High-throughput preparation method of high-entropy alloy nanoparticles

Abstract

The invention discloses a high-throughput preparation method of high-entropy alloy nanoparticles, which comprises the following steps: 1) preparing 1-8 different or same precursor solutions, each precursor solution being prepared by dissolving at least five soluble metal salts in a solvent; 2) mixing a reducing agent and a flocculating agent, and dissolving the mixture in an alkaline solvent to prepare a reducing solution; (3) the 1-8 kinds of precursor solutions and the reducing solutions make contact in parallel pipelines through peristaltic pumps to react, reaction solutions flow into different beakers through different outlet pipelines, products are collected after full stirring, and 1-8 kinds of corresponding high-entropy alloy coarse particles are prepared; and (4) all the high-entropy alloy coarse particles are subjected to aftertreatment, and 1-8 kinds of high-entropy alloy particles are obtained. The preparation method is completed under the mild conditions of room temperature and normal pressure; according to the method, eight kinds of high-entropy alloy nano-particles can be prepared at the same time at most, and the particle size is small and is about 5-100 nm.

Description

Technical Field

[0001] The present invention relates to the technical field of high-entropy alloys. More specifically, it relates to a high-throughput preparation method for high-entropy alloy nanoparticles. Background Art

[0002] High Entropy Alloys (HEAs) break through the traditional alloy design concept dominated by one or two metals. They are new alloys composed of 4 or more main elements, and the content of each main element does not exceed 35%. This unique design endows high-entropy alloys with high strength, high hardness, excellent corrosion resistance and heat resistance, as well as special electromagnetic properties. The innovative design of high-entropy alloys provides a broad space for the development of material functions and shows broad application prospects in fields such as advanced equipment and energy conversion. There are various preparation methods for high-entropy alloy nanoparticles. The following are several main preparation techniques:

[0003] Mechanical Alloying: Mechanical alloying is a process of combining powder materials through methods such as high-energy ball milling. Through long-term and high-energy grinding, the dispersion and uniform mixing of metal elements at the nanoscale can be achieved. This method is simple and easy to implement, and can synthesize high-entropy alloy nanoparticles at room temperature. After appropriate heat treatment, the growth of grains and phase transformation can be promoted to obtain the required material properties.

[0004] Chemical Vapor Deposition (CVD): CVD is a technique for depositing materials on a substrate through chemical reactions. In the synthesis of high-entropy alloys, the efficient deposition of different elements can be achieved by adjusting the composition of gases and reaction conditions. This method can control the size and morphology of particles to obtain uniform nanoparticles. In addition, the CVD technique can also be used in combination with other advanced techniques, such as in-situ growth, to achieve more complex nanostructures.

[0005] Solution-based Methods: Solution-based methods synthesize nanoparticles in solution through chemical reactions. Common methods include co-precipitation method, hydrothermal method, sol-gel method, etc. These methods can achieve precise control of reaction conditions, thereby obtaining high-entropy alloy nanoparticles with controllable particle sizes. The hydrothermal method is particularly suitable for preparing nanoparticles with uniform structures and controllable morphologies.

[0006] Laser Melting: Laser melting is a method that uses a laser beam to melt powder materials and rapidly cool them. This method can synthesize high-entropy alloy nanoparticles with high density and good microstructure in a relatively short time. Laser melting can control the energy input, adjust the temperature and cooling rate of the melting area, and thus regulate the phase structure of the alloy and the morphology of the particles.

[0007] Currently, a large number of research scholars are committed to optimizing the preparation methods of high-entropy alloys, hoping to quickly and high-throughput prepare different types of high-entropy alloys, accelerate the study of the structure-property relationships of new high-entropy alloys, and provide important support for the application of high-entropy alloys in fields such as advanced equipment and energy conversion. This innovative effort is expected to open up new opportunities for the wide application of high-entropy alloys.

[0008] In view of this, Chinese Patent Application No.: 202310819416.5, titled "A Method for Rapid High-Throughput Preparation of High-Entropy Alloys", discloses a method for rapid high-throughput preparation of high-entropy alloys. The method is carried out in the following steps in sequence: (1) Five or more of the elemental metal powders of Fe, Co, Ni, Cu, Al, Ti, and Cr with a diameter of 40-60 μm are placed in a mixer and mixed for 30 minutes to obtain a mixed powder, and the metal elements in the elemental metal powders are in equiatomic ratio; (2) The mixed powder is placed under an inductively coupled plasma. Under the conditions that the working gas, protective gas, and carrier gas are all argon, the flow rate of the carrier gas is 0.4-0.6 L / min, and the flow rates of the working gas and the protective gas are independently 10-15 L / min; and the power of the inductively coupled plasma is 1100 W, rapid high-throughput preparation of high-entropy alloys is carried out. However, this patented technical solution still has the following defects: 1) The preparation of high-entropy alloys in this technology requires the high-temperature effect of inductively coupled plasma to achieve in-situ preparation of complex high-entropy alloys, and has high requirements for reaction equipment; 2) The preparation of high-entropy alloys in this technology requires an atmosphere where the working gas, protective gas, and carrier gas are all argon, and has relatively strict requirements for reaction conditions; 3) In this technology, the inside of the high-entropy alloy preparation platform needs to maintain water at 18°C flowing continuously at 15.0 ml / min through a water flow channel, and has high requirements for the reaction device; 4) The high-entropy alloy prepared by inductively coupled plasma in this technology is a high-entropy alloy bulk, and the size of the prepared high-entropy alloy is relatively large.

[0009] In summary, the current high-throughput preparation methods of high-entropy alloy nanoparticles still have the following problems: The synthesis methods involving high-temperature effects have overly demanding requirements for the experimental environment and equipment; the high-entropy alloys prepared by inductively coupled plasma synthesis methods are relatively large in size, and cannot meet the requirements for high-throughput preparation of high-entropy alloy nanoparticles at the nanoscale. To address the above problems, the present invention aims to propose a high-throughput preparation method for high-entropy alloy nanoparticles with a wide preparation range, high preparation efficiency, mild preparation conditions, small high-entropy alloy particle size, and uniform composition. Summary of the Invention

[0010] The technical problem to be solved by the present invention is to provide a high-throughput preparation method for high-entropy alloy nanoparticles; the preparation method of the present invention is completed under mild conditions of room temperature and normal pressure; the present invention can simultaneously prepare up to 8 kinds of high-entropy alloy nanoparticles at most, and the particle size is small, about 5nm - 100nm; the atomic ratio of each element in each high-entropy alloy nanoparticle is between 5% - 30%, which conforms to the element composition definition of high-entropy alloys.

[0011] To solve the above technical problems, the technical solution adopted by the present invention is as follows :

[0012] A high-throughput preparation method for high-entropy alloy nanoparticles, comprising the following steps:

[0013] 1) Prepare 1 - 8 kinds of precursor solutions, which can be different or the same. Each precursor solution is prepared by dissolving at least five soluble metal salts in a solvent;

[0014] 2) Mix a reducing agent and a flocculant and dissolve them in an alkaline solvent to obtain a reducing solution;

[0015] 3) Contact and react 1 - 8 kinds of precursor solutions and the reducing solution respectively through peristaltic pumps in parallel pipelines. The reaction solution flows into different beakers through different outlet pipelines, and after sufficient stirring, the products are collected to obtain the corresponding 1 - 8 kinds of high-entropy alloy crude particles;

[0016] 4) Post-treat all the high-entropy alloy crude particles to obtain 1 - 8 kinds of high-entropy alloy particles.

[0017] As an implementation method, in step 1), the soluble metal salt is selected from one of the following substances: ferrous sulfate, potassium chloropalladite, potassium chloropalladite, cobalt nitrate, nickel nitrate, manganese chloride, magnesium chloride, cobalt chloride, nickel chloride, copper chloride, lead acetate trihydrate.

[0018] As an implementation method, in step 1), the solvent is selected from one or more of the following substances: deionized water, ethanol, methanol, ethylene glycol, isopropanol, ether.

[0019] As an implementation manner, in step 2), the reducing agent is sodium borohydride; the flocculant is polyvinylpyrrolidone.

[0020] As an implementation manner, in step 2), the pH of the alkaline solvent is 10 - 14; more preferably, the pH of the alkaline solvent is 12.

[0021] As an implementation manner, in step 2), the mass ratio of the reducing agent to the flocculant is 2 - 8:1; more preferably, the mass ratio of the flocculant to the reducing agent is 5:1.

[0022] As an implementation manner, in step 3), the flow rates of the precursor solution and the reducing solution are 5 - 15 ml / min; more preferably, the flow rates of the precursor solution and the reducing solution are 8 - 13 ml / min; the inner diameter size of the parallel pipelines is 1.50 - 1.70 mm.

[0023] As an implementation manner, in step 3), the stirring speed is 300 - 1000 rmp / min; more preferably, the stirring speed is 800 rmp / min; the stirring time is 30 min - 180 min; more preferably, the stirring time is 120 min.

[0024] As an implementation manner, in step 4), the post - treatment includes one or more of washing and centrifugation.

[0025] As an implementation manner, the detergent used for washing is selected from one or more of the following substances: ethanol, water, ether, acetone.

[0026] As an implementation manner, the centrifugation speed is 500 - 12000 rmp; more preferably, the centrifugation speed is 800 - 11000 rmp.

[0027] Any range described in the present invention includes the end values and any numerical value between the end values, as well as any sub - range formed by any numerical value between the end values or the end values.

[0028] Unless otherwise specified, each raw material in the present invention can be obtained by purchasing from the market, and the equipment used in the present invention can be a conventional equipment in the field or can be referred to the existing technology in the field.

[0029] Compared with the prior art, the present invention has the following beneficial effects :

[0030] 1) The present invention can simultaneously synthesize up to 8 different types of high - entropy alloy nanoparticles, and the particle size is small, about between 5 nm and 100 nm, and the size distribution is uniform.

[0031] 2) The method for preparing the high-entropy alloy catalyst nanoparticles of the present invention has mild conditions, with low temperature and low pressure during the preparation process (the present invention is carried out under room temperature and atmospheric pressure conditions);

[0032] 3) The high-entropy alloy catalyst particles prepared by the present invention have a uniform element distribution, and the atomic ratio of each element is between 5% and 30%;

[0033] 4) The method for preparing high-entropy alloy nanoparticles of the present invention has a high yield, with a yield greater than 80%, low cost, low biological toxicity, simple operation, and is easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The following further describes in detail the specific embodiments of the present invention with reference to the drawings.

[0035] Figure 1 is the technical route diagram of the high-throughput preparation method of the high-entropy alloy nanoparticles of the present invention;

[0036] Figure 2 is the XRD pattern of the PdMgMnFeCo high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0037] Figure 3 is the particle size diagram of the PdMgMnCoNi high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0038] Figure 4 is the particle size diagram of the PdMgMnCuZn high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0039] Figure 5 is the XRD pattern of the PdPtMnFeCo high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0040] Figure 6 is the XRD pattern of the PdPtNiCuZn high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0041] Figure 7 is the XRD pattern of the PdPtFeCoNi high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0042] Figure 8 is the XRD pattern of the PdPtCoNiCu high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0043] Figure 9 is the particle size diagram of the PdPtCoCuZn high-entropy alloy nanoparticles prepared in Example 1 of the present invention;

[0044] Figure 10 is the XRD pattern of the PdPtMnFeNi high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0045] Figure 11 XRD pattern of the PdPtMnFeCu high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0046] Figure 12 XRD pattern of the PdPtMnFeZn high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0047] Figure 13 XRD pattern of the PdPtMnCoNi high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0048] Figure 14 XRD pattern of the PdPtFeCoCu high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0049] Figure 15 XRD pattern of the PdPtFeCoZn high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0050] Figure 16 XRD pattern of the PdPtFeNiCu high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0051] Figure 17 XRD pattern of the PdPtFeNiZn high-entropy alloy nanoparticles prepared in Example 2 of the present invention;

[0052] Figure 18 Electron micrograph of the high-entropy alloy catalyst particles prepared in Comparative Example 2 of the present invention;

[0053] Figure 19 Electron micrograph of the high-entropy alloy catalyst particles prepared in Comparative Example 3 of the present invention. Detailed Description of the Invention

[0054] To more clearly illustrate the present invention, the present invention will be further described below in conjunction with preferred embodiments and the accompanying drawings. Similar components in the drawings are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

[0055] Various cross-sectional views according to the disclosed embodiments of the present invention are shown in the drawings. These figures are not drawn to scale, where for the purpose of clear illustration, some details are enlarged and some details may be omitted. The shapes of various regions and layers shown in the figures, as well as their relative sizes and positional relationships, are merely exemplary, and may actually deviate due to manufacturing tolerances or technical limitations, and those skilled in the art can design regions / layers with different shapes, sizes, and relative positions according to actual needs.

[0056] As an aspect of the present invention, a high-throughput preparation method of high-entropy alloy nanoparticles of the present invention comprises the following steps:

[0057] 1) Prepare 1-8 different or identical precursor solutions, each precursor solution being prepared by dissolving at least five soluble metal salts in a solvent;

[0058] 2) Mix a reducing agent and a flocculant and dissolve them in an alkaline solvent to obtain a reducing solution;

[0059] 3) Contact 1-8 precursor solutions and the reducing solution respectively through peristaltic pumps in parallel pipelines to carry out reactions. The reaction solutions flow into different beakers through different outlet pipelines, and the products are collected after sufficient stirring to obtain corresponding 1-8 kinds of high-entropy alloy crude particles;

[0060] 4) Post-treat all the high-entropy alloy crude particles to obtain 1-8 kinds of high-entropy alloy particles.

[0061] According to certain embodiments of the present invention, in step 1), the soluble metal salt is selected from one of the following substances: ferrous sulfate, potassium chloropalladite, potassium chloropalladite, cobalt nitrate, nickel nitrate, manganese chloride, magnesium chloride, cobalt chloride, nickel chloride, copper chloride, lead acetate trihydrate. Those skilled in the art understand that due to the fact that soluble salts can dissolve in solvents, using soluble salts as metal precursors can prepare catalysts by liquid-phase synthesis methods. Using other salts with poor solubility cannot prepare catalysts by liquid-phase reduction methods.

[0062] According to certain embodiments of the present invention, in step 1), the solvent is selected from one or more of the following substances: deionized water, ethanol, methanol, ethylene glycol, isopropanol, ether. Other solvents are not suitable for dissolving soluble salts or are not miscible with reduction.

[0063] According to certain embodiments of the present invention, in step 2), the reducing agent is sodium borohydride; the flocculant is polyvinylpyrrolidone. It should be noted that in the present invention, selecting other reducing agents is not suitable for reducing metal ions or is not miscible with the flocculant.

[0064] According to certain embodiments of the present invention, in step 2), the pH of the alkaline solvent is 10-14; more preferably, the pH of the alkaline solvent is 12.

[0065] According to certain embodiments of the present invention, in step 2), the mass ratio of the reducing agent to the flocculant is 2-8:1; more preferably, the mass ratio of the flocculant to the reducing agent is 5:1.

[0066] According to certain embodiments of the present invention, in step 3), the flow rates of the precursor solution and the reducing solution are 5-15 ml / min; more preferably, the flow rates of the precursor solution and the reducing solution are 8-13 ml / min; the inner diameter size of the parallel pipelines is 1.50-1.80 mm.

[0067] According to certain embodiments of the present invention, in step 3), the stirring speed is 300-1000 rmp / min; more preferably, the stirring speed is 800 rmp / min; the stirring time is 30 min-180 min; more preferably, the stirring time is 120 min.

[0068] According to certain embodiments of the present invention, in step 4), the post-treatment includes one or more of washing and centrifugation.

[0069] According to certain embodiments of the present invention, the detergent used for washing is selected from one or more of the following substances: ethanol, water, ether, acetone.

[0070] According to certain embodiments of the present invention, the centrifugation speed is 500-12000 rmp; more preferably, the centrifugation speed is 800-11000 rmp.

[0071] Example 1

[0072] A high-throughput preparation method of high-entropy alloy nanoparticles, comprising the following steps:

[0073] 1) Dissolve 9.52 mg of MgCl 2 , 12.58 mg of MnCl 2 , 15.19 mg of FeSO 4 , 29.1 mg of Co(NO 3 ) 2 , 32.5 mg of K 2 PdCl 4 in 50 mL of H 2 O to obtain the first metal precursor solution;

[0074] Dissolve 9.52 mg of MgCl 2 , 12.58 mg of MnCl 2 , 12.95 mg of NiCl 2 , 29.1 mg of Co(NO 3 ) 2 , 32.5 mg of K 2 PdCl 4 in 50 mL of H 2 O to obtain the second metal precursor solution;

[0075] Dissolve 9.52 mg of MgCl 2 , 12.58 mg of MnCl 2 , 13.44 mg of CuCl 2 , 13.63 mg of ZnCl 2 , 32.5 mg of K 2 PdCl 4 in 50 mL of H 2 O to obtain the third metal precursor solution;

[0076] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 12.58 mg of MnCl 2 , 16.2 mg of FeCl 3 , 29.1 mg of Co(NO 3 ) 2 in 50 mL of H 2 O to obtain the fourth metal precursor solution;

[0077] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 12.95 mg of NiCl 2 , 13.44 mg of CuCl 2 , 13.63 mg of ZnCl 2 in 50 mL of H 2 O to obtain the fifth metal precursor solution;

[0078] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 16.2 mg of FeCl 3 , 29.1 mg of Co(NO 3 ) 2 , 12.95 mg of NiCl 2 in 50 mL of H 2 O to obtain the sixth metal precursor solution;

[0079] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 29.1 mg of Co(NO 3 ) 2, 12.95 mg NiCl 2 , 13.44 mgCuCl 2 Dissolve in 50 mL HO 2 O contains the metal precursor solution No. 7;

[0080] 32.5 mg K 2 PdCl 4 ,41.5mg K 2 PtCl 4 ,29.1mg Co(NO 3 ) 2 , 13.63 mg ZnCl 2 , 13.44 mgCuCl 2 Dissolve in 50 mL HO 2 O contains the metal precursor solution No. 8;

[0081] 2) Dissolve 800 mg of polyvinyl pyrrolidone (PVP) and 4 g of sodium borohydride in 400 ml of a sodium hydroxide solution having a pH of 12, and stir thoroughly to dissolve to prepare a reducing solution;

[0082] 3) 10 mL min -1 Eight metal precursor solutions were pumped into the parallel pipelines at a speed of 10 mL min -1 The reaction liquid is contacted with the reducing liquid at a high speed to react, and the reaction liquid flows into a beaker placed on a magnetic stirring table from the outlet pipe of the three-way pipe. After being fully stirred, the product is collected to obtain crude high entropy alloy nanoparticles;

[0083] 4) The high entropy alloy nanoparticles are washed multiple times with a mixed solution of water and ethanol, collected by centrifugation and dried in vacuum at room temperature to obtain PdMgMnFeCo, PdMgMnCoNi, PdMgMnCuZn, PdPtMnFeCo, PdPtNiCuZn, PdPtFeCoNi, PdPtCoNiCu, and PdPtCoCuZn high entropy alloy nanoparticles.

[0084] The XRD pattern of the PdMgMnFeCo high entropy alloy nanoparticles prepared in this example is as follows: Figure 2 As shown;

[0085] The particle size of the PdMgMnCoNi high entropy alloy nanoparticles prepared in this embodiment is shown in FIG. Figure 3 As shown;

[0086] The particle size of the PdMgMnCuZn high entropy alloy nanoparticles prepared in this embodiment is shown in FIG. Figure 4 As shown;

[0087] The XRD pattern of the PdPtMnFeCo high entropy alloy nanoparticles prepared in this example is as follows:Figure 5 as shown;

[0088] The XRD pattern of the PdPtNiCuZn high-entropy alloy nanoparticles prepared in this example is as shown in Figure 6 as shown;

[0089] The XRD pattern of the PdPtFeCoNi high-entropy alloy nanoparticles prepared in this example is as shown in Figure 7 as shown;

[0090] The XRD pattern of the PdPtCoNiCu high-entropy alloy nanoparticles prepared in this example is as shown in Figure 8 as shown;

[0091] The particle size diagram of the PdPtCoCuZn high-entropy alloy nanoparticles prepared in this example is as shown in Figure 9 as shown.

[0092] Example 2

[0093] A high-throughput preparation method of high-entropy alloy nanoparticles, comprising the following steps:

[0094] 1) Dissolve 2.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 12.58 mg of MnCl 2 , 16.2 mg of FeCl 3 , 12.95 mg of NiCl 2 in 50 mL of H 2 O to obtain the ninth metal precursor solution;

[0095] Dissolve 2.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 12.58 mg of MnCl 2 , 16.2 mg of FeCl 3 , 13.44 mg of CuCl 2 in 50 mL of H 2 O to obtain the tenth metal precursor solution;

[0096] Dissolve 2.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 12.58 mg of MnCl 2 , 16.2 mg of FeCl 3 , 13.63 mg of ZnCl 2Dissolved in 50 mL of H 2 O to form the precursor solution of metal No. 11;

[0097] Dissolve 2.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 16.2 mg of FeCl 3 , 29.1 mg of Co(NO 3 ) 2 , 12.95 mg of NiCl 2 Dissolved in 50 mL of H 2 O to form the precursor solution of metal No. 12;

[0098] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 16.2 mg of FeCl 3 , 29.1 mg of Co(NO 3 ) 2 , 13.44 mg of CuCl 2 Dissolved in 50 mL of H 2 O to form the precursor solution of metal No. 13;

[0099] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 16.2 mg of FeCl 3 , 29.1 mg of Co(NO 3 ) 2 , 13.63 mg of ZnCl 2 Dissolved in 50 mL of H 2 O to form the precursor solution of metal No. 6;

[0100] Dissolve 32.5 mg of K 2 PdCl 4 , 41.5 mg of K 2 PtCl 4 , 16.2 mg of FeCl 3 , 12.95 mg of NiCl 2 , 13.44 mg of CuCl 2 Dissolved in 50 mL of H 2 O to form the precursor solution of metal No. 7;

[0101] Dissolve 32.5 mg of K 2 PdCl 4, 41.5 mg K 2 PtCl 4 , 16.2 mg FeCl 3 , 12.95 mg NiCl 2 , 13.63 mg ZnCl 2 Dissolved in 50 mL H 2 O to form the eighth metal precursor solution;

[0102] 2) Dissolve 800 mg of polyvinylpyrrolidone (PVP) and 4 g of sodium borohydride in 400 ml of sodium hydroxide solution with pH = 12, and stir well to dissolve to make the reducing solution;

[0103] 3) Pump the eight metal precursor solutions into the parallel pipeline at a rate of 10 mL·min -1 to contact with the reducing solution at a rate of 10 mL·min -1 for reaction. The reaction solution flows into a beaker placed on a magnetic stirring table through the outlet pipeline of the three-way pipeline. After sufficient stirring, the product is collected to obtain crude high-entropy alloy nanoparticles;

[0104] 4) Wash the high-entropy alloy nanoparticles multiple times with a mixed solution of water and ethanol, collect by centrifugation, and vacuum dry at room temperature to obtain PdPtMnFeNi, PdPtMnFeCu, PdPtMnFeZn, PdPtMnCoNi, PdPtFeCoCu, PdPtFeCoZn, PdPtFeNiCu, PdPtFeNiZn high-entropy alloy nanoparticles.

[0105] The XRD pattern of the PdPtMnFeNi high-entropy alloy nanoparticles prepared in this example is as Figure 10 shown;

[0106] The XRD pattern of the PdPtMnFeCu high-entropy alloy nanoparticles prepared in this example is as Figure 11 shown;

[0107] The XRD pattern of the PdPtMnFeZn high-entropy alloy nanoparticles prepared in this example is as Figure 12 shown;

[0108] The XRD pattern of the PdPtMnCoNi high-entropy alloy nanoparticles prepared in this example is as Figure 13 shown;

[0109] The XRD pattern of the PdPtFeCoCu high-entropy alloy nanoparticles prepared in this example is as Figure 14 shown;

[0110] The XRD pattern of the PdPtFeCoZn high-entropy alloy nanoparticles prepared in this example is as Figure 15 shown;

[0111] The XRD pattern of the PdPtFeNiCu high-entropy alloy nanoparticles prepared in this example is as Figure 16 shown;

[0112] The XRD pattern of the PdPtFeNiZn high-entropy alloy nanoparticles prepared in this example is as Figure 17 shown.

[0113] Comparative Example 1

[0114] Repeat Example 1, with the difference that the pH of the alkaline solvent is 7; the precursor solutions are all PdPtMnCuZn.

[0115] Upon detection, the product obtained in this comparative example did not form a high-entropy alloy because sodium borohydride decomposed in a non-alkaline solvent, resulting in a decrease in the concentration of the reducing agent and a weakened reduction ability for the metal salt solution precursor, making it impossible to successfully obtain high-entropy alloy nanoparticles.

[0116] Comparative Example 2

[0117] Repeat Example 1, with the difference that the amount of polyvinylpyrrolidone (PVP) is 1.2 g; the precursor solutions are all PdPtMnCuZn.

[0118] Upon detection, the high-entropy alloy nanoparticles obtained in this comparative example had a larger particle size and a wider particle size distribution because the proportion of the flocculant was too large, causing the particles to aggregate faster, and at the same time, agglomeration occurred between the particles, producing larger particles.

[0119] The electron micrograph of the high-entropy alloy catalyst particles prepared in this comparative example is as Figure 18 shown.

[0120] Comparative Example 3

[0121] Repeat Example 1, with the difference that the inner diameter of the parallel pipeline is 2.00 mm; the precursor solutions are all PdPtMnCuZn.

[0122] Upon detection, the high-entropy alloy nanoparticles obtained in this comparative example had a larger size and a wider particle size distribution because the increase in the inner diameter of the pipeline weakened the confinement effect during the reaction, resulting in the aggregation of the high-entropy alloy nanoparticles and the formation of clusters between the particles, leading to an increase in the size of the obtained high-entropy alloy nanoparticles.

[0123] The electron micrograph of the high-entropy alloy catalyst particles prepared in this comparative example is as Figure 19 shown.

[0124] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to enumerate all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A high-throughput preparation method of high-entropy alloy nanoparticles, characterized in that: The steps include: 1) preparing 1 to 8 different or identical precursor solutions, each precursor solution being prepared by dissolving at least five soluble metal salts in a solvent; 2) mixing a reducing agent and a flocculant and dissolving them in an alkaline solvent to prepare a reducing solution; 3) contacting and reacting 1 to 8 kinds of precursor solutions and reducing solutions in parallel pipes through peristaltic pumps respectively, and the reaction solutions flow into different beakers through different outlet pipes, and the products are collected after being fully stirred to obtain corresponding 1 to 8 kinds of high entropy alloy crude particles; 4) All the crude high entropy alloy particles are post-processed to obtain 1-8 types of high entropy alloy particles.

2. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 1), the soluble metal salt is selected from one of the following substances: ferrous sulfate, potassium chloropalladate, potassium chloropalladate, cobalt nitrate, nickel nitrate, manganese chloride, magnesium chloride, cobalt chloride, nickel chloride, cupric chloride, lead acetate trihydrate.

3. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 1), the solvent is selected from one or more of the following substances: deionized water, ethanol, methanol, ethylene glycol, isopropanol, and diethyl ether.

4. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 2), the reducing agent is sodium borohydride; and the flocculant is polyvinyl pyrrolidone.

5. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 2), the pH of the alkaline solvent is 10-14; more preferably, the pH of the alkaline solvent is 12.

6. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 2), the mass ratio of the reducing agent to the flocculant is 2-8:1; more preferably, the mass ratio of the flocculant to the reducing agent is 5:

1.

7. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 3), the flow rate of the precursor solution and the reducing solution is 5-15 ml / min; more preferably, the flow rate of the precursor solution and the reducing solution is 8-13 ml / min; the inner diameter of the parallel pipeline is 1.50-2.00 mm.

8. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 3), the stirring speed is 300-1000 rpm / min; more preferably, the stirring speed is 800 rpm / min; the stirring time is 30 min-180 min; more preferably, the stirring time is 120 min.

9. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 1, characterized in that: In step 4), the post-treatment includes one or more of washing and centrifugation.

10. The high-throughput preparation method of high-entropy alloy nanoparticles according to claim 9, characterized in that: The detergent used for washing is selected from one or more of the following substances: ethanol, water, ether, acetone; Preferably, the centrifugal speed is 500-12000 rpm; more preferably, the centrifugal speed is 800-11000 rpm.

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