Preparation method of porous structure Pt-based high-entropy alloy

Abstract

The application discloses a preparation method of a porous Pt-based high-entropy alloy, and comprises the following steps: dissolving a certain amount of a surfactant in deionized water as a reaction solvent; dissolving a precursor platinum salt, a precursor nickel salt, a precursor copper salt and a precursor cobalt salt in the reaction solvent according to a preset molar ratio to obtain a precursor solution A; dissolving a certain amount of a reducing agent in the reaction solvent to obtain a reducing solution; stirring the precursor solution A, heating and dissolving a precursor B of bismuth on a magnetic stirrer into the solvent, and then adding the precursor B into the precursor solution A; adding the reducing solution into a precursor solution C, wherein the precursor solution C is a mixed solution of the precursor solution A and the precursor solution B, to obtain a reaction solution. After stirring the reaction solution, the reaction solution is left to stand at room temperature of 0 DEG C to 80 DEG C for 2 to 10 days, and after the standing is completed, the obtained sample is cleaned and dried at 50 DEG C to 100 DEG C for 6 to 12 hours to obtain the Pt-based high-entropy alloy.

Description

Technical Field

[0001] This invention belongs to the field of new energy materials technology, specifically relating to a method for preparing a porous Pt-based high-entropy alloy. Background Technology

[0002] Direct methanol fuel cells (DMFCs), as a type of proton exchange membrane fuel cell using methanol as fuel, possess advantages such as low operating temperature, high specific energy density, easy packaging and portability of liquid fuel, simple battery structure, and good safety. The efficiency of a methanol fuel cell is primarily determined by the activity of the anode catalyst. Pt, due to its excellent physicochemical properties, is the most effective anode catalyst for DMFCs. However, Pt's low abundance in the Earth's crust, high price, and susceptibility to poisoning by methanol oxidation intermediates (especially CO) hinder its commercial development. Therefore, research into the reaction mechanism of methanol oxidation, the adsorption mechanism of CO on the catalyst, and how oxygen-containing substances that can remove CO function are crucial for understanding catalyst synthesis. Currently, catalysts used for methanol oxidation include pure Pt catalysts, binary alloys, and ternary alloy catalysts. High-entropy alloys containing five or more elements, due to their four core effects—high-entropy effect, cocktail effect, lattice distortion effect, and slow diffusion effect—possess high efficiency and high stability, making them a key research focus for fuel cell anode catalysts. However, there are few reports on high-entropy alloys used in methanol oxidation, and some of the catalytic mechanisms of methanol oxidation remain unclear. Therefore, the application of high-entropy alloys in methanol oxidation faces the following challenges: how to adjust the synergistic effect between elements to achieve ideal methanol oxidation catalytic activity; the easy adsorption of CO, a MOR intermediate, on its surface, which occupies the active sites on the Pt surface, leading to catalyst poisoning and loss of catalytic activity; and the unclear MOR reaction mechanism on the surface of Pt-based nanocatalysts, with unclear reasons for intermediate catalyst poisoning, which restricts the optimal design of catalysts. Summary of the Invention

[0003] Technical problems to be solved:

[0004] This application addresses the shortcomings of existing technologies, solving the technical problems of low Pt reserves in the Earth's crust, high price, and susceptibility to poisoning by methanol oxidation intermediates (especially CO), leading to loss of activity. It provides a method for preparing a porous Pt-based high-entropy alloy. This catalyst preparation process is simple and has low requirements for production conditions. The porous Pt-based high-entropy alloy prepared by this method overcomes the structural stability defects of traditional alloys, achieving improvements in alloy size, morphology, and synergistic effects among multiple elements. This improves the adsorption of hydroxides by Pt-based nanomaterials, while the multi-element regulation of Pt's electronic structure weakens its CO adsorption, thereby inhibiting CO poisoning and improving the material's activity and stability in catalyzing MOR (Methanol-Related Oxidation). Furthermore, based on changes in electrode surface structure and composition, the structure-activity relationship between Pt-based composite materials and MOR is revealed, further guiding the synthesis of novel, highly efficient Pt-based composite materials.

[0005] Technical solution:

[0006] To achieve the above objectives, this application provides the following technical solution:

[0007] A method for preparing a porous Pt-based high-entropy alloy, comprising the following steps:

[0008] Step 1: Dissolve a certain amount of surfactant in deionized water as a reaction solvent, wherein the concentration of surfactant in the reaction solvent is greater than or equal to 0.04 mol / L;

[0009] Step 2: Dissolve the precursor platinum salt, precursor nickel salt, precursor copper salt, and precursor cobalt salt in the reaction solvent according to a preset molar ratio to obtain precursor solution A;

[0010] Step 3: Dissolve a certain amount of reducing agent in the reaction solvent to obtain a reduced solution;

[0011] Step 4: Stir the precursor solution A at a speed of 500-1000 r / min for 10-30 min.

[0012] Step 5: Dissolve 0.1-1g of the precursor bismuth salt in 10-500mL of reaction solvent by heating at 50-150℃ on a magnetic stirrer to obtain bismuth precursor solution B. Then add 1-5mL of bismuth precursor solution B to 10-100mL of precursor solution A (stirred in step 4) at a rate of 1-10mL per second to obtain precursor solution C.

[0013] Step 6: Add 1-10 mL of the reduction solution to 10-100 mL of the precursor solution C at a rate of 1-20 mL per second to obtain the reaction solution. Stir the reaction solution at a speed of 200-2000 r / min for 1-12 h.

[0014] Step 7: After stirring, let it stand at room temperature of 0℃-80℃ for 2-10 days. After standing, clean the sample and dry it at 50℃-100℃ for 6-12 hours to obtain Pt-based high-entropy alloy.

[0015] Furthermore, in the first step, the surfactant is one or a combination of several of cyclodextrin, PVP, and CTAB, and the concentration of the surfactant in the reaction solvent is 0.04-1 mol / L.

[0016] Furthermore, in the precursor solution A, the concentration of platinum ions is 0.02-0.04 mol / L, and the preset molar ratio of the precursor platinum salt, precursor nickel salt, precursor copper salt, and precursor cobalt salt is 1:0.2-1:0.2-1:0.2-1. In the precursor solution C, the concentration of bismuth ions is 0.03-0.06 mol / L.

[0017] Furthermore, the molar ratio of platinum ions to bismuth ions, nickel ions, cobalt ions, and copper ions in the precursor solution C is 1:(1-3):(0.1-1):(0.1-1):(0.1-1).

[0018] Further, the precursor platinum salt is potassium chloroplatinate and / or potassium chloroplatinate; the precursor bismuth salt is bismuth neododecanoate and / or anhydrous bismuth nitrate; the precursor nickel salt is nickel acetate and / or nickel chloride; the precursor cobalt salt is cobalt nitrate and / or cobalt chloride; and the precursor copper salt is copper sulfate and / or copper chloride.

[0019] Further, the reducing agent is sodium borohydride and / or ascorbic acid, and the concentration of the reducing agent in the reducing solution is 0.08-1 mol / L.

[0020] The principle behind the preparation method of the aforementioned porous Pt-based high-entropy alloy is as follows: A solution prepared by dissolving a surfactant in deionized water is used to dissolve precursors of five elements at room temperature. Then, a reducing agent is used to reduce the elements in the precursors. The surfactant generates a porous morphology, and at room temperature, the reducing agent reduces the ions to metal at a relatively slow rate. This results in a high-entropy material with tunable elements and controllable morphology, which can be well applied to methanol oxidation reactions.

[0021] Beneficial effects:

[0022] This application provides a method for preparing a porous Pt-based high-entropy alloy, which has the following advantages compared with the prior art:

[0023] 1. The alloys prepared by this method are composed of 3-6 elements, mainly Pt and Bi, and transition elements such as Ni, Co, Cu, Fe, Mo, and Zn.

[0024] 2. The porous Pt-based high-entropy alloy prepared by this method can overcome the structural stability defects of traditional alloys, and achieve the synergistic effect of alloy size, morphology, structure and multiple elements. It improves the adsorption of hydroxides by Pt-based nanomaterials, and at the same time, the multi-element regulation of Pt electronic structure weakens its adsorption of CO, thereby achieving the purpose of inhibiting CO poisoning and improving the activity and stability of the material in catalyzing MOR.

[0025] 3. Simultaneously, based on the changes in electrode surface structure and composition, the structure-property relationship between Pt-based composite materials and MOR is revealed, further guiding the synthesis of novel and highly efficient Pt-based composite materials.

[0026] 4. During the experimental testing, we measured the mass activity of the Pt-based high-entropy alloy in a 0.5M H₂SO₄ + 0.5M CH₃OH electrolyte solution using cyclic voltammetry to be 0.9 A mg. -1 The result obtained from commercial Pt / C measurements is 0.26 mg. -1 The activity was 3.5 times that of the target; the stability of the Pt-based high-entropy alloy after 3600 s was determined by chronoamperometry in a 0.5 M H₂SO₄ + 0.5 M CH₃OH electrolyte solution, and the remaining activity was 0.1 A mg after the 3600 s stability test. -1 It is a commercial Pt / C (0.018A mg) -1 It is about 5.5 times higher; therefore, it can be seen that the Pt-based high-entropy alloy we prepared has high activity and stability. Attached Figure Description

[0027] Figure 1 The PtBi obtained in Example 1 of this application 1.5 Ni 0.2 Co 0.2 Cu 0.2 Scanning electron microscope (SEM) and transmission electron microscope (TEM) images of high-entropy alloy catalysts, where a represents PtBi. 1.5 Ni 0.2 Co 0.2 Cu 0.2 Scanning electron microscope image of high-entropy alloy catalyst, b is PtBi 1.5 Ni 0.2 Co 0.2 Cu 0.2Transmission electron microscope image of a high-entropy alloy catalyst;

[0028] Figure 2 The PtBi obtained in Example 1 of this invention 1.5 Ni 0.2 Co 0.2 Cu 0.2 Transmission electron microscopy diffraction pattern of high-entropy alloy catalyst;

[0029] Figure 3 The PtBi obtained in Example 1 of this invention 1.5 Ni 0.2 Co 0.2 Cu 0.2 X-ray diffraction pattern of high-entropy alloy catalyst;

[0030] Figure 4 The PtBi obtained in Example 1 of this invention 1.5 Ni 0.2 Co 0.2 Cu 0.2 X-ray photoelectron spectroscopy of high-entropy alloy catalysts;

[0031] Figure 5 The PtBi obtained in Example 1 of this invention 1.5 Ni 0.2 Co 0.2 Cu 0.2 Cyclic voltammetry curves of the catalytic activity of high-entropy alloy catalysts and commercial Pt / C catalysts for methanol oxidation; the small squares in the figure represent PtBi. 1.5 Ni 0.2 Co 0.2 Cu 0.2 Cyclic voltammetric curves of the catalytic activity of high-entropy alloy catalysts for methanol oxidation reaction; small circles represent cyclic voltammetric curves of the catalytic activity of commercial Pt / C catalysts for methanol oxidation reaction.

[0032] Figure 6 The PtBi obtained in Example 1 of this invention 1.5 Ni 0.2 Co 0.2 Cu 0.2 Current-time curves for methanol oxidation reaction using high-entropy alloy catalysts and commercial Pt / C catalysts, where the square lines represent PtBi catalysts. 1.5 Ni 0.2 Co 0.2 Cu 0.2 The current-in-time curves of the methanol oxidation reaction catalytically activated by the high-entropy alloy catalyst are shown. The circular line represents the current-in-time curve of the methanol oxidation reaction catalytically activated by the commercial Pt / C catalyst. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Example 1:

[0035] A method for preparing a porous Pt-based high-entropy alloy, the method specifically includes the following steps:

[0036] Step 1: Mix 4.2562g of cyclodextrin with 250mL of deionized water and sonicate for 30min to obtain the reaction solvent;

[0037] Step 2: Potassium chloroplatinate in a molar ratio of 1:0.2:0.2:0.2 is dissolved in 2 mL of reaction solvent with copper sulfate, nickel acetate, and cobalt nitrate, and then sonicated for 10 s to obtain precursor solution A; wherein, in precursor solution A, platinum ions, copper ions, ...

[0038] The concentrations of nickel ions and cobalt ions were 0.06 mol / L, 0.012 mol / L, 0.012 mol / L, and 0.012 mol / L, respectively.

[0039] Step 3: Add sodium borohydride to 6 mL of reaction solvent and mix, then sonicate for 10 s to obtain a reduced solution; wherein, the concentration of sodium borohydride in the reduced solution is 0.08 mol / L;

[0040] Step 4: Stir the precursor solution A at a speed of 500-1000 r / min for 10-30 min.

[0041] Step 5: Add 20-100 mg of bismuth neododecaned to 3 mL of reaction solvent and dissolve at 120 °C for 15 minutes to obtain bismuth precursor solution B. Add bismuth precursor solution B to precursor solution A at a rate of 1-10 mL per second to obtain precursor solution C.

[0042] Step 6: Add 6 mL of the reduction solution to 54 mL of precursor solution C at a rate of 1-20 mL per second to obtain the reaction solution. Stir the reaction solution at a speed of 700 r / min for 2 h.

[0043] Step 7: After stirring, let it stand at 25℃ for 3 days. After standing, wash the reaction solution at 50℃-100℃.

[0044] The black solid powder is obtained by drying for 6-12 hours. The black solid powder is a Pt-based high-entropy alloy.

[0045] The Pt-based high-entropy alloy catalysts obtained above were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), such as... Figure 1 As shown in figure a, the morphology of the obtained Pt-based high-entropy alloy is a porous structure, further as shown in figure a. Figure 1 As shown in b, the nanosheet exhibits distinct lattice fringes with a lattice spacing of 0.21 nm, corresponding to the (111) plane of pure Pt. Meanwhile, as... Figure 2 The image shows the observation of PtBi using the diffraction mode (SEAD) of a transmission electron microscope. 1.5 Ni 0.2 Co 0.2 Cu 0.2 The high-entropy alloy catalyst was found to have a polycrystalline structure.

[0046] The above-mentioned PtBi 1.5 Ni 0.2 Co 0.2 Cu 0.2 The high-entropy alloy catalyst was scanned using an X-ray diffractometer, and the results are as follows: Figure 3 As shown, it can be seen that all XRD spectral peaks correspond to the face-centered cubic phase of Pt (JCPDF, 04-0802). Among them, the diffraction peaks 2θ = 39.9°, 46.4°, 67.7° and 81.6° can be indexed as the (111), (200), (220) and (311) planes of pure Pt.

[0047] Further X-ray photoelectron spectroscopy was used to detect PtBi. 1.5 Ni 0.2 Co 0.2 Cu 0.2 The valence states of Pt components in high-entropy alloy catalysts, such as Figure 4 As shown, for the Pt element, a pair of peaks appears at 72.6 eV and 69.1 eV, which can be attributed to Pt. 0 and Pt 3+ The existence of PtBi in the above system can therefore be proven. 1.5 Ni 0.2 Co 0.2 Cu 0.2 High-entropy alloys are high-entropy alloys with Pt as the main metal.

[0048] Methanol Oxidation (MOR) Catalytic Activity Test:

[0049] (1) Preparation of catalytic electrode

[0050] The PtBi prepared above 1.5 Ni 0.2 Co 0.2 Cu0.2 High-entropy alloy catalyst and Vulcan XC-72 carbon (40% of the Pt catalyst) were dispersed in 1 mL of water and Nafion solution (where Vwater / VNafion solution = 1:0.03), and then sonicated for 30 min to form a homogeneous ink. The amount of Pt in the catalyst was controlled based on ICP test data, and the Pt loading was maintained at 35 μg / cm2. 2 2.8 μL of ink was dropped onto a glassy carbon electrode with an area of ​​3 mm, and then allowed to air dry at room temperature before use.

[0051] (2) MOR test

[0052] MOR was performed at a scan rate of 50 mV / s in Ar-saturated 0.5 mol / L H₂SO₄ + 0.5 mol / L CH₃OH. Long-term stability of the prepared samples was determined by chronoamperometry at 0.66 V (relative to a saturated calomel electrode, SCE) in a 0.5 mol / L H₂SO₄ solution containing 0.5 mol / L CH₃OH. For comparison, commercial Pt / C (20 wt% Pt nanoparticles supported on Vulcan XC-72 carbon, Aladdin) was prepared using the same procedures and testing methods.

[0053] PtBi obtained in Example 1 1.5 Ni 0.2 Co 0.2 Cu 0.2 The MOR performance of the high-entropy alloy catalyst was tested using a KOST workstation in a three-electrode system. In the three-electrode system, a saturated calomel electrode and a Pt mesh were used as the reference electrode and counter electrode, respectively.

[0054] Figure 5 PtBi of Example 1 1.5 Ni 0.2 Co 0.2 Cu 0.2 Cyclic voltammetry curves of high-entropy alloy catalysts in a 0.5 mol / L H₂SO₄ solution containing 0.5 mol / L CH₃OH, with a potential range of -0.2 V to 1 V (relative to a saturated calomel electrode, SCE) and a scan rate of 50 mV / s, are presented. The small squares in the figure represent PtBi. 1.5 Ni 0.2 Co 0.2 Cu 0.2 Cyclic voltammetric curves of the catalytic activity of high-entropy alloy catalysts for methanol oxidation; the small circles represent the cyclic voltammetric curves of commercial Pt / C catalysts for methanol oxidation. Figure 5 It can be concluded that PtBi 1.5 Ni 0.2 Co 0.2 Cu0.2 The MOR activity of the high-entropy alloy catalyst is 0.91 A mg. -1 In contrast, the activity of commercial Pd / C is only 0.26 mg. -1 .

[0055] Figure 6 PtBi of Example 1 1.5 Ni 0.2 Co 0.2 Cu 0.2 The potential change of a high-entropy alloy catalyst after 3600 s in a 0.5 mol / L H₂SO₄ solution containing 0.5 mol / L CH₃OH at a potential of 0.66 V (relative to a saturated calomel electrode, SCE) is shown. The square lines represent PtBi. 1.5 Ni 0.2 Co 0.2 Cu 0.2 The current-time curves for the methanol oxidation reaction of high-entropy alloy catalysts are shown. The circular line represents the current-time curve for the methanol oxidation reaction of commercial Pt / C catalysts. Figure 6 It can be concluded that after the 3600s stability test, PtBi 1.5 Ni 0.2 Co 0.2 Cu 0.2 The activity of the high-entropy alloy catalyst decreased by 60%. In contrast, the activity of commercial Pt / C decreased by 97% after a 3600s stability test, and its activity almost approached zero, i.e., it lost its activity.

[0056] Example 2:

[0057] A method for preparing a porous Pt-based high-entropy alloy, the method specifically includes the following steps:

[0058] Step 1: Mix 4.2562g of cyclodextrin with 250mL of deionized water and sonicate for 30min to obtain the reaction solvent;

[0059] Step 2: Potassium chloroplatinate in a molar ratio of 1:1:1:1 is mixed with copper sulfate, nickel acetate and cobalt nitrate in 2 mL of reaction solvent and sonicated for 10 s to obtain precursor solution A; wherein the concentration of platinum ions, copper ions, nickel ions and cobalt ions in precursor solution A is 0.06 mol / L.

[0060] Step 3: Add sodium borohydride to 6 mL of reaction solvent and mix, then sonicate for 10 s to obtain a reduced solution; wherein, the concentration of sodium borohydride in the reduced solution is 0.08 mol / L;

[0061] Step 4: Stir the precursor solution A at a speed of 700 r / min for 10 min.

[0062] Step 5: Add 30 mg of bismuth neododecaned to 2 mL of reaction solvent and dissolve at 120 °C for 15 minutes to obtain bismuth precursor solution B; add 2 mL of bismuth precursor solution B to 52 precursor solution A at a rate of 1-10 mL per second to obtain precursor solution C;

[0063] Step 6: Add 6 mL of the reduction solution to 54 mL of precursor solution C at a rate of 1-20 mL per second to obtain the reaction solution. Stir the reaction solution at a speed of 700 r / min for 2 h.

[0064] Step 7: After stirring, let it stand at 25℃ for 3 days. After standing, wash the reaction solution at 50℃-100℃.

[0065] The black solid powder is obtained by drying for 6-12 hours. The black solid powder is a Pt-based high-entropy alloy.

[0066] The Pt-based high-entropy alloy catalysts obtained above were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), such as... Figure 1 As shown in figure a, the morphology of the obtained Pt-based high-entropy alloy is a porous structure, further as shown in figure a. Figure 1 As shown in b, the nanosheet exhibits distinct lattice fringes with a lattice spacing of 0.21 nm, corresponding to the (111) plane of pure Pt. Meanwhile, as... Figure 2 The image shows the observation of PtBi using the diffraction mode (SEAD) of a transmission electron microscope. 1.5 Ni 0.2 Co 0.2 Cu 0.2 The high-entropy alloy catalyst was found to have a polycrystalline structure.

[0067] The above-mentioned PtBi 1.5 Ni 0.2 Co 0.2 Cu 0.2 The high-entropy alloy catalyst was scanned using an X-ray diffractometer, and the results are as follows: Figure 3 As shown, it can be seen that all XRD spectral peaks correspond to the face-centered cubic phase of Pt (JCPDF, 04-0802). Among them, the diffraction peaks 2θ = 39.9°, 46.4°, 67.7° and 81.6° can be indexed as the (111), (200), (220) and (311) planes of pure Pt.

[0068] Further X-ray photoelectron spectroscopy was used to detect PtBi. 1.5 Ni 0.2Co 0.2 Cu 0.2 The valence states of Pt components in high-entropy alloy catalysts, such as Figure 4 As shown, for the Pt element, a pair of peaks appears at 72.6 eV and 69.1 eV, which can be attributed to Pt. 0 and Pt 3+ The existence of PtBi in the above system can therefore be proven. 1.5 Ni 0.2 Co 0.2 Cu 0.2 High-entropy alloys are high-entropy alloys with Pt as the main metal.

[0069] Example 3:

[0070] A method for preparing a porous Pt-based high-entropy alloy, the method specifically includes the following steps:

[0071] Step 1: Mix 4.2562g of cyclodextrin with 250mL of deionized water and sonicate for 30min to obtain the reaction solvent;

[0072] Step 2: Potassium chloroplatinate in a molar ratio of 1:0.4:0.4:0.4 is dissolved in 2 mL of reaction solvent with copper sulfate, nickel acetate, and cobalt nitrate, and then sonicated for 10 s to obtain precursor solution A. The concentrations of platinum ions, copper ions, nickel ions, and cobalt ions in precursor solution A are 0.06 mol / L, 0.024 mol / L, 0.024 mol / L, and 0.024 mol / L, respectively.

[0073] Step 3: Add sodium borohydride to 6 mL of reaction solvent and mix, then sonicate for 10 s to obtain a reduced solution; wherein, the concentration of sodium borohydride in the reduced solution is 0.08 mol / L;

[0074] Step 4: Stir the precursor solution A at a speed of 700 r / min for 10 min.

[0075] Step 5: Add 43 mg of bismuth neododecaned to 3 mL of reaction solvent and dissolve at 120 °C for 15 minutes to obtain bismuth precursor solution B. Add 3 mL of bismuth precursor solution B to 51 mL of precursor solution A at a rate of 1-10 mL per second to obtain precursor solution C.

[0076] Step 6: Add 6 mL of the reduction solution to 54 mL of precursor solution C at a rate of 1-20 mL per second to obtain the reaction solution. Stir the reaction solution at a speed of 700 r / min for 2 h.

[0077] Step 7: After stirring, let it stand at 25℃ for 3 days. After standing, wash the reaction solution at 50℃-100℃.

[0078] The black solid powder is obtained by drying for 6-12 hours. The black solid powder is a Pt-based high-entropy alloy.

[0079] In summary, the PtBi prepared by the method of the present invention 1.5 Ni 0.2 Co 0.2 Cu 0.2 High-entropy alloy catalysts exhibit excellent catalytic activity for methanol oxidation (MOR), and also demonstrate superior stability. Furthermore, their preparation process is simple, low-cost, and suitable for large-scale industrial production.

[0080] The foregoing description has fully disclosed the specific embodiments of the present invention. It should be noted that any modifications made to the specific embodiments of the present invention by those skilled in the art do not depart from the scope of the claims. Accordingly, the scope of the claims is not limited to the foregoing specific embodiments.

Claims

1. A method for preparing a porous Pt-based high-entropy alloy, characterized in that, Specifically, the steps include the following: Step 1: Dissolve a certain amount of surfactant in deionized water as a reaction solvent, wherein the concentration of surfactant in the reaction solvent is greater than or equal to 0.04 mol / L; Step 2: Dissolve the precursor platinum salt, precursor nickel salt, precursor copper salt, and precursor cobalt salt in the reaction solvent according to a preset molar ratio to obtain precursor solution A; Step 3: Dissolve a certain amount of reducing agent in the reaction solvent to obtain a reduced solution; Step 4: Stir the precursor solution A at a speed of 500-1000 r / min for 10-30 min. Step 5: Dissolve 0.1-1g of the precursor bismuth salt in 10-500mL of reaction solvent by heating at 50-150℃ on a magnetic stirrer to obtain bismuth precursor solution B. Then add 1-5mL of bismuth precursor solution B to 10-100mL of precursor solution A after stirring in step 4 at a rate of 1-10mL per second to obtain precursor solution C. Step 6: Add 1-10 mL of the reducing solution to 10-100 mL of the precursor solution C at a rate of 1-20 mL per second to obtain the reaction solution. Stir the reaction solution at a speed of 200-2000 r / min for 1-12 h. Step 7: After stirring, let it stand at room temperature of 0℃-80℃ for 2-10 days. After standing, clean the sample and dry it at 50℃-100℃ for 6-12 hours to obtain Pt-based high-entropy alloy. In the precursor solution A, the concentration of platinum ions is 0.02-0.04 mol / L, and the preset molar ratio of precursor platinum salt, precursor nickel salt, precursor copper salt, and precursor cobalt salt is 1:0.2-1:0.2-1:0.2-1. In the precursor solution C, the concentration of bismuth ions is 0.03-0.06 mol / L. The molar ratio of platinum ions to bismuth ions, nickel ions, cobalt ions and copper ions in the precursor solution C is 1:(1-3):(0.1-1):(0.1-1):(0.1-1).

2. The method for preparing the porous Pt-based high-entropy alloy according to claim 1, characterized in that: In the first step, the surfactant is one or a combination of several of cyclodextrin, PVP, and CTAB, and the concentration of the surfactant in the reaction solvent is 0.04-1 mol / L.

3. The method for preparing the porous Pt-based high-entropy alloy according to claim 1, characterized in that: The precursor platinum salt is potassium chloroplatinate and / or potassium chloroplatinate; the precursor bismuth salt is bismuth neododecanoate and / or anhydrous bismuth nitrate; the precursor nickel salt is nickel acetate and / or nickel chloride; the precursor cobalt salt is cobalt nitrate and / or cobalt chloride; and the precursor copper salt is copper sulfate and / or copper chloride.

4. The method for preparing the porous Pt-based high-entropy alloy according to claim 1, characterized in that: The reducing agent is sodium borohydride and / or ascorbic acid, and the concentration of the reducing agent in the reducing solution is 0.08-1 mol / L.

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