CN113346094A

CN113346094A - Macro preparation method of supported high-dispersion small-size platinum-based ordered alloy electrocatalyst

Info

Publication number: CN113346094A
Application number: CN202110599610.8A
Authority: CN
Inventors: 王尧; 廖逸飞; 陈云贵; 吴朝玲
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2021-05-31
Filing date: 2021-05-31
Publication date: 2021-09-03
Anticipated expiration: 2041-05-31
Also published as: CN113346094B

Abstract

The invention relates to the technical field of preparation of a platinum-based catalyst of a proton exchange membrane fuel cell, in particular to a macro preparation method of a supported high-dispersion small-size platinum-based ordered alloy electrocatalyst. According to the scheme, metal precursor liquid is used for impregnating mesoporous silicon to obtain powder I; carrying out heat treatment on the powder I to obtain powder II; annealing the powder II to obtain powder III; dispersing the powder III and a carrier in a dispersion solvent to obtain a dispersion liquid; then etching the mesoporous silicon in the dispersion liquid to obtain the catalyst. The technical problem that the catalytic activity of the catalyst formed by alloying the transition metal element and the platinum is not ideal is solved. The prepared catalyst nano particles have high dispersibility, the size of the nano particles is about 3-5nm, and the alloy structure is an intermetallic compound structure. The preparation method is simple in preparation process, environment-friendly and suitable for large-scale production; the prepared catalyst has higher oxygen reduction activity and stability, and can be directly applied to fuel cells.

Description

Macro preparation method of supported high-dispersion small-size platinum-based ordered alloy electrocatalyst

Technical Field

The invention relates to the technical field of preparation of a platinum-based catalyst of a proton exchange membrane fuel cell, in particular to a macro preparation method of a supported high-dispersion small-size platinum-based ordered alloy electrocatalyst.

Background

Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high energy density, no restriction by carnot cycle, zero pollutant emission, and the like, and can be widely applied to the fields of transportation, fixed power generation, portable power sources, and the like. The operating principle of PEMFCs is based on anodic Hydrogen Oxidation (HOR) and cathodic oxygen reduction (ORR). ORR has a larger overpotential and slower reaction kinetics compared to HOR. To meet the high power requirements of PEMFCs, the industry has to increase the amount of catalyst used. However, the price of platinum resources is high and the reserves in China are low, which severely limits the popularization and development of the fuel cell industry.

In order to increase the activity of the catalyst and reduce the amount of platinum used, the academic community usually alloys transition metal elements (such as Fe, Co, Ni, etc.) with platinum to reduce oxygen-containing substances (such as-OH)^*、-OH₂ ^*Etc.) bind to platinum, increasing its catalytic reaction kinetics. Cui et al (Chunhua Cui, et al, Compositional grading in shaped Pt alloy nanoparticles and the same structural catalyst along with electrochemical catalysis, Nature Materials,2013,12, 765-. However, after long-term use, Ni atoms are eluted in large amounts, so that the coordination number of Pt atoms on the surface rapidly decreases and surface atomic rearrangement starts to occur. The catalyst gradually changes from an octahedral structure to a spherical structure, resulting in a sharp decline in its catalytic activity. Even if the surface unstable base metal atoms are removed in advance by chemical and electrochemical means to improve the durability of the catalyst for a short time, the rough alloy surface obtained is still difficult to maintain for a long time (Deli Wang, et al, Tuning Oxygen Reduction Reaction Activity of a Controllable porous alloying: A Model Study of Ordered Cu)₃Pt/C Intermetallic Nanocatalysts,Nano Letters,2012,12,5230-5238.)。

To inhibit the reaction processThe base metal is dissolved out, the interaction force between Pt atoms and base metal atoms is required to be improved, and a layer of dense platinum shell is formed on the outer surface of the alloy nano particles to prevent the base metal atoms from being segregated to the surface. The platinum-based ordered alloy (i.e., intermetallic compound alloy) has highly ordered arrangement of Pt atoms and base metal atoms, has stronger interaction force than that of a solid solution alloy, and theoretically has stronger corrosion resistance. Wang et al (Deli Wang, et al, structural ordered intermetallic coatings with enhanced activity and reactivity as oxygen reduction catalysts, Nature Materials,2012,12,81-87.) prepare ordered alloys Pt with a core-shell structure by a dip-pyrolysis method₃Co @ Pt catalyst. Compared with disordered Pt₃Co/C catalyst, prepared ordered alloy Pt with core-shell structure₃The Co @ Pt catalyst has good promotion on the catalytic activity, and the durability is obviously improved. After a long period of use, the activity of the catalyst was well maintained and no significant elution of Co atoms occurred. Even ordered alloys PtM with higher base metal content₃The @ Pt catalyst is also capable of retarding the dissolution of base metal atoms over long periods of use, exhibiting excellent catalytic stability (Zhongxiang Wang, et al, structural Ordered Low-Pt Interactive electrolytes fabricated Dual High Oxygen Reduction Reaction Activity, accepted Functional Materials,2019,1902987.). However, to obtain PtM alloy nanoparticles with ordered atomic arrangement, it is necessary to satisfy not only thermodynamic stability (e.g., L1)₀T of PtCo alloy⁰800 c) and also needs to provide enough energy to satisfy its atomic diffusion kinetics. That is, high temperature heat treatment is inevitable in order to obtain PtM alloy nanoparticles with ordered atomic arrangement. The nano particles can be obviously sintered in the high-temperature treatment process and then coarsened into larger particles, so that the utilization rate of platinum atoms is reduced, and the quality activity of the catalyst is reduced. Therefore, the development of the platinum-based ordered alloy catalyst with high dispersion and small size has great significance for reducing the usage amount of the platinum catalyst and improving the catalytic activity and stability of the platinum-based catalyst.

Disclosure of Invention

The invention aims to provide a macroscopic preparation method of a supported high-dispersion small-size platinum-based ordered alloy electrocatalyst, so as to solve the technical problem that the catalytic activity and stability of a catalyst formed by alloying a transition metal element and platinum are not ideal.

In order to achieve the purpose, the invention adopts the following technical scheme:

a macroscopic preparation method of a supported high-dispersion small-size platinum-based ordered alloy electrocatalyst is characterized in that mesoporous silicon is impregnated by using metal precursor liquid to obtain powder I; carrying out heat treatment on the powder I to obtain powder II; annealing the powder II to obtain powder III; dispersing the powder III and a carrier in a dispersion solvent to obtain a dispersion liquid; then etching the mesoporous silicon in the dispersion liquid to obtain the catalyst.

The principle and the advantages of the scheme are as follows: according to the scheme, the precursor solution (such as the precursor solution containing platinum and base metal) is filled into the pore channel of the mesoporous silicon by a precursor solution dipping method, the nano-confinement effect of the mesoporous silicon is utilized to inhibit the sintering phenomenon of nano particles, and the platinum-based ordered alloy is prepared in a small size under the high-temperature condition. In addition, the method controllably disperses the ordered platinum alloy nanoparticles on the surface of the carrier by controlling the mesoporous silicon removal step, so that the alloy nanoparticles are prevented from self-agglomerating.

When preparing a catalyst formed by alloying a transition metal element with platinum, the problems of undesirable catalytic activity and stability of the catalyst often occur. The prior art has attempted to address this by making the platinum-base metal alloy octahedral. However, the octahedral materials have high synthesis difficulty, slow cycle and difficulty in macro preparation, and require a large amount of organic solvents and surfactants, thereby causing environmental pollution. And the octahedral alloy is in a solid solution structure, so that base metal atoms are easy to dissolve out to cause catalyst deactivation under the actual working condition. The synthetic method of the scheme completely breaks through the thinking mode of the prior art, and the mesoporous silicon hard template used in the synthetic process assists the preparation of the ordered alloy catalyst. And the use of the mesoporous silicon hard template is also found through a large amount of screening and experiments on candidate materials, and the effect of the scheme can be obtained by using the mesoporous silicon relative to other materials. By adopting the synthesis method of the scheme, the catalytic activity of the catalyst can be improved, the problem of base metal ion dissolution can be avoided, the electrochemical stability is excellent, the platinum-base metal ordered alloy can be prepared massively, the expanded production of the catalyst is realized, the preparation method is simple and easy, and the period is short.

Further, the metal precursor liquid includes a platinum salt and a non-platinum metal salt. Platinum is one of the important raw materials for producing proton exchange membrane fuel cells, and transition metal elements are alloyed with platinum to reduce oxygen-containing species (e.g., -OH)^*、-OH₂ ^*Etc.) binding energy with platinum, improving the catalytic ability of platinum.

Further, the platinum salt is one of potassium chloroplatinate, chloroplatinic acid and platinum acetylacetonate; the non-platinum metal salt is one of chloride salt, sulfate, nitrate and acetylacetone salt; the metal in the non-platinum metal salt is one of iron, cobalt, nickel, copper and zinc; the molar ratio of the platinum salt to the non-platinum metal salt is 1:3 to 3: 1. Potassium chloroplatinate, chloroplatinic acid and platinum acetylacetonate are in the form of conventional platinum salts and can be used as one of the components of the precursor solution. The chloride, sulfate, nitrate and acetylacetonate are all conventional forms of non-platinum metal salts and may also be used as raw materials for the precursor solution. PtFe, PtCo, PtNi and PtCu are conventional platinum-based alloys, and can improve the catalytic performance of the platinum-based catalyst. In the scheme, the molar ratio of the platinum salt to the non-platinum metal salt is maintained at 1:3-3:1, and the produced catalyst has the characteristics of good catalytic effect, good dispersity and small size.

Further, the temperature of the heat treatment is 800-1100 ℃, the time is 1-10h, and the atmosphere is argon or a hydrogen-argon mixed gas. In order to ensure the uniform mixing of the metal atoms, a heat treatment temperature of 800-1100 ℃ is adopted. The high temperature treatment can reduce platinum salt and base metal salt and accelerate the mutual diffusion of platinum atoms and base metal atoms to form solid solution.

Further, the temperature of the annealing treatment is 200-600 ℃, the time is 0.5-10h, and the atmosphere is argon or a hydrogen-argon mixed gas. The low temperature annealing can ensure that the solid solution alloy finishes ordered phase transformation.

Further, the carrier includes a carbon material and/or a metal compound, and the dispersion solvent is water; the method for dispersing powder III and the carrier in water is as follows: adding the powder III and the carrier into water, and then carrying out ultrasonic treatment for 3-5 h. The ultrasonic treatment enables the powder III and the carrier to be uniformly dispersed in water, so that the carrier can effectively capture alloy nanoparticles generated by etching the mesoporous silicon.

Further, the carbon material is one or a mixture of two or more of activated carbon, mesoporous carbon, graphene and carbon nanotubes. The activated carbon, the mesoporous carbon, the graphene and the carbon nano tube are all conventional carbon materials, have high surface area, high conductivity and excellent electrochemical stability, can be replaced and used in the preparation of the catalyst, and achieve similar effects.

Further, the dosage ratio of the mesoporous silicon to the platinum salt to the carrier to the hydrofluoric acid is as follows: 0.01-0.12mol of 1mol, 50-1000mg, 10 mol. The platinum-base metal catalyst prepared by adopting the raw materials in the proportion has the advantages of small size, good catalytic performance and the like.

Further, the method for etching the mesoporous silicon in the dispersion liquid comprises the following steps: dripping 40 wt.% of hydrofluoric acid into the dispersion liquid until the concentration of the hydrofluoric acid in the dispersion liquid reaches 10 wt.%, and the dripping speed is less than or equal to 2 wt.% h^-1Subsequently, the dispersion was stirred. Too fast a drop rate can result in too fast exposure of the nanoparticles formed by the platinum and base metal, which can lead to self-agglomeration of the particles and non-uniform dispersion on the support.

Further, after etching the mesoporous silicon in the dispersion liquid, obtaining a suspension, taking a solid phase in the suspension, washing the solid phase until the pH value is 6-7, and then drying and grinding the solid phase to obtain the catalyst. Through washing, remove impurity, through grinding again, obtain the catalyst powder of this scheme.

Drawings

FIG. 1 is an SEM image of ordered mesoporous silicon used in example 1 of the present invention.

FIG. 2 is an SEM photograph of the catalyst prepared in example 1 of the present invention.

FIG. 3 is a TEM image of the catalyst obtained in example 1 of the present invention.

FIG. 4 is an HRTEM image of the catalyst prepared in example 1 of the present invention.

FIG. 5 is an XRD spectrum of the catalysts prepared in examples 1-3 of the present invention.

FIG. 6 shows that the catalysts obtained in examples 1 to 3 of the present invention were used in the presence of 0.1mol/L HClO₄LSV curve in solution.

Fig. 7 is an XRD spectrum of the catalyst prepared in comparative example 1 of the present invention.

FIG. 8 is an electron micrograph of a silicon sphere synthesized in comparative example 1 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following examples are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents and the like used are all commercially available.

Example 1

Step 1: mixing 112mg of Pt (acac)₂(platinum (II) acetylacetonate, platinum salt) and 205mg Co (acac)₃(cobalt (III) acetylacetonate, base metal salt) was dissolved in 8mL of N, N-Dimethylformamide (DMF) to obtain a transparent precursor solution, slowly dropped into 6g of ordered mesoporous silicon (MCM-48, SEM picture see FIG. 1) and uniformly mixed and vacuum-dried to obtain powder I. Compared with general mesoporous silicon, the ordered mesoporous silicon has more regular hole patterns and more concentrated pore diameters, and is a preferred scheme. More specifically, MCM-48 used in this example had a BJH pore size of 3.2nm and a BET specific surface area of 1100m²G, BJH pore volume of 0.98m³(ii) in terms of/g. In the scheme, common mesoporous silicon (such as various mesoporous silicon materials including SBA-15, KIT-6, MSU and the like) is used, the effect of the scheme can be achieved, and the method can be applied to synthesis of small-size alloy particles. In the scheme, the aim of vacuum drying is to completely volatilize a solvent (DMF) of the precursor liquid, and allow a platinum salt and a base metal salt in the precursor liquid to better enter a pore channel of the mesoporous silicon and be dried in the pore channel.

Step 2: and (3) putting the dried powder I into a tube furnace, heating for 3h (wherein, the heating time is called as the heat treatment temperature in the table 1) in the argon atmosphere at 800 ℃ (the heating time can be up to alloying within 1-10 h), and naturally cooling to obtain powder II. The argon atmosphere may be replaced by a hydrogen-argon mixture atmosphere, both atmospheres being conventional in the art.

And step 3: the obtained powder ii was annealed for 3 hours at 600 ℃ (referred to as annealing temperature in table 1) in an argon atmosphere to obtain powder iii. The argon atmosphere may be replaced by a hydrogen-argon mixture atmosphere, both atmospheres being conventional in the art.

And 4, step 4: the obtained powder III and 300mg of Vulcan XC-72 (the dosage of the carrier can achieve the target effect within 50-1000 mg) are dispersed in 1500mL of deionized water together, and ultrasonic dispersion is carried out for 3h (ultrasonic treatment can achieve full dispersion of the powder III and the carrier in the deionized water within 3-5 h). The purpose of the above operation is to uniformly disperse the powder iii and the carrier in water so that the carrier can effectively capture alloy nanoparticles generated by etching the mesoporous silicon. In 2 wt.% h^-140 wt.% hydrofluoric acid solution was added dropwise to the suspension at a rate such that the concentration of hydrofluoric acid in the suspension reached 10 wt.%. After the addition was completed, the mixture was stirred vigorously for 24 hours to obtain a suspension. In the scheme, the amount of hydrofluoric acid (pure compound) is 10mol, i.e. the molar ratio of the mesoporous silicon to the hydrofluoric acid is 1: 10; the amount of water used was 2000ml, which is the sum of the amount of water of the dispersion powder III and of the carrier and of the amount of water for the preparation of the hydrofluoric acid solution. In the scheme, the carbon material is Vulcan XC-72, and other activated carbon, mesoporous carbon, graphene and carbon nano tubes which have high surface area, high conductivity and excellent electrochemical stability can be selected and used as a carrier for replacement when the catalyst is prepared. In this case, the control of the dropping speed of the hydrofluoric acid solution is very important and needs to be maintained at 2 wt.% h^-1Otherwise too fast a rate would result in too fast exposure of the nanoparticles formed by platinum and base metal, resulting in self-agglomeration of the particles and non-uniform dispersion on the support. In particular, the inventors attempted to use more than 2 wt.% h^-1The hydrofluoric acid solution is dripped into the suspension at the speed of (1), the particles are self-agglomerated, and the obtained catalyst has poor dispersity.

And 5: centrifuging the obtained suspension, washing with water until the pH value is close to neutral, drying in an oven at 60 ℃ overnight (namely over 8-10 h) to obtain powder IV (black), and fully grinding the obtained black powder IV to obtain the catalyst.

SEM, TEM and HRTEM images of the prepared catalyst are shown in fig. 2, 3 and 4. It can be seen from fig. 2 and 3 that the catalyst particles obtained by the preparation have good dispersibility, and the particle size statistics of fig. 3 show that the particles obtained by the preparation have a particle size of 3 to 5 nm.

Examples 2-8 were prepared in the same manner as in example 1, except that the parameters in Table 1 were different, and examples 2-8 all used 112mg of Pt (acac)₂The mass of the mesoporous silicon template used in all the examples was uniform and was 6 g. XRD spectra of catalysts prepared in examples 1-3 referring to FIG. 5, catalysts prepared in examples 1-3 were treated at 0.1mol/L HClO₄The LSV curve in the solution is shown in fig. 6. The XRD spectrum of fig. 5 shows that the catalyst particles obtained by the preparation have a size of about 3 to 5 nm.

In examples 1 to 8, cobalt salts were used to prepare the catalysts, and those skilled in the art also used iron, nickel, copper and zinc salts instead of cobalt salts to prepare the catalysts, and PtFe, PtCo, PtNi and PtCu were conventional platinum-based alloys, which are conventional technical means in the art, so that the process of preparing the catalysts using iron, nickel, copper and zinc salts is not shown in detail in the examples. The inventors also verified through experiments that when preparing platinum-based alloys such as PtFe, PtCo, PtNi, and PtCu, the catalyst obtained by using mesoporous silicon according to the method of example 1 has the characteristics of high dispersion and small size. And the ordered very close electrocatalyst of PtFe, PtCo, PtNi and PtCu synthesized by using mesoporous silicon has higher E compared with the electrocatalyst without using mesoporous silicon_1/2Values (V vs RHE) and MA @0.9V vs RHE values (mA mgPt^-1) Thereby having higher catalytic activity.

Table 1: process parameter settings for examples 1-8

Comparative example 1: the preparation process is the same as that of example 1, except that the ordered mesoporous silicon is replaced by silicon spheres (self-made in laboratories, the surface of the ordered mesoporous silicon has no pore channels, the ordered mesoporous silicon is a non-porous material synthesized by the stober method, the particle size is 150nm, and an electron microscope image thereof is shown in figure 8). The XRD spectrum of the prepared catalyst is shown in fig. 7. As can be seen from fig. 7, the XRD image shows that the mesoporous structure confinement effect is absent, and PtCo crystal grains are significantly large, which is not favorable for synthesizing a catalyst with good dispersion degree and small size, thereby proving that the macroscopic preparation of the platinum-based ordered alloy electrocatalyst with high dispersion and small size can be realized by using the structure confinement effect of the mesoporous silicon. In the comparative example, because no mesoporous confinement effect exists, the PtCo alloy after heat treatment is seriously agglomerated into non-nanoscale particles, and the carbon-supported PtCo alloy catalyst is not prepared, so that the electrochemical test cannot be performed. The Size and dispersibility of the alloy both seriously affect the catalyst activity (J.Quanson, et al, inquiring particulate Size Effects in Catalysis by Applying a Size-Controlled and Surfactant-Free Synthesis of Colloidal Nanoparticles in Alkaline Ethylene Glycol: Case Study of the ozone Reduction Reaction Pt, ACS Catal.,2018,8,6627-6635.), so the catalytic performance of the alloy material synthesized by the present comparative example is poor, further demonstrating the important role of using mesoporous silicon in the catalyst Synthesis process.

Experimental example 1: catalyst activity detection

Catalytic activity assay experiments were performed on examples 1-10 as well as comparative example 1 and commercial Pt/C (20 wt.% Pt/C from Johnson Matthey corporation) to assay E_1/2(V vs RHE) and MA (mA mg)_Pt ^-1) Two indicators, detection methods are described in literature (Deli Wang, et al, structural ordered interactive display-substrate-shell nanoparticles with enhanced activity and viability as oxygen reduction analytes, Nature Materials,2012,12, 81-87). The detection results are shown in table 2, and experiments prove that the catalyst material synthesized by the scheme has high catalytic activity and can meet the requirements of practical application. Catalysts prepared in examples 1-3 and commercial Pt/C at 0.1mol/L HClO₄The LSV curve in the solution is shown in fig. 6.

Table 2: e_1/2(V vs RHE) and MA (mA mgPt)^-1) The result of the detection

The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.

Claims

1. A macro preparation method of a supported high-dispersion small-size platinum-based ordered alloy electrocatalyst is characterized by comprising the following steps of: immersing mesoporous silicon by using metal precursor liquid to obtain powder I; carrying out heat treatment on the powder I to obtain powder II; annealing the powder II to obtain powder III; dispersing the powder III and a carrier in a dispersion solvent to obtain a dispersion liquid; then etching the mesoporous silicon in the dispersion liquid to obtain the catalyst.

2. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 1, characterized in that: the metal precursor liquid includes a platinum salt and a non-platinum metal salt.

3. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 2, characterized in that: the platinum salt is one of potassium chloroplatinate, chloroplatinic acid and platinum acetylacetonate; the non-platinum metal salt is one of chloride salt, sulfate, nitrate and acetylacetone salt; the metal in the non-platinum metal salt is one of iron, cobalt, nickel, copper and zinc; the molar ratio of the platinum salt to the non-platinum metal salt is 1:3 to 3: 1.

4. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 3, characterized in that: the temperature of the heat treatment is 800-1100 ℃, the time is 1-10h, and the atmosphere is argon or hydrogen-argon mixed gas.

5. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 4, characterized in that: the temperature of the annealing treatment is 300-600 ℃, the time is 0.5-3h, and the atmosphere is argon or a hydrogen-argon mixed gas.

6. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 5, characterized in that: the carrier comprises a carbon material and/or a metal compound, and the dispersion solvent is water; the method for dispersing powder III and the carrier in water is as follows: adding the powder III and the carrier into water, and then carrying out ultrasonic treatment for 3-5 h.

7. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 6, characterized in that: the carbon material is one substance or a mixture of more than two substances of activated carbon, mesoporous carbon, graphene and carbon nanotubes.

8. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 7, characterized in that: etching the mesoporous silicon by hydrofluoric acid; the dosage ratio of the mesoporous silicon to the platinum salt to the carrier to the hydrofluoric acid is as follows: 0.01-0.12mol of 1mol, 50-1000mg, 10 mol.

9. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 8, characterized in that: the method for etching the mesoporous silicon in the dispersion liquid comprises the following steps: 40 wt.% of hydrofluoric acid is added dropwise to the dispersion until the dispersion is reachedThe concentration of hydrofluoric acid reaches 10 wt.%, and the dropping speed is less than or equal to 2 wt.% h^-1Subsequently, the dispersion was stirred.

10. The macro preparation method of the supported high-dispersion small-size platinum-based ordered alloy electrocatalyst according to claim 1, characterized in that: and etching the mesoporous silicon in the dispersion liquid to obtain a suspension, taking a solid phase in the suspension, washing the solid phase until the pH value is 6-7, and then drying and grinding the solid phase to obtain the catalyst.