Preparation method and application of non-noble metal material loaded noble metal electrocatalyst

Abstract

This invention discloses a method for preparing a noble metal electrocatalyst supported on a non-noble metal material and its application. The preparation method includes: Step 1, dissolving a non-noble metal precursor and a noble metal precursor in a mixed solvent; Step 2, adding a carbon support and ultrasonically dispersing until homogeneous; Step 3, rotary evaporation to obtain a solid phase; Step 4, treating the solid phase with NH3 gas and then with Ar gas; Step 5, ultrasonically dispersing the treated solid phase in a sulfuric acid aqueous solution and refluxing to obtain a refluxed solid phase; Step 6, washing the refluxed solid phase with water until the pH of the filtrate is neutral, and drying the washed solid phase to obtain the noble metal electrocatalyst supported on a non-noble metal material. In electrochemical tests conducted in an HClO4 aqueous solution, this noble metal electrocatalyst supported on a non-noble metal material exhibits a half-wave potential above 0.875 V vs. RHE and a specific activity above 310 mA / mg. Pt It exhibits significantly enhanced catalytic activity for oxygen reduction reactions.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalysis technology, specifically relating to the preparation method and application of noble metal electrocatalysts supported on non-noble metal materials. Background Technology

[0002] Fuel cells are a clean energy technology that directly converts the chemical energy of fuel into electrical energy, offering advantages such as high energy conversion efficiency and environmental friendliness. Hydrogen fuel cell catalysts are mainly divided into two categories: carbon-supported noble metal and non-noble metal MN / C materials. Traditional carbon-supported noble metal catalysts suffer from problems such as noble metal particle detachment, Ostwald aging, and agglomeration under battery conditions due to the lack of interaction between the support and noble metal particles, affecting catalyst lifespan. Newer non-noble metal MN / C materials, due to insufficient active site density, still exhibit lower catalytic performance than noble metal catalysts. Furthermore, hydrogen peroxide, a byproduct of the oxygen reduction reaction at the cathode, causes irreversible damage to the active sites of MN / C. Combining these two approaches can effectively overcome these problems. Using MN / C material as a support for noble metals significantly improves the interaction between the support and noble metal particles. The addition of noble metals can compensate for the lack of active sites in non-noble metals and effectively promote hydrogen peroxide decomposition, improving the overall durability of the catalyst.

[0003] In 2020, Xiang Ao et al. (Energy & Environmental Science, 2020, 13, 3032-3040) prepared Fe-NC material by co-coordinating zinc nitrate, 2-methylimidazole and ferric chloride and pyrolyzing them at 900 °C. They then supported Pt on the Fe-NC matrix by ethylene glycol synthesis in an oil bath at 160 °C. The resulting electrocatalyst showed a half-wave potential decay of only 7 mV after 5000 potential scans, which is superior to commercial Pt / C catalysts. In 2022, Minhua Shao et al. (Journal of the American Chemical Society, 2022, 10.1021 / jacs.2c08305) obtained a ZIF-8 material by coordinating zinc nitrate with 2-methylimidazole, followed by ball milling with Fe2O3 and pyrolysis at 1000 °C to obtain a Fe-NC support. Subsequently, Pt was loaded onto the Fe-NC surface via formaldehyde reduction to finally prepare a Pt / Fe-NC catalyst. This catalyst achieved a half-wave potential of 0.84 V (vs. RHE) under acidic conditions, and after 10,000 cycles, the electrochemical active area (ECSA) decreased by only 1%. Both of these methods effectively improve the activity and durability of fuel cell catalysts by preparing non-noble metal and noble metal composite catalysts. However, the synergy between the active component and the support is poor, and the synthesis process is complex. For example, both methods require the prior synthesis of the Fe-NC support before Pt loading, resulting in cumbersome processes and long cycles. In addition, the yield of Fe-NC prepared using ZIF-8 as a precursor is low (usually 1-5%) and the cost is high, which is not conducive to future scale-up preparation. Summary of the Invention

[0004] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing a method for preparing and applying a noble metal electrocatalyst supported on a non-noble metal material. This method involves dissolving a non-noble metal precursor and a noble metal precursor in a mixed solvent, adding a carbon support, and rotary evaporating to obtain a solid phase. The solid phase is then subjected to NH3 atmosphere treatment and Ar atmosphere treatment followed by sulfuric acid reflux to obtain the noble metal electrocatalyst supported on a non-noble metal material. Electrochemical tests in an HClO4 aqueous solution show a half-wave potential above 0.88 V vs. RHE and a specific activity above 310 mA / mg. Pt， It exhibits significantly enhanced catalytic activity for oxygen reduction reactions.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, characterized in that it includes:

[0006] Step 1: Dissolve the non-precious metal precursor and the precious metal precursor in a mixed solvent to obtain system A;

[0007] Step 2: Add carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 8-10 to obtain system B;

[0008] Step 3: Rotary evaporate the system B to obtain a solid phase;

[0009] Step 4: Treat the solid phase at 350 ℃~400 ℃ for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 650 ℃~850 ℃ for 60 min~180 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0010] Step 5: The atmosphere-treated solid phase is ultrasonically dispersed in a 0.5 mol / L to 1.5 mol / L sulfuric acid aqueous solution and refluxed at 70 ℃ to 90 ℃ for 3 h to 6 h to obtain the refluxed solid phase;

[0011] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase to obtain a non-precious metal material supported on a precious metal electrocatalyst.

[0012] The above-mentioned method for preparing noble metal electrocatalysts supported on non-noble metal materials is characterized in that, in step one, the concentration of the noble metal precursor in system A is 1 mmol / L to 7 mmol / L, and the concentration of the non-noble metal precursor is 0.9 g / L to 3 g / L; in step one, the non-noble metal precursor is hematoxylin, tetra-p-tolylporphyrin iron, tetra-p-chlorophenylporphyrin iron, tetra-p-methoxyphenylporphyrin iron, phthalocyanine iron, μ-oxo-bistetraphenylporphyrin iron, bistetrachlorophenylporphyrin, 5,10,15,20-tetra(pentafluorophenyl)porphyrin iron, tetra(2-naphthyl)porphyrin iron, cobalt phthalocyanine, tetra-p-methoxyphenylporphyrin cobalt, 5,10,15,20-tetra(4-carboxyphenyl)porphyrin One or more of cobalt porphyrin and manganese phthalocyanine; in step one, the noble metal precursor is one or more of chloroplatinic acid, chloroplatinous acid, potassium chloroplatinate, potassium chloroplatinous, sodium chloroplatinate, sodium chloroplatinous, ammonium chloroplatinate, and ammonium chloroplatinous; in step one, the mixed solvent is a mixture of water and an organic solvent, wherein the volume of the organic solvent in the mixed solvent is 1 to 6 times the volume of water, and the organic solvent is one or more of N,N-dimethylformamide, glacial acetic acid, methanol, ethanol, formamide, dimethyl sulfoxide, and acetonitrile.

[0013] The above-mentioned method for preparing a noble metal electrocatalyst supported on a non-noble metal material is characterized in that, in step one, the non-noble metal precursor is one or more of hematoxylin, tetra-p-tolylporphyrin iron, tetra-p-chlorophenylporphyrin iron, and tetra-p-methoxyphenylporphyrin iron; in step one, the noble metal precursor is one or more of chloroplatinic acid, chloroplatinic acid, potassium chloroplatinate, and potassium chloroplatinic acid; in step one, the organic solvent is N,N-dimethylformamide and / or glacial acetic acid.

[0014] The above-mentioned method for preparing a noble metal electrocatalyst supported on a non-noble metal material is characterized in that, in step two, the carbon support is one or more of carbon black EC600JD, carbon black BP2000, carbon black EC300JD, carbon black VXC-72, activated carbon, carbon nanotubes, carbon fibers, graphene, fullerene, and foamed carbon.

[0015] The above-mentioned method for preparing a noble metal electrocatalyst supported on a non-noble metal material is characterized in that, in step two, the carbon support is one or more of carbon black EC600JD, carbon black BP2000, carbon black EC300JD, and carbon black VXC-72.

[0016] The above-mentioned method for preparing a noble metal electrocatalyst supported on a non-noble metal material is characterized in that, in step two, the pH is adjusted to 8-10 by using an alkaline solution, wherein the alkaline solution is one or more of potassium hydroxide solution, ammonia water, sodium hydroxide solution, sodium bicarbonate solution, potassium carbonate solution, lithium hydroxide solution, sodium carbonate solution, sodium oxalate solution, and sodium phosphate solution.

[0017] The method for preparing the above-mentioned non-precious metal material supported precious metal electrocatalyst is characterized in that, in step two, the alkaline solution is one or more of potassium hydroxide solution, ammonia water, sodium hydroxide solution, sodium bicarbonate solution and potassium carbonate solution.

[0018] The above-mentioned method for preparing a noble metal electrocatalyst supported on a non-noble metal material is characterized in that, in step two, the concentration of the alkaline solution is 0.05 mol / L to 5 mol / L; and in step two, the carbon support content in system B is 2 g / L to 8 g / L.

[0019] The method for preparing the above-mentioned non-precious metal material supported precious metal electrocatalyst is characterized in that, in step five, the volume of the sulfuric acid aqueous solution is 0.5 to 2 times the volume of the mixed solvent in step one.

[0020] Furthermore, this invention also provides an application of a non-precious metal material-supported precious metal electrocatalyst prepared by the above-mentioned method for preparing a non-precious metal material-supported precious metal electrocatalyst in a proton exchange membrane fuel cell.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] The method for preparing the non-precious metal material-supported noble metal electrocatalyst of the present invention involves dissolving a non-precious metal precursor and a noble metal precursor in a mixed solvent, adding a carbon support, and rotary evaporating to obtain a solid phase. The solid phase is then subjected to NH3 atmosphere treatment and Ar atmosphere treatment followed by sulfuric acid reflux to obtain the non-precious metal material-supported noble metal electrocatalyst. In electrochemical tests conducted in HClO4 aqueous solution, the half-wave potential is above 0.875 V vs. RHE, and the specific activity is higher than 310 mA / mgPt, exhibiting significantly improved oxygen reduction reaction catalytic activity.

[0023] The non-precious metal material supported on precious metal electrocatalyst prepared by the method of the present invention has a dispersed central atom in the non-precious metal material with no aggregation of active centers. After loading Pt particles, the Pt particles are uniformly dispersed on the surface of the support material and have significantly improved durability.

[0024] The preparation process of this invention is simple, has a short cycle, and achieves an electrocatalyst yield of over 90%, with low material loss.

[0025] The preparation method of this invention can be adapted to a variety of non-precious metal materials, has wide applicability, and greatly enriches the preparation process of proton exchange membrane fuel cell electrocatalysts.

[0026] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0027] Figure 1 This is a transmission electron microscope (TEM) image of a noble metal electrocatalyst supported on a non-noble metal material, as shown in Example 1.

[0028] Figure 2 This is a transmission electron microscope (TEM) image of the electrocatalyst in Comparative Example 1.

[0029] Figure 3 This is a schematic diagram of the electrochemical performance of the noble metal electrocatalyst supported on a non-noble metal material in Example 1, determined by the standard three-electrode method. Detailed Implementation

[0030] All reagents used in the following examples are commercially available. Among them, the preferred reagents, hematoxylin, tetra-p-tolylporphyrin iron, tetra-p-chlorophenylporphyrin iron, tetra-p-methoxyphenylporphyrin iron, phthalocyanine iron, μ-oxo-bistetraphenylporphyrin iron, bis-tetrachlorophenylporphyrin, 5,10,15,20-tetra(pentafluorophenyl)porphyrin iron, tetra(2-naphthyl)porphyrin iron, cobalt phthalocyanine, tetra-p-methoxyphenylporphyrin cobalt, 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt, and manganese phthalocyanine were purchased from Maclean's. Example 1

[0031] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0032] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is hemocyanin, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0033] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 2 mol / L, and the alkaline solution is potassium hydroxide solution;

[0034] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0035] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0036] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0037] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst.

[0038] Comparative Example 1

[0039] This comparative example is the same as Example 1, except that the mass of hemolysin is 5g.

[0040] Comparative Example 2

[0041] This comparative example is the same as Example 1, except that the volume of the mixed solvent is 0.5L, and the volume of the organic solvent in the mixed solvent is 0.5 times the volume of the water.

[0042] Comparative Example 3

[0043] This comparative example is the same as Example 1, except that the pH is 14 and the alkali concentration is 4 mol / L.

[0044] Comparative Example 4

[0045] This comparative example is the same as Example 1, except that the NH3 atmosphere temperature is 500 °C.

[0046] Comparative Example 5

[0047] This comparative example is the same as Example 1, except that the Ar atmosphere is 900 °C.

[0048] Comparative Example 6

[0049] This comparative example is the same as Example 1, except that the reflux temperature is 100 °C. Example 2

[0050] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0051] Step 1: Dissolve 1.9 g of a non-precious metal precursor and 3.2 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetra-p-tolylporphyrin iron, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0052] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 2 mol / L, and the alkaline solution is potassium hydroxide solution;

[0053] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0054] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0055] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0056] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 3

[0057] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0058] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1.5 L of a mixed solvent to obtain system A; the non-precious metal precursor is hemocyanin, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is glacial acetic acid, and the volume of the organic solvent in the mixed solvent is 3 times the volume of the water; the dissolution can be performed by heating.

[0059] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 2 mol / L, and the alkaline solution is potassium hydroxide solution;

[0060] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0061] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0062] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0063] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 4

[0064] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0065] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is hemocyanin, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0066] Step 2: Add 4g of carbon carrier to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon carrier is carbon black BP2000, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution with a concentration of 2 mol / L, which is a potassium hydroxide solution.

[0067] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0068] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0069] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0070] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 5

[0071] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0072] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is hemocyanin, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0073] Step 2: Add 4g of carbon carrier to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 9.5 to obtain system B; the carbon carrier is carbon black EC600JD, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 3mol / L, and the alkaline solution is ammonia water;

[0074] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0075] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0076] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0077] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 6

[0078] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0079] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is hemocyanin, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0080] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 2 mol / L, and the alkaline solution is potassium hydroxide solution;

[0081] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0082] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 850 °C for 60 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0083] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0084] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 7

[0085] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0086] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is hemocyanin, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0087] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 2 mol / L, and the alkaline solution is potassium hydroxide solution;

[0088] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0089] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0090] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 1 mol / L sulfuric acid aqueous solution and refluxed at 80 °C for 4 h to obtain the refluxed solid phase;

[0091] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 8

[0092] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0093] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 0.5 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetrachlorophenylporphyrin iron, the precious metal precursor is chloroplatinic acid, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0094] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 8 to obtain system B; the carbon support is carbon black EC300JD, the ultrasonic dispersion time can be 30min, the pH is adjusted by using an alkaline solution with a concentration of 2 mol / L, and the alkaline solution is sodium hydroxide solution;

[0095] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0096] Step 4: Treat the solid phase at 380 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 650 °C for 180 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0097] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 1.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 3 h to obtain the refluxed solid phase;

[0098] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 9

[0099] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0100] Step 1: Dissolve 1.9 g of a non-precious metal precursor and 3.2 mmol of a precious metal precursor in 2 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetramethoxyphenylporphyrin iron, the precious metal precursor is potassium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0101] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black VXC-72, the ultrasonic dispersion time can be 30min, the pH is adjusted by using an alkaline solution with a concentration of 2 mol / L, and the alkaline solution is sodium bicarbonate solution;

[0102] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0103] Step 4: Treat the solid phase at 400 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0104] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 1 mol / L sulfuric acid aqueous solution and refluxed at 80 °C for 6 h to obtain the refluxed solid phase;

[0105] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 10

[0106] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0107] Step 1: Dissolve 1.9 g of a non-precious metal precursor and 3.2 mmol of a precious metal precursor in 2 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetrakis(p-tolylporphyrin) iron and tetrakis(p-methoxyphenylporphyrin) iron, with a mass ratio of 1:1; the precious metal precursor is potassium chloroplatinate; the mixed solvent is a mixture of water and an organic solvent, the organic solvent being N,N-dimethylformamide and glacial acetic acid, with a volume ratio of 1:1, and the volume of the organic solvent in the mixed solvent being twice the volume of the water; the dissolution can be performed by heating.

[0108] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD and carbon black BP2000, the mass ratio of carbon black EC600JD and carbon black BP2000 is 1:1, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution, the concentration of which is 2mol / L, and the alkaline solution is a potassium carbonate solution;

[0109] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0110] Step 4: Treat the solid phase at 400 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0111] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 1 mol / L sulfuric acid aqueous solution and refluxed at 80 °C for 6 h to obtain the refluxed solid phase;

[0112] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 11

[0113] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0114] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 0.5 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetrachlorophenylporphyrin iron, the precious metal precursor is chloroplatinic acid and potassium chloroplatinate, the molar ratio of chloroplatinic acid and potassium chloroplatinate is 1:1, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of water; the dissolution can be performed by heating.

[0115] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 8 to obtain system B; the carbon support is carbon black EC300JD, carbon black BP2000, and carbon black VXC-72, and the mass ratio of carbon black EC300JD, carbon black BP2000, and carbon black VXC-72 is 1:2:1; the ultrasonic dispersion time can be 30min; the pH is adjusted with an alkaline solution, which is a mixture of sodium hydroxide solution and potassium hydroxide solution, and the concentration of sodium hydroxide solution and potassium hydroxide solution in the mixture is 2 mol / L, with a volume ratio of 1:1;

[0116] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0117] Step 4: Treat the solid phase at 380 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 650 °C for 180 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0118] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 1.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 3 h to obtain the refluxed solid phase;

[0119] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 12

[0120] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0121] Step 1: Dissolve 1.9 g of a non-precious metal precursor and 3.2 mmol of a precious metal precursor in 2 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetra-p-methoxyphenylporphyrin iron, the precious metal precursor is potassium chloroplatinate and potassium chloroplatinate, the molar ratio of potassium chloroplatinate to potassium chloroplatinate is 1:2, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is N,N-dimethylformamide, and the volume of the organic solvent in the mixed solvent is twice the volume of water; the dissolution can be performed by heating.

[0122] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon black EC600JD, carbon black BP2000, and carbon black EC300JD, and the mass ratio of carbon black EC600JD, carbon black BP2000, and carbon black EC300JD is 1:1:2; the ultrasonic dispersion time can be 30min; the pH is adjusted with an alkaline solution, which is a mixture of ammonia water and sodium hydroxide solution, the concentration of both ammonia water and sodium hydroxide solution in the mixture is 2 mol / L, and the volume ratio of ammonia water and sodium hydroxide solution is 1:1;

[0123] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0124] Step 4: Treat the solid phase at 400 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0125] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 1 mol / L sulfuric acid aqueous solution and refluxed at 80 °C for 6 h to obtain the refluxed solid phase;

[0126] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 13

[0127] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0128] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is iron phthalocyanine, the precious metal precursor is sodium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is methanol, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0129] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is activated carbon, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution with a concentration of 2 mol / L, which is a lithium hydroxide solution.

[0130] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0131] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0132] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 90℃ for 4 h to obtain the refluxed solid phase;

[0133] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 14

[0134] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0135] Step 1: Dissolve 1.9 g of a non-precious metal precursor and 3.2 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is μ-oxy-bis(tetraphenylporphyrin) iron, the precious metal precursor is sodium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is anhydrous ethanol, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0136] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is graphene, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution with a concentration of 2 mol / L, which is a lithium hydroxide solution.

[0137] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0138] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0139] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0140] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 15

[0141] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0142] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1.5 L of a mixed solvent to obtain system A; the non-precious metal precursor is bis(tetrachlorophenyl)ferroporphyrin, the precious metal precursor is sodium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is formamide, and the volume of the organic solvent in the mixed solvent is 3 times the volume of the water; the dissolution can be performed by heating.

[0143] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon nanotubes, the ultrasonic dispersion time can be 30min, and the pH is adjusted by using an alkaline solution with a concentration of 2 mol / L, which is a sodium carbonate solution.

[0144] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0145] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0146] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 90℃ for 4 h to obtain the refluxed solid phase;

[0147] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 16

[0148] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0149] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is 5,10,15,20-tetra(pentafluorophenyl)porphyrin iron, the precious metal precursor is ammonium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is dimethyl sulfoxide, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0150] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is carbon fiber, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution with a concentration of 2 mol / L, which is a sodium oxalate solution.

[0151] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0152] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0153] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 70℃ for 4 h to obtain the refluxed solid phase;

[0154] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 17

[0155] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0156] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetra(2-naphthyl)porphyrin iron, the precious metal precursor is ammonium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is acetonitrile, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0157] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 9.5 to obtain system B; the carbon support is fullerene, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 3mol / L, and the alkaline solution is sodium phosphate solution.

[0158] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0159] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0160] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 75℃ for 4 h to obtain the refluxed solid phase;

[0161] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 18

[0162] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0163] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is cobalt phthalocyanine, the precious metal precursor is ammonium platinocyanate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is anhydrous ethanol and formamide, the volume ratio of anhydrous ethanol to formamide is 1:1, and the volume of the organic solvent in the mixed solvent is twice the volume of water; the dissolution can be performed by heating.

[0164] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is foamed carbon, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution with a concentration of 5 mol / L, which is a lithium hydroxide solution.

[0165] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0166] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 850 °C for 60 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0167] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0168] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 19

[0169] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0170] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is tetratetramethoxyphenylporphyrin cobalt, the precious metal precursor is ammonium chloroplatinate, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is dimethyl sulfoxide and acetonitrile, the volume ratio of dimethyl sulfoxide to acetonitrile is 2:1, and the volume of the organic solvent in the mixed solvent is twice the volume of the water; the dissolution can be performed by heating.

[0171] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 9.5 to obtain system B; the carbon support is activated carbon and carbon nanotubes, the mass ratio of activated carbon to carbon nanotubes is 1:1, the ultrasonic dispersion time can be 30min, and the pH is adjusted with an alkaline solution, the concentration of which is 0.05mol / L, and the alkaline solution is a sodium carbonate solution;

[0172] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0173] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0174] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0175] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 20

[0176] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0177] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin cobalt, the precious metal precursor is ammonium chloroplatinate and ammonium chloroplatinate, the molar ratio of ammonium chloroplatinate to ammonium chloroplatinate is 1:1, the mixed solvent is a mixture of water and an organic solvent, the organic solvent is methanol, anhydrous ethanol and formamide, the volume ratio of methanol, anhydrous ethanol and formamide is 1:2:1, and the volume of the organic solvent in the mixed solvent is 1 times the volume of water; the dissolution can be performed by heating.

[0178] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 10 to obtain system B; the carbon support is activated carbon, carbon fiber, and graphene, with a mass ratio of activated carbon, carbon fiber, and graphene of 2:1:1; the ultrasonic dispersion time can be 30min; the pH is adjusted using an alkaline solution, which is an aqueous solution containing sodium carbonate and sodium oxalate, with a concentration of 2 mol / L and a molar ratio of 1:1;

[0179] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0180] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 850 °C for 60 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0181] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0182] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst. Example 21

[0183] This embodiment provides a method for preparing a noble metal electrocatalyst supported on a non-noble metal material, including:

[0184] Step 1: Dissolve 1.5 g of a non-precious metal precursor and 3.5 mmol of a precious metal precursor in 1 L of a mixed solvent to obtain system A; the non-precious metal precursor is manganese phthalocyanine, and the precious metal precursor is sodium chloroplatinate and sodium chloroplatinate, with a molar ratio of 1:1; the mixed solvent is a mixture of water and an organic solvent, wherein the organic solvent is methanol, formamide, dimethyl sulfoxide, and acetonitrile, with a volume ratio of 1:2:1:1; and the volume of the organic solvent in the mixed solvent is 6 times the volume of the water; the dissolution can be performed by heating.

[0185] Step 2: Add 4g of carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 9.5 to obtain system B; the carbon support is graphene and fullerene, the mass ratio of graphene to fullerene is 1:3, the ultrasonic dispersion time can be 30min, the pH is adjusted with an alkaline solution, the concentration of the alkaline solution is 3mol / L, and the alkaline solution is sodium phosphate solution;

[0186] Step 3: The solvent in system B is evaporated by rotary evaporation at 100 °C to obtain a solid phase;

[0187] Step 4: Treat the solid phase at 350 °C for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 700 °C for 120 min in an Ar atmosphere to obtain the atmosphere-treated solid phase.

[0188] Step 5: The solid phase after atmosphere treatment is ultrasonically dispersed in 1 L of 0.5 mol / L sulfuric acid aqueous solution and refluxed at 80℃ for 4 h to obtain the refluxed solid phase;

[0189] Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase at 80 °C to obtain a non-precious metal material supported on a precious metal electrocatalyst.

[0190] Performance evaluation:

[0191] Figure 1 This is a transmission electron microscope (TEM) image of a noble metal electrocatalyst supported on a non-noble metal material, as described in Example 1. Figure 1 It can be seen that the Pt particles in the catalyst are uniformly supported on the surface of the support.

[0192] Figure 2 The image shown is a transmission electron microscope (TEM) image of the electrocatalyst in Comparative Example 1, based on... Figure 2 It is evident that, after changing the amount of non-precious metal precursor added, both non-precious metals and precious metals exhibited varying degrees of aggregation.

[0193] Figure 3This is a schematic diagram illustrating the electrochemical performance determination of the non-noble metal material-supported noble metal electrocatalyst of Example 1 using the standard three-electrode method. Table 1 shows the electrochemical performance results of Examples 1-21 and Comparative Examples 1-6 determined using the standard three-electrode method. The test method included: fabricating a thin-film working electrode from the non-noble metal material-supported noble metal electrocatalyst, forming a three-electrode electrochemical system with a reference electrode RHE and a platinum counter electrode, and placing them together in an electrode reaction cell. The test was conducted in an oxygen-saturated 0.1 mol / L HClO4 aqueous solution at 25 °C. The potential scan was performed at a voltage of 0-1.2 V (vs. RHE), and the results are shown in Table 1. According to Table 1, the half-wave potential of the electrocatalyst in Example 1 is 0.891 V (vs. RHE), and the specific activity at 0.9 V is 349 mA / mg. Pt -1 .

[0194] In Example 1, the electrocatalyst exhibited a half-wave potential decay of only 3 mV after 30,000 cycles of potentiodynamic scanning (0.6~1.0 V).

[0195] A comparison of the half-wave potential and mass-to-specific activity of the electrocatalysts prepared in different embodiments is shown in Table 1. The mass-to-specific activity was calculated as follows: MA = I K / [L pt *A g ]

[0196] Among them: I K =I lim *i / (I lim -i);

[0197] MA: Mass-specific activity, unit mA / mg;

[0198] I K Dynamic current, measured in mA;

[0199] L pt The loading of noble metals on the thin-film working electrode; unit: mg. pt cm -2 , of which mg pt For the quality of precious metals;

[0200] A g The area of ​​the thin-film working electrode, in cm². 2 ;

[0201] I lim Limiting current, in mA;

[0202] i: LSV measured current at a given voltage (0.9V), in mA.

[0203] Table 1 Half-wave potential and mass ratio activity

[0204] Half-wave potential (V vs. RHE) <![CDATA[Specific activity by mass (mA / mg Pt )]]> Example 1 0.891 349 Example 2 0.884 330 Example 3 0.890 378 Example 4 0.895 391 Example 5 0.889 344 Example 6 0.902 402 Example 7 0.889 377 Example 8 0.878 315 Example 9 0.880 320 Example 10 0.881 322 Example 11 0.882 318 Example 12 0.881 326 Example 13 0.876 312 Example 14 0.877 320 Example 15 0.878 315 Example 16 0.878 322 Example 17 0.877 317 Example 18 0.876 312 Example 19 0.875 312 Example 20 0.876 316 Example 21 0.875 310 Comparative Example 1 0.814 201 Comparative Example 2 0.801 194 Comparative Example 3 0.771 141 Comparative Example 4 0.830 225 Comparative Example 5 0.799 197 Comparative Example 6 0.851 277

[0205] As shown in Table 1, the non-noble metal material-supported noble metal electrocatalyst prepared by the method of this invention, when used as the working electrode, exhibits a half-wave potential above 0.875 V vs. RHE and a specific activity above 310 mA / mg. Pt， It exhibits significantly higher electrocatalytic performance than the comparative example.

[0206] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation on the present invention. Any simple modifications, alterations, or equivalent structural changes made to the above embodiments based on the technical essence of the invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a non-noble metal supported noble metal electrocatalyst, characterized in that, include: Step 1: Dissolve the non-precious metal precursor and the precious metal precursor in a mixed solvent to obtain system A; In system A, the concentration of the noble metal precursor is 1 mmol / L to 7 mmol / L, and the concentration of the non-noble metal precursor is 0.9 g / L to 3 g / L. The non-noble metal precursor is hematoxylin, tetra-p-tolylporphyrin iron, tetra-p-chlorophenylporphyrin iron, tetra-p-methoxyphenylporphyrin iron, phthalocyanine iron, μ-oxo-bis(tetraphenylporphyrin iron), bis(tetrachlorophenylporphyrin), 5,10,15,20-tetra(pentafluorophenyl)porphyrin iron, tetra(2-naphthyl)porphyrin iron, cobalt phthalocyanine, tetra-p-methoxyphenylporphyrin cobalt, 5,10,1 The mixture contains one or more of 5,20-tetra(4-carboxyphenyl)porphyrin cobalt and manganese phthalocyanine; the noble metal precursor is one or more of chloroplatinic acid, chloroplatinic acid, potassium chloroplatinate, potassium chloroplatinic acid, sodium chloroplatinic acid, sodium chloroplatinic acid, ammonium chloroplatinate, and ammonium chloroplatinic acid; the mixed solvent is a mixture of water and an organic solvent, wherein the volume of the organic solvent in the mixed solvent is 1 to 6 times the volume of water, and the organic solvent is one or more of N,N-dimethylformamide, glacial acetic acid, methanol, ethanol, formamide, dimethyl sulfoxide, and acetonitrile; Step 2: Add carbon support to system A, ultrasonically disperse until homogeneous, and adjust the pH of the system to 8-10 to obtain system B; Step 3: Rotary evaporate the system B to obtain a solid phase; Step 4: Treat the solid phase at 350℃~400℃ for 60 min in an NH3 atmosphere, allow it to cool naturally to room temperature, and then treat it at 650℃~850℃ for 60 min~180 min in an Ar atmosphere to obtain the atmosphere-treated solid phase. Step 5: The atmosphere-treated solid phase is ultrasonically dispersed in a 0.5 mol / L to 1.5 mol / L sulfuric acid aqueous solution and refluxed at 70℃ to 90℃ for 3h to 6h to obtain the refluxed solid phase; Step 6: Wash the refluxed solid phase with water until the pH of the filtrate is neutral, and dry the washed solid phase to obtain a non-precious metal material supported on a precious metal electrocatalyst.

2. The method of claim 1, wherein the non-noble metal material is selected from the group consisting of transition metals, post-transition metals, metalloids, and mixtures thereof. In step one, the non-precious metal precursor is one or more of hematoxylin, tetra-p-tolylporphyrin iron, tetra-p-chlorophenylporphyrin iron, and tetra-p-methoxyphenylporphyrin iron; in step one, the precious metal precursor is one or more of chloroplatinic acid, chloroplatinous acid, potassium chloroplatinate, and potassium chloroplatinous acid; in step one, the organic solvent is N,N-dimethylformamide and / or glacial acetic acid.

3. The method for preparing a noble metal electrocatalyst supported on a non-noble metal material according to claim 1, characterized in that, In step two, the carbon carrier is one or more of the following: carbon black EC600JD, carbon black BP2000, carbon black EC300JD, carbon black VXC-72, activated carbon, carbon nanotubes, carbon fibers, graphene, fullerene, and carbon foam.

4. The method of claim 3, wherein the non-noble metal material is selected from the group consisting of transition metals, post-transition metals, metalloids, and mixtures thereof. In step two, the carbon carrier is one or more of carbon black EC600JD, carbon black BP2000, carbon black EC300JD, and carbon black VXC-72.

5. The method of claim 1, wherein the non-noble metal material is selected from the group consisting of transition metals, post-transition metals, metalloids, and mixtures thereof. In step two, the pH is adjusted to 8-10 using an alkaline solution, which is one or more of the following: potassium hydroxide solution, ammonia water, sodium hydroxide solution, sodium bicarbonate solution, potassium carbonate solution, lithium hydroxide solution, sodium carbonate solution, sodium oxalate solution, and sodium phosphate solution.

6. The method of claim 5, wherein the non-noble metal material is selected from the group consisting of transition metals, post-transition metals, metalloids, and mixtures thereof. In step two, the alkaline solution is one or more of potassium hydroxide solution, ammonia water, sodium hydroxide solution, sodium bicarbonate solution, and potassium carbonate solution.

7. The method of claim 6, wherein the non-noble metal material is selected from the group consisting of transition metals, post-transition metals, metalloids, and mixtures thereof. In step two, the concentration of the alkali solution is 0.05 mol / L to 5 mol / L; in step two, the carbon support content in system B is 2 g / L to 8 g / L.

8. The method of claim 1, wherein the non-noble metal material is selected from the group consisting of transition metals, post-transition metals, metalloids, and mixtures thereof. In step five, the volume of the sulfuric acid aqueous solution is 0.5 to 2 times the volume of the mixed solvent in step one.

9. The application of a non-precious metal supported precious metal electrocatalyst prepared by the preparation method of the non-precious metal supported precious metal electrocatalyst according to claim 1 in a proton exchange membrane fuel cell.

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