Preparation method of non-noble metal medium / high-entropy alloy aerogel electrocatalytic material

Abstract

The invention discloses a preparation method of a non-noble metal medium / high-entropy alloy aerogel electro-catalytic material, which comprises the following steps: dissolving at least three metal salts in equal molar ratio or approximate equal molar ratio in a solvent, then adding polyvinylpyrrolidone, uniformly stirring, then adding a chelating agent, and uniformly mixing to obtain a solution B; adding an alkali solution into a reducing agent, providing an alkaline condition with the pH value greater than or equal to 10 for the reducing agent to obtain a solution C, then adding the solution C into the solution B, and stirring for reaction to obtain a reaction solution; standing the reaction liquid to form integral gel, so as to obtain a crude product, namely high-entropy alloy wet gel; and washing the high-entropy alloy wet gel with a solvent for 3-5 times, and freeze-drying the washed product to obtain the high-entropy alloy aerogel. The process provided by the invention has the advantages of low energy consumption, low cost, high product stability and the like, and has good large-scale production potential.

Description

Technical Field

[0001] This invention relates to the field of medium / high entropy alloy aerogel technology. Specifically, it relates to a method for preparing a non-precious metal medium / high entropy alloy aerogel electrocatalytic material. Background Technology

[0002] Electrocatalytic hydrogen evolution reaction (HER) is a core component of water electrolysis hydrogen production technology, and the efficiency and cost of its catalysts directly affect the feasibility of a green hydrogen economy. Currently, the best-performing platinum-based catalysts are limited by their extreme scarcity in the Earth's crust and high cost. Furthermore, their slow kinetics in alkaline media and susceptibility to nanoparticle aggregation and deactivation under long-term operation severely restrict their large-scale industrial application. Although non-precious metal materials such as transition metal phosphides and sulfides offer low-cost alternatives, they typically suffer from inherent drawbacks such as limited active site density, poor intrinsic activity, and insufficient stability over a wide pH range. To overcome these bottlenecks, material design concepts are evolving from single-component to multi-component synergistic approaches.

[0003] Since the concept of "high entropy" was first proposed by British scholar Cantor in 2004 (Cantor B, Chang IT H, et al. Materials Science and Engineering: A, 2004, 375:213-2), high entropy materials have become a hot topic in materials science research, providing new ideas for the optimized design and performance improvement of materials. High entropy alloys (HEAs), with their unique "cocktail effect" and continuous lattice distortion effect, provide a novel electronic structure platform for precisely controlling the adsorption / desorption behavior of reaction intermediates. Studies have shown that high entropy alloys composed of five or more principal components can form multi-site synergistic catalytic centers in their complex surface chemical environment, thereby significantly enhancing intrinsic activity and improving durability. However, the synthesis of high entropy alloy nanomaterials, especially avoiding phase separation and obtaining uniform composition, still faces the challenge of huge differences in the reduction kinetics of different metal precursors. At the same time, the design of the macroscopic structure of the material is also crucial: traditional powder catalysts are prone to stacking during electrode preparation, resulting in the burial of a large number of active sites, and hindering electrolyte penetration and product bubble release.

[0004] For example, Chinese patent application CN120901278A discloses a general synthesis method for medium-entropy / high-entropy alloy nanoparticles and its application; including the following steps: 1) Dissolving three or more metal precursor salts in deionized water according to the required molar ratio, and sonicating until completely dissolved to obtain metal precursor solution A; 2) Adding polyvinylpyrrolidone as a stabilizer to solution A and stirring evenly; 3) Slowly adding 0.3-0.5M sodium borohydride solution as a reducing agent to solution A under stirring conditions to form reaction solution B; 4) Reacting reaction solution B at a constant temperature of 60-80℃ for 4-5 hours to form a uniform nanoparticle colloid; 5) Centrifuging, washing, and freeze-drying the nanoparticle colloid to obtain black powdered alloy nanoparticles. The reaction temperature of this preparation method is <90℃; the overpotential exhibited by the alloy nanoparticles in HER is <30mV@10mA / cm. 2 However, the above-mentioned patented technology still has the following drawbacks: if the concentration of polyvinylpyrrolidone is too high, the synthesized high-entropy alloy particles are prone to agglomeration, resulting in a large number of active sites being blocked.

[0005] Against this backdrop, aerogel structures with three-dimensional continuous porous networks have emerged as a promising solution. Their ultra-high specific surface area and open pore structure not only create conditions for exposing high-density active sites, but also provide an ideal way to achieve rapid mass transfer of reactants and instantaneous detachment of bubbles.

[0006] Therefore, the innovative integration of the high economic efficiency of non-precious metal elements, the electronic structure optimization capability of high-entropy alloys, and the superior macroscopic structural characteristics of aerogels to construct non-precious metal medium / high-entropy alloy aerogels is expected to synergistically solve the balance problem between activity, stability, and mass transfer efficiency, opening up a very promising research direction for the development of next-generation high-performance, low-cost HER catalysts. Summary of the Invention

[0007] The technical problem to be solved by this invention is to provide a method for preparing non-precious metal medium / high entropy alloy aerogel electrocatalysts. This method combines the synergistic effect of non-precious metal elements and high entropy alloy components with the advantages of the three-dimensional porous structure of aerogels, thereby obtaining a hydrogen evolution reaction (HER) electrocatalyst with high activity, high stability, and excellent mass transfer performance. This method is simple, low-cost, and suitable for large-scale production. The product obtained by this invention is a three-dimensional porous nanosheet.

[0008] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: A method for preparing a non-noble metal medium / high entropy alloy aerogel electrocatalytic material includes the following steps: 1) Dissolve at least three metal salts in an equimolar or approximately equimolar ratio in a solvent to obtain a mixed metal precursor solution; 2) Add polyvinylpyrrolidone as a stabilizer to the mixed metal precursor solution, stir until homogeneous, and obtain solution A; 3. Add a chelating agent to solution A and mix well to obtain solution B; 4) Add the alkaline solution to the reducing agent to provide alkaline conditions with a pH value greater than 10, to obtain solution C. Then add solution C to solution B and stir to react, to obtain the reaction solution. 5) The reaction solution is allowed to stand to form a whole gel, and the crude product high-entropy alloy wet gel is obtained. 6) Wash the obtained high-entropy alloy wet gel with solvent 3-5 times, and then freeze-dry the washed product under vacuum to finally obtain high-entropy alloy aerogel.

[0009] Preferably, in step 1), the metal salt is selected from at least three of the following metal salts: cobalt salt, platinum salt, copper salt, nickel salt, manganese salt, iron salt, palladium salt, zinc salt, bismuth salt, chromium salt, rhodium salt, and ruthenium salt.

[0010] Preferably, the cobalt salt is one of cobalt sulfate, cobalt chloride hexahydrate, cobalt acetate, and cobalt nitrate; the platinum salt is one of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, and platinum chloride; the copper salt is one of copper nitrate pentahydrate, copper sulfate, copper carbonate, and copper chloride trihydrate; the nickel salt is one of nickel chloride, nickel nitrite, nickel sulfate, and nickel acetate; the manganese salt is one of manganese chloride and manganese sulfate; the iron salt is one of ferric chloride, ferrous chloride, ferric nitrate, and ferrous nitrate; the palladium salt is one of palladium chloride, potassium chloropalladate, and sodium tetrachloropalladate; the zinc salt is zinc chloride; the bismuth salt is bismuth chloride; the chromium salt is chromium chloride; the rhodium salt is rhodium chloride; and the ruthenium salt is ruthenium trichloride.

[0011] Preferably, in step 1), the concentration of each metal salt in the mixed metal precursor solution is 0.02~0.08 mol / L; more preferably, it is 0.03~0.05 mol / L.

[0012] Preferably, in step 1), the solvent is selected from one or more of the following substances: purified water, ethanol, and isopropanol.

[0013] Preferably, in step 2), the ratio of polyvinylpyrrolidone to metal salt is 20 mg: 0.1 mmol.

[0014] Preferably, in step 3), the chelating agent is selected from one or more of the following substances: ethylenediaminetetraacetic acid tetranatate (EDTA-Na), sodium citrate (NaCA), salicylic acid (SA), 4,4-bipyridine, 4,5-imidazolium dicarboxylic acid; the ratio of the chelating agent to a metal salt is 0.06 mmol:0.1 mmol.

[0015] Preferably, in step 4), the alkali is one of sodium hydroxide and potassium hydroxide.

[0016] Preferably, in step 4), the reducing agent is one of sodium borohydride, potassium borohydride, and lithium borohydride.

[0017] Preferably, in step 4), the molar ratio of the reducing agent to the alkali is 1 mol / L: 0.3~0.8 mol / L; more preferably, it is 1 mol / L: 0.4~0.6 mol / L.

[0018] Preferably, in step 4), the concentration of the reducing agent in solution C is 0.1~0.5 mol / L; more preferably, it is 0.2~0.3 mol / L.

[0019] Preferably, in step 4), the stirring reaction time is 2-5 hours; more preferably, the stirring reaction time is 1.5-2 hours.

[0020] Preferably, in step 5), the settling time is 5-8 hours; more preferably, the settling time is 5-6 hours.

[0021] Preferably, in step 6), the solvent is one or more of pure water, ethanol, methanol, and isopropanol.

[0022] Preferably, in step 6), the freezing temperature of the low-temperature freeze-drying vacuum drying is -50℃ to -150℃, and the preferred freezing temperature is -90℃; the time is 20-30 h.

[0023] Any range described in this invention includes the endpoint, any value between the endpoints, and any subrange consisting of the endpoint or any value between the endpoints.

[0024] Unless otherwise specified, all raw materials used in this invention can be obtained commercially, and the equipment used in this invention can be conventional equipment in the relevant field or refer to existing technology in the relevant field.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1) The preparation route of the present invention, which is a one-step liquid phase chemical reduction combined with freeze drying, is simple, has mild reaction conditions (room temperature and pressure), does not require complex equipment or high-temperature post-treatment, and has low energy consumption and high safety.

[0027] 2) This invention achieves synergistic optimization of material properties by innovatively integrating non-precious metal elements, high-entropy alloying strategies, and aerogel structures.

[0028] 3) The non-precious metal medium / high entropy alloy aerogel prepared by this invention has a cost that is much lower than that of precious metal aerogel, and has a significant cost advantage. Attached Figure Description

[0029] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings. Figure 1 This is a high-magnification transmission electron microscope image of the high-entropy alloy aerogel prepared in Example 1 of this invention; Figure 2 This is the energy spectrum of the high-entropy alloy aerogel prepared in Example 1 of the present invention; Figure 3 This is a high-magnification transmission electron microscope image of the high-entropy alloy aerogel prepared in Comparative Example 1 of this invention. Figure 4 This is a high-magnification transmission electron microscope image of the medium-entropy alloy aerogel prepared in Example 2 of this invention; Figure 5 This is the energy spectrum of the medium-entropy alloy aerogel prepared in Example 2 of this invention. Detailed Implementation

[0030] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0031] Various cross-sectional views of embodiments of the present invention are shown in the accompanying drawings. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0032] As one aspect of the present invention, a method for preparing a non-noble metal medium / high entropy alloy aerogel electrocatalytic material includes the following steps: 1) Dissolve at least three metal salts in an equimolar or approximately equimolar ratio in a solvent to obtain a mixed metal precursor solution; 2) Add polyvinylpyrrolidone as a stabilizer to the mixed metal precursor solution, stir until homogeneous, and obtain solution A; 3. Add a chelating agent to solution A and mix well to obtain solution B; 4) Add the alkaline solution to the reducing agent to provide alkaline conditions with a pH value greater than 10, to obtain solution C. Then add solution C to solution B and stir to react, to obtain the reaction solution. 5) The reaction solution is allowed to stand to form a whole gel, and the crude product high-entropy alloy wet gel is obtained. 6) Wash the obtained high-entropy alloy wet gel with solvent 3-5 times, and then freeze-dry the washed product under vacuum to finally obtain high-entropy alloy aerogel.

[0033] According to certain embodiments of the present invention, in step 1), the metal salt is selected from at least three of the following metal salts: cobalt salt, platinum salt, copper salt, nickel salt, manganese salt, iron salt, palladium salt, zinc salt, bismuth salt, chromium salt, rhodium salt, and ruthenium salt.

[0034] According to certain embodiments of the present invention, the cobalt salt is one of cobalt sulfate, cobalt chloride hexahydrate, cobalt acetate, and cobalt nitrate; the platinum salt is one of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, and platinum chloride; the copper salt is one of copper nitrate pentahydrate, copper sulfate, copper carbonate, and copper chloride trihydrate; the nickel salt is one of nickel chloride, nickel nitrite, nickel sulfate, and nickel acetate; the manganese salt is one of manganese chloride and manganese sulfate; the iron salt is one of ferric chloride, ferrous chloride, ferric nitrate, and ferrous nitrate; the palladium salt is one of palladium chloride, potassium chloropalladate, and sodium tetrachloropalladate; the zinc salt is zinc chloride; the bismuth salt is bismuth chloride; the chromium salt is chromium chloride; the rhodium salt is rhodium chloride; and the ruthenium salt is ruthenium trichloride.

[0035] According to some embodiments of the present invention, in step 1), the concentration of each metal salt in the mixed metal precursor solution is 0.02~0.08 mol / L; preferably 0.03~0.05 mol / L.

[0036] According to certain embodiments of the present invention, in step 1), the solvent is selected from one or more of the following substances: purified water, ethanol, and isopropanol.

[0037] According to certain embodiments of the present invention, in step 2), the ratio of polyvinylpyrrolidone to metal salt is 20 mg: 0.1 mol.

[0038] According to certain embodiments of the present invention, in step 3), the chelating agent is selected from one or more of the following substances: ethylenediaminetetraacetic acid tetranatate (EDTA-Na), sodium citrate (NaCA), salicylic acid (SA), 4,4-bipyridine, 4,5-imidazolium dicarboxylic acid; the ratio of the chelating agent to a metal salt is 0.06 mmol:0.1 mmol.

[0039] According to certain embodiments of the present invention, in step 4), the alkali is one of sodium hydroxide and potassium hydroxide.

[0040] According to certain embodiments of the present invention, in step 4), the reducing agent is one of sodium borohydride, potassium borohydride, and lithium borohydride.

[0041] According to certain embodiments of the present invention, in step 4), the molar ratio of the reducing agent to the base is 1:0.3mol / L to 0.8mol / L; preferably 1mol / L:0.4 to 0.6mol / L.

[0042] According to some embodiments of the present invention, in step 4), the concentration of the reducing agent in solution C is 0.1~0.5 mol / L; more preferably 0.2~0.3 mol / L.

[0043] According to certain embodiments of the present invention, the stirring reaction time is 2-5 hours; preferably, the stirring reaction time is 1.5-2 hours.

[0044] According to some embodiments of the present invention, the settling time is 5 to 8 hours; preferably, the settling time is 5 to 6 hours.

[0045] According to certain embodiments of the present invention, the solvent is one or more of purified water, ethanol, methanol, and isopropanol.

[0046] According to certain embodiments of the present invention, the freezing temperature of the low-temperature freeze-drying is -50°C to -150°C, preferably -90°C; and the time is 20-30 hours. Example 1

[0047] A method for preparing a non-noble metal high-entropy alloy aerogel electrocatalytic material includes the following steps: 1) Mix ferric chloride, nickel chloride, cobalt chloride hexahydrate, copper chloride trihydrate, and zinc chloride in equal proportions of 0.1 mmol, dissolve in 40 ml of deionized water to obtain a mixed metal precursor solution; mix the mixed metal precursor solution by ultrasonication until homogeneous. 2) Add 100 mg of polyvinylpyrrolidone (PVP) to the mixed metal precursor solution and stir until homogeneous to obtain solution A; 3. Then add 100 mg of ethylenediaminetetraacetic acid to solution A and mix well to obtain solution B; 4) Dissolve 1.6 g of sodium hydroxide in 40 ml of deionized water, then add 100 mg of sodium borohydride reducing agent and mix well to obtain solution C; add the prepared solution C to solution B and stir to react to obtain the reaction solution; 5) The reaction solution was allowed to stand to form a black hydrogel, yielding the crude product FeCoNiCuZn high-entropy alloy wet gel. 6) The obtained FeCoNiCuZn high-entropy alloy wet gel was washed 5 times with deionized water. The washed product was then subjected to freeze-drying at -90℃ for 24h to finally obtain FeCoNiCuZn high-entropy alloy aerogel.

[0048] Figure 1 This is a high-magnification transmission electron microscope image of the FeCoNiCuZn high-entropy alloy aerogel prepared in this embodiment.

[0049] Figure 2 This is the energy spectrum of the FeCoNiCuZn high-entropy alloy aerogel prepared in this embodiment. Comparative Example 1

[0050] Repeat step 1: The only difference is that the metal precursor solution is injected into the reducing agent.

[0051] The results show that the high-entropy alloy aerogel catalyst prepared in this comparative example exhibits significant nanosheet aggregation. This is mainly because during the reaction, the metal precursor is rapidly reduced, resulting in newly formed nanosheets with extremely high surface energy and a lack of effective spatial barriers or structural support. This causes them to rapidly approach each other and aggregate uncontrollably under the influence of van der Waals forces. This intense aggregation behavior disrupts the possibility of forming an ideal three-dimensional porous network, instead forming dense and aggregated nanosheets, thus severely reducing the specific surface area and the number of exposed active sites.

[0052] Figure 3 The image shown is a high-magnification transmission electron microscope (TEM) image of the high-entropy alloy catalyst particles prepared in this comparative example. Example 2

[0053] A method for preparing a non-noble metal medium-entropy alloy aerogel electrocatalytic material includes the following steps: 1) Mix ferric chloride, nickel chloride, cobalt chloride hexahydrate, and copper chloride trihydrate in equal proportions of 0.1 mmol, dissolve in 40 ml of deionized water to obtain a mixed metal precursor solution; mix the mixed metal precursor solution by ultrasonication until homogeneous. 2) Add 80 mg of polyvinylpyrrolidone (PVP) to the mixed metal precursor solution and stir until homogeneous to obtain solution A; 3. Then add 80 mg of ethylenediaminetetraacetic acid to solution A and mix well to obtain solution B; 4) Dissolve 1.6 g of sodium hydroxide in 40 ml of deionized water, then add 80 mg of sodium borohydride reducing agent and mix well to obtain solution C; add the prepared solution C to solution B and stir to react to obtain reaction solution; 5) The reaction solution was allowed to stand to form a black hydrogel, yielding the crude product FeCoNiCu medium-entropy alloy wet gel. 6) The obtained FeCoNiCu medium-entropy alloy wet gel was washed 5 times with deionized water. The washed product was then subjected to freeze-drying at -90℃ for 24 h to finally obtain FeCoNiCu medium-entropy alloy aerogel.

[0054] Figure 4The image shown is a high-magnification transmission electron microscope (TEM) image of the FeCoNiCu medium-entropy alloy catalyst particles prepared in this comparative example.

[0055] Figure 5 This is the energy spectrum of the FeCoNiCu medium-entropy alloy aerogel prepared in this embodiment. Comparative Example 2

[0056] A method for preparing a low-cost, high-entropy alloy aerogel electrocatalytic material includes the following steps: A total of 0.075 mmol of palladium chloride, chloroplatinic acid, copper chloride trihydrate, nickel chloride hexahydrate, and ferric chloride hexahydrate in equimolar ratios were dissolved in 15 mL of deionized water and stirred at 20 °C until homogeneous. Sodium borohydride, a reducing agent, was added to the solution at a molar ratio of 1:1 (metal salt to sodium borohydride). The mixture was stirred at 20 °C for 30 min at a stirring speed of 200 r / min to prepare a co-precursor solution. The co-precursor solution was then frozen in liquid nitrogen for 2 min, followed by thawing in a 10 °C water bath. The thawed sample was stirred at 200 r / min for 2 h to form a monolithic gel. The resulting wet gel underwent solvent replacement three times with deionized water, with each replacement occurring 18 h apart. The replaced HEAs wet gel was then frozen in liquid nitrogen for 2 min, followed by freeze-drying at -60 °C for 8 h, ultimately yielding a low-cost, highly catalytically active, and multifunctional PdPtCuNiFe. High-entropy alloy aerogel appears as black lumps.

[0057] This comparative example uses the method disclosed in Chinese Patent (CN119581587A) to prepare PdPtCuNiFe pentagonal high-entropy alloy aerogel as a reference sample.

[0058] In comparison, the FeCoNiCuZn non-noble metal high-entropy alloy aerogel prepared in Example 1 of this invention exhibits significant advantages in both preparation process and cost.

[0059] In terms of process, this invention abandons the reliance on liquid nitrogen freezing in traditional methods, and instead adopts milder and more efficient freeze-drying conditions, significantly reducing energy consumption and process complexity. Regarding cost, the non-precious metal aerogels of this invention all use inexpensive non-precious metal salts, resulting in low cost. While achieving a green and low-carbon preparation process, this invention successfully obtains non-precious metal catalytic materials with superior performance, demonstrating excellent comprehensive advantages and application potential.

[0060] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is impossible to exhaustively list all embodiments here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A method for preparing a non-noble metal medium / high entropy alloy aerogel electrocatalytic material, characterized in that, Includes the following steps: 1) Dissolve at least three metal salts in an equimolar or approximately equimolar ratio in a solvent to obtain a mixed metal precursor solution; 2) Add polyvinylpyrrolidone as a stabilizer to the mixed metal precursor solution, stir until homogeneous, and obtain solution A; 3. Add a chelating agent to solution A and mix well to obtain solution B; 4) Add the alkaline solution to the reducing agent to provide alkaline conditions with a pH value greater than 10, to obtain solution C. Then add solution C to solution B and stir to react, to obtain the reaction solution. 5) The reaction solution is allowed to stand to form a whole gel, and the crude product high-entropy alloy wet gel is obtained. 6) Wash the obtained high-entropy alloy wet gel with solvent 3-5 times, and then freeze-dry the washed product under vacuum to finally obtain high-entropy alloy aerogel.

2. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 1), the metal salt is selected from at least three of the following metal salts: cobalt salt, platinum salt, copper salt, nickel salt, manganese salt, iron salt, palladium salt, zinc salt, bismuth salt, chromium salt, rhodium salt, and ruthenium salt.

3. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 2, characterized in that: The cobalt salt is one of cobalt sulfate, cobalt chloride hexahydrate, cobalt acetate, and cobalt nitrate; the platinum salt is one of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, and platinum chloride; the copper salt is one of copper nitrate pentahydrate, copper sulfate, copper carbonate, and copper chloride trihydrate; the nickel salt is one of nickel chloride, nickel nitrite, nickel sulfate, and nickel acetate; the manganese salt is one of manganese chloride and manganese sulfate; the iron salt is one of ferric chloride, ferrous chloride, ferric nitrate, and ferrous nitrate; the palladium salt is one of palladium chloride, potassium chloropalladate, and sodium tetrachloropalladate; the zinc salt is zinc chloride; the bismuth salt is bismuth chloride; the chromium salt is chromium chloride; the rhodium salt is rhodium chloride; and the ruthenium salt is ruthenium trichloride.

4. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 1), the concentration of each metal salt in the mixed metal precursor solution is 0.02~0.08 mol / L; preferably 0.03~0.05 mol / L.

5. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 1), the solvent is selected from one or more of the following substances: purified water, ethanol, and isopropanol.

6. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 2), the ratio of polyvinylpyrrolidone to metal salt is 20 mg: 0.1 mmol.

7. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 3), the chelating agent is selected from one or more of the following substances: tetrasodium ethylenediaminetetraacetate, sodium citrate, salicylic acid, 4,4-bipyridine, 4,5-imidazolium dicarboxylic acid; the ratio of the chelating agent to a metal salt is 0.06 mmol:0.1 mmol.

8. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 4), the alkali is either sodium hydroxide or potassium hydroxide; Preferably, in step 4), the reducing agent is one of sodium borohydride, potassium borohydride, and lithium borohydride; Preferably, in step 4), the molar ratio of the reducing agent to the base is 1 mol / L: 0.3~0.8 mol / L; more preferably, it is 1 mol / L: 0.4~0.6 mol / L. Preferably, in step 4), the concentration of the reducing agent in solution C is 0.1~0.5 mol / L; more preferably, it is 0.2~0.3 mol / L. Preferably, in step 4), the stirring reaction time is 2-5 h; more preferably, the stirring reaction time is 1.5-2 h.

9. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 5), the settling time is 5-8 hours; preferably, the settling time is 5-6 hours.

10. The preparation method of the non-noble metal medium / high entropy alloy aerogel electrocatalytic material according to claim 1, characterized in that: In step 6), the solvent is one or more of pure water, ethanol, methanol, and isopropanol; Preferably, in step 6), the freezing temperature of the low-temperature freeze-drying vacuum drying is -50℃ to -150℃, and the preferred freezing temperature is -90℃; the time is 20-30h.

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