparticles by a microwave ethylene glycol method to prepare an oxygen reduction catalyst Pt / C. The specific preparation steps are as follows:

[0041] 40 mg of carbon powder Ecp-600jd was dissolved in 60 ml of ethylene glycol-isopropanol mixed solution, wherein the volume ratio of ethylene glycol to isopropanol in the mixed solution was 4:1, and ultrasonic stirring was performed for 120 min. 0.95 ml of 0.0485 mol / L chloroplatinic acid-ethylene glycol solution was added and ultrasonic stirring was continued to ensure thorough mixing. Subsequently, 1 mol L -1 After the pH value of the mixed solution was adjusted to 12 with a NaOH-ethylene glycol solution, nitrogen was introduced into the mixed solution to remove dissolved air in the solution to protect the solution; the mixed solution was then placed in a microwave and heated for 100 seconds; after cooling, the pH value of the mixed solution was adjusted to 2 with a nitric acid-ethylene glycol solution and stirred for 12 hours; the mixed solution was then filtered and washed three times, the filter residue was taken out, and placed in a vacuum drying oven at a temperature of 80°C and vacuum dried for 8 hours to obtain a 20% Pt / C catalyst, which was ground and bottled for later use.

[0042] The XRD spectra of the PtCo / Co-NC@C catalyst prepared in Example 1 and the 0% Pt / C catalyst prepared in the comparative example are shown in FIG. Figure 2 As shown by Figure 2 It can be seen that the particles on the Co-NC@C support are PtCo (Pt3Co) particles, and there are no characteristic peaks of Co particles or oxides in the XRD pattern of PtCo / Co-NC@C. Therefore, it can be explained that the Co on the Co-NC@C support exists in the form of Co-Nx, rather than Co particles or oxides.

[0043] The PtCo / Co-NC@C catalyst prepared in Example 1, the Pt / Fe-NC@C prepared in Example 2, and the 20% Pt / C prepared in Comparative Example 1 were subjected to ORR polarization tests. The ORR polarization curves obtained are shown in FIG. Figure 3 As shown, the mass activity diagram is Figure 4 As shown, from Figure 3 and Figure 4 It can be seen that the mass activity (MA) of PtCo / Co-NC@C is 0.381 mA / μg Pt , which is about 3.4 times that of 20% Pt / C; the mass activity (MA) of PtFe / Fe-NC is 0.285A / mg Pt , which is about 2.5 times that of 20% Pt / C.

[0044] ORR aging test of PtCo / Co-NC@C catalyst prepared in Example 1 and 20% Pt / C catalyst prepared in Comparative Example 1 The ORR polarization diagrams before and after aging are shown in FIG. Figure 5 As shown in the figure, the mass specific activity of PtCo / Co-NC prepared in Example 1 and 20% Pt / C prepared in Comparative Example 1 before and after aging is shown in the figure Figure 6 As shown, from Figure 5 and Figure 6 It can be seen that the stability of PtCo / Co-NC@C is much better than that of 20%Pt / C.

[0045] Figure 7 The fuel cell polarization curves of PtCo / Co-NC prepared in Example 1, PtFe / Fe-NC prepared in Example 2 and 20% Pt / C prepared in Comparative Example 1 are shown. Figure 7 It can be seen that the peak power density of PtCo / Co-NC@C is 2.4W / cm 2 The peak power density of Pt / Fe-NC@C is 1.9 W / cm 2 , which are higher than the 20% Pt / C (1.8W / cm 2 ).

[0046] The M element in the non-noble metal M-doped carbon M-NC@C of the present invention is MN at the atomic level. xThe M in the carrier in the form of atomic dispersion can also form a PtM alloy structure with Pt during annealing. The PtM structure can effectively regulate the adsorption capacity of Pt nanoparticles to reaction intermediates and thus regulate the catalyst activity. At the same time, the MN in the carrier x The M-NC@C supports serve as deposition sites for Pt alloys, facilitating the uniform dispersion of Pt or PtM nanoparticles on the support surface. The strong interaction (SMSI) between the M-NC@C support and PtM NPs significantly enhances the catalytic activity and stability compared to Pt / C catalysts. Furthermore, the M-NC@C support exhibits excellent suitability for fuel cell applications, enabling the PtM / M-NC@C catalyst to exhibit excellent performance in fuel cells.

Claims

1. A non-precious metal M-doped carbon-supported PtM alloy catalyst, characterized in that The catalyst is a PtM alloy nanoparticle uniformly supported on a non-noble metal M-doped carbon carrier. Indicates that M exists in an atomically dispersed form, and M is Co, Fe, or Ni; the mass percentage of M in the non-noble metal M-doped carbon-supported PtM alloy catalyst is 5% to 15%, and the mass percentage of Pt is 5% to 30%; the preparation method of the catalyst is carried out according to the following steps:

1. Non-precious metal M-doped carbon supports Preparation: Add carbon powder to methanol and stir ultrasonically until the carbon powder is evenly dispersed to obtain a mixed solution A; then add an anhydrous methanol solution of a non-precious metal M salt and an anhydrous methanol solution of a ligand to the mixed solution A in sequence, and after the addition is complete, obtain a mixed solution B; stir the mixed solution B at room temperature for 1 to 2 hours to allow the complex of the M salt and the ligand to grow on the carbon; then evaporate the mixed solution B in a water bath to obtain a precursor; grind the precursor evenly, place it in a high-temperature furnace in an inert atmosphere at a temperature of 700 to 1100°C for 1 to 4 hours for carbonization treatment, and after natural cooling, grind it evenly to obtain a non-precious metal M-doped carbon support, and use express; The anhydrous methanol solution of the ligand is prepared by dissolving o-phenanthroline, o-bipyridine or dimethylimidazole in anhydrous methanol; 2. Microwave reduction of Pt: A non-noble metal M-doped carbon support is added to a dispersion and uniformly dispersed, followed by addition of a chloroplatinic acid solution and ultrasonic stirring to uniformly slurry the mixture to obtain a mixed solution C; the pH of the mixed solution C is adjusted to alkaline and an inert gas is introduced to expel oxygen from the solution; The mixture was reduced by microwave and cooled naturally, and the pH of the mixed solution was adjusted to acidic and stirred for 8 to 20 hours. After filtration and cleaning, it was vacuum dried and ground evenly to obtain a non-precious metal M-doped carbon support loaded with Pt. express; 3. High temperature annealing preparation The non-precious metal M-doped carbon support loaded with Pt was placed in a high-temperature furnace in a reducing atmosphere, maintained at a temperature of 700-1000 ° C for 0.5-3 h for annealing, cooled to room temperature, and ground uniformly to obtain a non-precious metal M-doped carbon-supported PtM alloy catalyst, which was recorded as .

2. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 1, characterized in that: The method proceeds as follows:

1. Non-precious metal M-doped carbon supports Preparation: Add carbon powder to methanol and stir ultrasonically until the carbon powder is evenly dispersed to obtain a mixed solution A; then add an anhydrous methanol solution of a non-precious metal M salt and an anhydrous methanol solution of a ligand to the mixed solution A in sequence, and after the addition is complete, obtain a mixed solution B; stir the mixed solution B at room temperature for 1 to 2 hours to allow the complex of the M salt and the ligand to grow on the carbon; then evaporate the mixed solution B in a water bath to obtain a precursor; grind the precursor evenly, place it in a high-temperature furnace in an inert atmosphere at a temperature of 700 to 1100°C for 1 to 4 hours for carbonization treatment, and after natural cooling, grind it evenly to obtain a non-precious metal M-doped carbon support, and use express; The anhydrous methanol solution of the ligand is prepared by dissolving o-phenanthroline, o-bipyridine or dimethylimidazole in anhydrous methanol; 2. Microwave reduction of Pt: A non-noble metal M-doped carbon support is added to a dispersion and uniformly dispersed, followed by addition of a chloroplatinic acid solution and ultrasonic stirring to uniformly slurry the mixture to obtain a mixed solution C; the pH of the mixed solution C is adjusted to alkaline and an inert gas is introduced to expel oxygen from the solution; The mixture was reduced by microwave and cooled naturally, and the pH of the mixed solution was adjusted to acidic and stirred for 8 to 20 hours. After filtration and cleaning, it was vacuum dried and ground evenly to obtain a non-precious metal M-doped carbon support loaded with Pt. express; 3. Preparation of PtM / M-NC@C by high temperature annealing: The non-precious metal M-doped carbon support loaded with Pt was placed in a high temperature furnace in a reducing atmosphere and annealed at a temperature of 700-1000°C for 0.5-3 h. After cooling to room temperature, the carbon support was ground uniformly to obtain a non-precious metal M-doped carbon-supported PtM alloy catalyst, which was denoted as .

3. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2, characterized in that: The carbon powder described in step 1 is XC-72C, Ecp-600jd, Ec-300 or BP-2000.

4. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2 or 3, characterized in that: The anhydrous methanol solution of the non-noble metal M salt described in step 1 is prepared by dissolving cobalt chloride, cobalt nitrate, cobalt sulfate, ferrous sulfate, ferric chloride, ferric nitrate, and nickel nitrate in anhydrous methanol.

5. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2 or 3, characterized in that: In the mixed solution B described in step 1, the concentration of carbon powder is 0.3~2 g / L, the concentration of non-precious metal M salt is 0.01~0.05 mol / L, and the concentration of ligand is 0.01~0.3 mol / L.

6. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2 or 3, characterized in that: The inert atmosphere described in step 1 is Ar or N2.

7. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2 or 3, characterized in that: The dispersion described in step 2 is a mixed solution of ethylene glycol and isopropyl alcohol in a volume ratio of (2-6):

1.

8. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2 or 3, characterized in that: The step 2 of adjusting the pH of the mixed solution C to be alkaline is to adjust the pH value to 11-13.

9. The method for preparing a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 2 or 3, characterized in that: The pH of the mixed solution is adjusted to be acidic in step 2, that is, the pH value is adjusted to 2-3.

10. The use of a non-noble metal M-doped carbon-supported PtM alloy catalyst according to claim 1, characterized in that: This application is to use non-precious metal M-doped carbon-supported PtM alloy catalyst in the cathode oxygen reduction reaction of proton exchange membrane fuel cells.

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