Preparation method of high-entropy alloy nano-heterojunction catalyst

Abstract

The application discloses a preparation method of a high-entropy alloy nano-heterojunction catalyst, and relates to the technical field of electrocatalytic materials. n+1 AX n powder, and the product is washed with deionized water and centrifuged, then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and the product is freeze-dried to obtain a first reactant; S2, in a protective atmosphere, the first reactant is added to deionized water and inorganic salt a, and ultrasonic dispersion is performed until uniform; metal salt and inorganic salt b are dissolved in deionized water and then added; reaction is performed under an oil bath condition to obtain a second reactant; S3, in a protective atmosphere, the second reactant is placed in a tube furnace for heat treatment to obtain a target product; the HEAs / MXenes nano-heterojunction catalyst obtained through the specific preparation method has high catalytic activity for OER, and solves the problems of low conductivity and insufficient active sites of HEAs and low electrocatalytic activity caused by easy agglomeration of MXenes nanosheets.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalytic materials, in particular to a preparation method of a high-entropy alloy nano-heterojunction catalyst. BACKGROUND

[0002] Oxygen evolution reaction (OER) is an important half-reaction in metal-air batteries, water splitting systems and other new energy conversion and storage devices. However, the slow kinetics of OER seriously hinders the large-scale application of these systems. Designing and developing efficient catalysts is the key to improving the efficiency of OER. At present, some noble metal-based materials such as IrO2 and RuO2 are the most active OER catalysts. However, due to the high cost, scarcity and poor stability of noble metals, their large-scale application is limited. Therefore, it is of great significance to explore and develop low-cost, efficient and stable catalysts to replace noble metal-based catalysts. In recent years, high-entropy alloy oxides (HEAs) formed by more than five elements in equal atomic ratio are considered as one of the potential OER non-noble metal-based catalysts due to their environmental friendliness and abundant reserves. However, on the one hand, the activity of HEAs still needs to be improved due to the lack of active sites and the unsatisfactory adsorption strength of oxygen-containing intermediates; on the other hand, due to its inherent semiconductor properties, the electronic conductivity of HEAs is weak, which leads to the fact that the catalytic efficiency of HEAs still cannot meet the demand of commercial application.

[0003] How to accelerate the slow kinetics of OER of HEAs is a key problem to improve the efficiency of water splitting. To solve this problem, the designed catalyst needs to have moderate oxygen intermediate binding energy on the one hand to balance the adsorption and desorption process of active intermediates and reduce the OER catalytic potential barrier (thermodynamics); on the other hand, the catalyst and the current collector substrate need to have enhanced contact strength and fast electron transport to regulate the active sites and electrochemical stability. Building a two-dimensional non-van der Waals heterostructure with chemical bonding on the current collector substrate is an ideal choice. Among them, the emerging two-dimensional material MXenes has excellent mechanical strength and electrical conductivity, which is an excellent platform for building two-dimensional heterostructures. However, due to the interaction of interlayer van der Waals force, there is a serious self-stacking tendency between MXenes nanosheets. This not only leads to a large loss of specific surface area, but also increases the difficulty of ion transfer and electrolyte diffusion. SUMMARY

[0004] Therefore, one object of the present application is to provide a preparation method of a high-entropy alloy nano-heterojunction catalyst with high OER activity.

[0005] Another object of the present application is to provide a high-entropy alloy nano-heterojunction catalyst with high OER activity.

[0006] To achieve the above object, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a preparation method of a high-entropy alloy nano-heterojunction catalyst with high OER activity, comprising the following steps:

[0008] S1, adding fluoride in an acidic solution, then adding M n+1 AX n powder, reacting under water bath conditions, washing and centrifuging the product with deionized water, then sequentially washing and centrifuging the product with anhydrous ethanol and deionized water, and freeze-drying the product to obtain a first reactant; wherein M n+1 AX n In M, A is a main group metal element, X is a main group non-metal element, and n = 1, 2, or 3.

[0009] S2, adding the first reactant into deionized water and inorganic salt a in a protective atmosphere, ultrasonically dispersing uniformly, dissolving metal salt and inorganic salt b in deionized water and then adding into it, and reacting under oil bath conditions to obtain a second reactant.

[0010] S3, placing the second reactant in a tube furnace for heat treatment in a protective atmosphere to obtain a target product.

[0011] Preferably, in step S1, the acidic solution is selected from one or two of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, oxalic acid, citric acid, perchloric acid, and hypochlorous acid.

[0012] Preferably, the fluoride is selected from one or two of LiF, NaF, KF, RbF, CsF, NH4F, NaHF2, KHF2, NH4HF2, BaF2, ZnF2, MnF2, and BiF3.

[0013] Preferably, M in the M n+1 AX n is selected from Y, Hf, Sc, W, Cr, Mo, Nb, Ti, V, Zr, or Ta.

[0014] A is selected from Al, Si, P, Ga, Ge, As, In, or Sn.

[0015] X is selected from C or N.

[0016] Preferably, the inorganic salt a is selected from one or two of potassium ferricyanide, potassium cobalticyanide, sodium ferrocyanide, potassium ferrocyanide, potassium nickelocyanide, and potassium zincocyanide.

[0017] Preferably, the metal salt is selected from at least four of iron sulfate, iron nitrate, iron acetate, iron oxalate, iron perchlorate, iron chloride, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt perchlorate, cobalt chloride, nickel sulfate, nickel nitrate, nickel acetate, nickel oxalate, nickel perchlorate, nickel chloride, copper sulfate, copper nitrate, copper acetate, copper oxalate, copper perchlorate, copper chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxalate, zinc perchlorate, zinc chloride, manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese perchlorate, manganese chloride, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum oxalate, aluminum perchlorate, aluminum chloride, cadmium sulfate, cadmium nitrate, cadmium acetate, cadmium oxalate, cadmium perchlorate, cadmium chloride, molybdenum chloride, sodium molybdate, molybdenum hexacarbonyl, tungsten chloride, sodium tungstate, tungsten hexacarbonyl, palladium sulfate, palladium nitrate, palladium chloride, platinum nitrate, chloroplatinic acid, ruthenium chloride, ammonium hexachlororuthenate, gold chloride, chloroauric acid, iridium chloride, chloroiridic acid, ammonium chloroiridate, silver nitrate, silver acetate.

[0018] Preferably, the inorganic salt b is selected from one or two of sodium citrate, sodium salicylate, sodium fumarate, sodium sorbate, sodium laurate, sodium glycinate, sodium cinnamate, sodium oxamate, sodium tartrate.

[0019] Preferably, in step S1, the reaction temperature of the water bath condition is 20-100°C, more preferably, the reaction temperature is 25-80°C, most preferably, the reaction temperature is 30-70°C, and the reaction time is 1-120 hours, more preferably, the reaction time is 12-110 hours, most preferably, the reaction time is 24-100 hours.

[0020] Preferably, in step S2, the reaction temperature of the oil bath condition is 80-300°C, more preferably, the reaction temperature is 90-200°C, most preferably, the reaction temperature is 100-150°C, and the reaction time is 1-120 hours, more preferably, the reaction time is 4-60 hours, most preferably, the reaction time is 6-24 hours.

[0021] Preferably, in step S3, the heat treatment temperature is 100-1200°C, more preferably, the heat treatment temperature is 200-1000°C, most preferably, the heat treatment temperature is 300-800°C, the heat treatment heating rate is 1-15°C / min, more preferably, the heat treatment heating rate is 2-10°C / min, most preferably, the heat treatment heating rate is 3-8°C / min, and the heat treatment holding time is 0.5-48 hours, more preferably, the heat treatment holding time is 1-24 hours, most preferably, the heat treatment holding time is 1-12 hours.

[0022] Preferably, in steps S2 and S3, the protective atmosphere is selected from one of nitrogen, hydrogen, oxygen, argon, or hydrogen / argon mixed gas.

[0023] In a second aspect, the application provides a high-entropy alloy nanoheterojunction catalyst prepared by the preparation method described above.

[0024] Compared with the prior art, the application has the beneficial effects that:

[0025] HEAs catalysts exhibit excellent multifunctional catalytic performance due to the synergistic effect of multiple metal components. However, the insufficient active sites and electrical conductivity of HEAs affect its catalytic efficiency in OER. Two-dimensional (2D) transition metal carbides, nitrides and carbonitrides, commonly known as MXenes. Their general formula is M n+1 X n T x wherein M represents an early transition metal, X represents a carbon and / or nitrogen compound, and T x represents a termination group. Since Ti3C2T x MXene was first prepared in 2011, more than 30 kinds of MXenes have been synthesized. In recent years, the inherent physical and chemical properties of MXenes have been extensively studied, revealing that MXenes have the advantages of metallic conductivity, high mechanical strength, diverse surface chemical properties, and high electrochemical activity. However, the application of MXenes is greatly affected by the non-negligible stacking problem. It is necessary to solve the stacking problem common to 2D MXene materials to promote their wide application. Among them, the heterostructure electrocatalyst based on MXenes exhibits superior electrocatalytic performance due to the improvement of physical or chemical properties. Therefore, in view of the problems of HEAs and MXenes, HEAs precursor nanometer arrays are in-situ grown on 2D MXene nanosheets, and then further calcination is performed to anchor the HEAs precursor nanometer arrays on the surface of the MXene nanosheets, thereby obtaining a HEAs / MXenes nanoheterojunction catalyst. The MXene nanosheet not only serves as a conductive carrier for HEAs to improve the electrical conductivity of the catalyst, but also can inhibit the stacking problem of the MXene nanosheet itself.

[0026] Compared with the existing preparation of high-entropy alloy nanocatalysts, the application introduces MXenes with high electrical conductivity and excellent mechanical stability to stabilize and uniformly disperse HEAs, so that HEAs and MXenes combine to form a strong heterojunction interface, and a synergistic effect between the two is generated, thereby designing and constructing a HEAs / MXenes nanoheterojunction catalyst. The heterojunction interface not only contributes more exposed active sites for OER and promotes the reaction kinetics, but also realizes fast electron transfer between different components.

[0027] The synergistic effect between the chemical components in the HEAs / MXenes nanoheterojunction catalyst of the application makes it have excellent electrocatalytic performance, the HEAs / MXenes nanoheterojunction catalyst obtained by the specific preparation method of the application shows high catalytic activity for OER, and solves the problems of low conductivity and insufficient active sites of HEAs and low electrocatalytic activity caused by easy agglomeration of MXenes nanosheets. In addition, the preparation method of the HEAs / MXenes nanoheterojunction catalyst of the application also has the advantages of simple process, low cost and easy scaling. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0029] Figure 1 The first reactant prepared in the embodiment 1 of the application is Ti3C2T x MXene scanning electron microscope image.

[0030] Figure 2 The second reactant prepared in the embodiment 1 of the application is CoNiCuZnFe-PBA / Ti3C2T x MXene scanning electron microscope image.

[0031] Figure 3 CoNiCuZnFeO x / Ti3C2T x MXene scanning electron microscope image.

[0032] Figure 4 CoNiCuZnFeO x / V2CT x MXene scanning electron microscope image.

[0033] Figure 5 CoNiCuZnFeO x / Nb2CT x MXene scanning electron microscope image.

[0034] Figure 6 CoNiCuZnFeO x / Ta4C3T x MXene scanning electron microscope image.

[0035] Figure 7 CoNiCuZnAlCrFeO prepared for the present application embodiment 20 x / Ti3C2T x MXene scanning electron microscope image.

[0036] Figure 8 CoNiCuCrPdAgAuRuIrFeO prepared for the present application embodiment 23 x / Ti3C2T x MXene scanning electron microscope image. DETAILED DESCRIPTION

[0037] In order to make the objects, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below. The following gives several embodiments of the present application. However, the present application can be realized in many different forms, and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive:

[0038] Embodiment 1

[0039] The present embodiment provides a first high-entropy alloy nano-heterojunction catalyst, and its preparation method is as follows:

[0040] S1, 1g of LiF was added to 50mL of hydrochloric acid and stirred to obtain a solution a; then, 1g of Ti3AlC2 powder was added to the solution a, and the reaction was stirred magnetically at 45℃ water bath for 24 hours, the product was washed with deionized water and centrifuged, then washed with anhydrous ethanol and deionized water and centrifuged, and the product was freeze-dried to obtain the first reactant, i.e. Ti3C2T x MXene.

[0041] S2, the Ti3C2T x MXene obtained in the above step S1 was first added to deionized water and ultrasonically dispersed uniformly, then potassium ferricyanide was added to obtain a solution b; then, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and sodium citrate were dissolved in deionized water to obtain a solution c, then the solution c was slowly added to the solution b, and the reaction was stirred magnetically at 100℃ in an oil bath under nitrogen protection gas for 24 hours, then washing, filtering and freeze-drying were sequentially carried out to obtain the second reactant.

[0042] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment, and was heated from room temperature to 500℃ at a heating rate of 3℃ / min under argon protection gas, and reacted at the temperature for 6 hours to obtain Ti3C2T xMXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuZnFeO x / Ti3C2T x MXene).

[0043] From Figures 1-3 It can be seen from the change that the high-entropy alloy nanoheterojunction catalyst prepared in the embodiment has more active sites exposed and basically no agglomeration phenomenon.

[0044] Example 2

[0045] The second high-entropy alloy nanoheterojunction catalyst is provided in the embodiment, and the preparation method is as follows:

[0046] S1, 1g of NaF was added to 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Ti3AlC2 powder was added to the a solution, and the reaction was stirred magnetically at 45℃ under water bath condition for 24 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, i.e., Ti3C2T x MXene.

[0047] S2, the Ti3C2T x MXene obtained in the above step S1 was first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide was added thereto to obtain a b solution; then, cobalt nitrate, nickel nitrate, manganese nitrate, aluminum nitrate and sodium citrate were dissolved in deionized water to obtain a c solution, and then the c solution was slowly added to the b solution; under the protection of nitrogen gas, the reaction was stirred magnetically in an oil bath at 100℃ for 24 hours, and then sequentially washed, filtered and freeze-dried to obtain a second reactant.

[0048] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment, and was heated from room temperature to 500℃ at a heating rate of 3℃ / min under the protection of argon gas, and reacted at the temperature for 6 hours to obtain Ti3C2T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiMnAlFeO x / Ti3C2T x MXene).

[0049] Example 3

[0050] The third high-entropy alloy nanoheterojunction catalyst is provided in the embodiment, and the preparation method is as follows:

[0051] S1. Add 1g KF to 50mL hydrochloric acid and stir to obtain solution a; then, add 1g Ti3AlC2 powder to solution a, and react magnetically at 45℃ for 24 hours. Wash the product with deionized water and centrifuge, then wash with anhydrous ethanol and deionized water successively and centrifuge. Freeze-dry the product to obtain the first reactant, namely Ti3C2T. x MXene.

[0052] S2, Take the Ti3C2T obtained in step S1 above... x MXene was first added to deionized water and ultrasonically dispersed evenly. Then, potassium ferricyanide was added to obtain solution b. Next, cobalt nitrate, nickel nitrate, cadmium nitrate, silver nitrate, and sodium citrate were dissolved in deionized water to obtain solution c. Then, solution c was slowly added to solution b. The reaction was carried out under nitrogen protection in an oil bath at 100°C with magnetic stirring for 24 hours. Then, the mixture was washed, filtered, and freeze-dried to obtain the second reactant.

[0053] S3. The second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment. Under an argon protective gas atmosphere, the temperature is increased from room temperature to 500°C at a rate of 3°C / min, and the reaction is carried out at this temperature for 6 hours to obtain Ti3C2T. x MXene-supported high-entropy alloy nanoheterojunction catalyst (CoNiCrAgFeO) x / Ti3C2T x MXene).

[0054] Example 4

[0055] This embodiment provides a fourth type of high-entropy alloy nanoheterojunction catalyst, the preparation method of which is as follows:

[0056] S1. Add 1g of NH4F to 50mL of hydrochloric acid and stir to obtain solution a; then, add 1g of Ti3AlC2 powder to solution a, and react magnetically at 45℃ for 24 hours. Wash the product with deionized water and centrifuge, then wash with anhydrous ethanol and deionized water successively and centrifuge. Freeze-dry the product to obtain the first reactant, namely Ti3C2T. x MXene.

[0057] S2, Take the Ti3C2T obtained in step S1 above... xMXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, palladium nitrate, chloroauric acid and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath under magnetic stirring for 24 hours, and then washing, filtering and freeze-drying are sequentially performed to obtain a second reactant.

[0058] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and under the protection of argon gas, the temperature is raised from room temperature to 500℃ at a rate of 3℃ / min, and reacted at this temperature for 6 hours to obtain Ti3C2T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiPdAuFeO x / Ti3C2T x MXene).

[0059] Example 5

[0060] This example provides a fifth high-entropy alloy nanoheterojunction catalyst, and the preparation method is as follows:

[0061] S1, 1g of NaHF2 is added to 50mL of hydrochloric acid and stirred to obtain solution a; then, 1g of Ti3AlC2 powder is added to solution a, and the reaction is carried out under magnetic stirring at 45℃ water bath for 24 hours, the product is washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and the product is freeze-dried to obtain a first reactant, i.e. Ti3C2T x MXene.

[0062] S2, the Ti3C2T x MXene obtained in the above step S1 is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, platinum nitrate, ruthenium chloride and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath under magnetic stirring for 24 hours, and then washing, filtering and freeze-drying are sequentially performed to obtain a second reactant.

[0063] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and under the protection of argon gas, the temperature is raised from room temperature to 500℃ at a rate of 3℃ / min, and reacted at this temperature for 6 hours to obtain Ti3C2T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiPtRuFeO x / Ti3C2T x MXene).

[0064] Embodiment 6

[0065] The embodiment provides a sixth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0066] S1, 1g of LiF was added into 50mL of hydrofluoric acid and stirred to obtain a solution; then, 1g of V2AlC powder was added into the a solution, and the reaction was stirred under the condition of a 35℃ water bath for 100 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, namely V2CT x MXene.

[0067] S2, the V2CT x MXene obtained in the above step S1 was first added into deionized water and ultrasonically dispersed uniformly, and then potassium cobalt cyanide was added into the deionized water to obtain a b solution; then, iron sulfate, nickel sulfate, copper sulfate, zinc sulfate and sodium citrate were dissolved in deionized water to obtain a c solution; then, the c solution was slowly added into the b solution, and the reaction was stirred under the condition of a 100℃ oil bath and nitrogen protection for 24 hours; then, the washing, filtration and freeze-drying treatment were sequentially performed to obtain a second reactant.

[0068] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment, and was heated from room temperature to 500℃ at a heating rate of 5℃ / min under the protection of argon gas, and reacted at the temperature for 6 hours to obtain a V2CT x MXene supported high-entropy alloy nano-heterojunction catalyst (CoNiCuZnFeO x / V2CT x MXene).

[0069] Embodiment 7

[0070] The embodiment provides a seventh high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0071] S1, 1g of NaF was added into 50mL of hydrofluoric acid and stirred to obtain a solution; then, 1g of V2AlC powder was added into the a solution, and the reaction was stirred under the condition of a 40℃ water bath for 60 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, namely V2CT x MXene.

[0072] S2, the V2CT xMXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium cobalt cyanide is added to obtain solution b; then, copper sulfate, nickel sulfate, manganese sulfate, aluminum sulfate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, under the protection of nitrogen gas, and magnetically stirred at 100°C in an oil bath for 24 hours, and then sequentially subjected to washing, filtration and freeze-drying treatment to obtain a second reactant.

[0073] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, under the protection of argon gas, and heated from room temperature to 500°C at a rate of 5°C / min, and reacted at this temperature for 6 hours to obtain V2CT x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuMnAlO x / V2CT x MXene).

[0074] Example 8

[0075] This example provides an eighth high-entropy alloy nanoheterojunction catalyst, and the preparation method is as follows:

[0076] S1, 1g of KF is added to 50mL of hydrofluoric acid and stirred to obtain solution a; then, 1g of V2AlC powder is added to solution a, and magnetically stirred at 50°C in a water bath for 48 hours, the product is washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and the product is freeze-dried to obtain a first reactant, i.e., V2CT x MXene.

[0077] S2, the V2CT x MXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium cobalt cyanide is added to obtain solution b; then, copper sulfate, nickel sulfate, manganese sulfate, aluminum sulfate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, under the protection of nitrogen gas, and magnetically stirred at 100°C in an oil bath for 24 hours, and then sequentially subjected to washing, filtration and freeze-drying treatment to obtain a second reactant.

[0078] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, under the protection of argon gas, and heated from room temperature to 500°C at a rate of 5°C / min, and reacted at this temperature for 6 hours to obtain V2CT x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCrAgPdO x / V2CT x MXene).

[0079] Example 9

[0080] This embodiment provides a ninth high-entropy alloy nano-heterojunction catalyst, and the preparation method is as follows:

[0081] S1, 1g of NH4F was added to 50mL of hydrofluoric acid and stirred to obtain a solution; then, 1g of V2AlC powder was added to the a solution, and the reaction was stirred under a 50℃ water bath for 48 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, i.e., V2CT x MXene.

[0082] S2, the V2CT x MXene obtained in the above step S1 was first added to deionized water and ultrasonically dispersed uniformly, and then potassium cobalt cyanide was added to obtain a b solution; then, nickel sulfate, palladium nitrate, platinum nitrate, chloroauric acid and sodium citrate were dissolved in deionized water to obtain a c solution, and then the c solution was slowly added to the b solution; under the protection of nitrogen gas, the reaction was stirred under an oil bath at 100℃ for 24 hours, and then sequentially washed, filtered and freeze-dried to obtain a second reactant.

[0083] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment, and was heated from room temperature to 500℃ at a heating rate of 5℃ / min under the protection of argon gas, and reacted at the temperature for 6 hours to obtain a V2CT x MXene supported high-entropy alloy nano-heterojunction catalyst (CoNiPdPtAuO x / V2CT x MXene).

[0084] Example 10

[0085] This embodiment provides a tenth high-entropy alloy nano-heterojunction catalyst, and the preparation method is as follows:

[0086] S1, 1g of NaHF2 was added to 50mL of hydrofluoric acid and stirred to obtain a solution; then, 1g of V2AlC powder was added to the a solution, and the reaction was stirred under a 45℃ water bath for 50 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, i.e., V2CT x MXene.

[0087] S2, the V2CT xMXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium cobalt cyanide is added to obtain solution b; then, copper sulfate, nickel nitrate, iridium chloride, ruthenium chloride and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours under magnetic stirring, and then washing, filtering and freeze-drying are sequentially carried out to obtain a second reactant.

[0088] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and under the protection of argon gas, the temperature is raised from room temperature to 500℃ at a rate of 5℃ / min, and reacted at this temperature for 6 hours to obtain V2CT x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuIrRuO x / V2CT x MXene).

[0089] Example 11

[0090] This example provides an eleventh high-entropy alloy nanoheterojunction catalyst, and the preparation method is as follows:

[0091] S1, 1g of LiF is added to 50mL of hydrochloric acid and stirred to obtain solution a; then, 1g of Nb2AlC powder is added to solution a, and the reaction is carried out under magnetic stirring at 55℃ water bath for 65 hours, the product is washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and the product is freeze-dried to obtain a first reactant, i.e. Nb2CT x MXene.

[0092] S2, the Nb2CT x MXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium cobalt cyanide is added to obtain solution b; then, copper sulfate, nickel nitrate, iridium chloride, ruthenium chloride and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours under magnetic stirring, and then washing, filtering and freeze-drying are sequentially carried out to obtain a second reactant.

[0093] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and under the protection of argon gas, the temperature is raised from room temperature to 500℃ at a rate of 5℃ / min, and reacted at this temperature for 6 hours to obtain V2CT x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuZnFeO x / Nb2CT x MXene).

[0094] Embodiment 12

[0095] The embodiment provides a twelfth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0096] S1, 1g of LiF was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Nb2AlC powder was added into the a solution, and the reaction was stirred under the condition of a 55℃ water bath and a magnetic force for 65 hours; the product was washed and centrifuged with deionized water, and then washed and centrifuged with anhydrous ethanol and deionized water in sequence; the product was freeze-dried to obtain a first reactant, namely Nb2CT x MXene.

[0097] S2, the Nb2CT x MXene obtained in the step S1 was first added into deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide was added into the deionized water to obtain a b solution; then, copper chloride, nickel chloride, manganese chloride, aluminum nitrate and sodium citrate were dissolved in deionized water to obtain a c solution, and then the c solution was slowly added into the b solution; the reaction was stirred under the condition of a 100℃ oil bath and a magnetic force under the protection of nitrogen gas for 24 hours; and then washing, filtering and freeze-drying were sequentially performed to obtain a second reactant.

[0098] S3, the second reactant obtained in the step S2 was placed in a tube furnace for high-temperature heat treatment; the temperature was raised from room temperature to 600℃ at a temperature raising rate of 3℃ / min under the protection of argon gas, and the reaction was performed at the temperature for 5 hours to obtain a Nb2CT x MXene supported high-entropy alloy nano-heterojunction catalyst (CoNiCuMnAlO x / Nb2CT x MXene).

[0099] Embodiment 13

[0100] The embodiment provides a thirteenth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0101] S1, 1g of KF was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Nb2AlC powder was added into the a solution, and the reaction was stirred under the condition of a 55℃ water bath and a magnetic force for 60 hours; the product was washed and centrifuged with deionized water, and then washed and centrifuged with anhydrous ethanol and deionized water in sequence; the product was freeze-dried to obtain a first reactant, namely Nb2CT x MXene.

[0102] S2, the Nb2CT xMXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, cadmium nitrate, silver nitrate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours under magnetic stirring, and then washing, filtering and freeze-drying are sequentially performed to obtain the second reactant.

[0103] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and the temperature is raised from room temperature to 600℃ at a rate of 3℃ / min under the protection of argon gas, and reacted at this temperature for 5 hours to obtain Nb2CT x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCrAgFeO x / Nb2CT x MXene).

[0104] Example 14

[0105] The fourteenth high-entropy alloy nanoheterojunction catalyst is provided, and the preparation method is as follows:

[0106] S1, 1g of NH4F is added to 50mL of hydrochloric acid and stirred to obtain solution a; then, 1g of Nb2AlC powder is added to solution a, and the reaction is carried out at 55℃ in a water bath for 60 hours under magnetic stirring, and then the product is washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and then the product is freeze-dried to obtain the first reactant, i.e., Nb2CT x MXene.

[0107] S2, the Nb2CT x MXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, cadmium nitrate, silver nitrate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours under magnetic stirring, and then washing, filtering and freeze-drying are sequentially performed to obtain the second reactant.

[0108] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and the temperature is raised from room temperature to 600℃ at a rate of 3℃ / min under the protection of argon gas, and reacted at this temperature for 5 hours to obtain Nb2CT x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCrAgFeO x / Nb2CT x MXene).

[0109] Embodiment 15

[0110] This embodiment provides a fifteenth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0111] S1, 1g of NaHF2 was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Nb2AlC powder was added into the a solution, and the reaction was carried out under the condition of a 45℃ water bath and magnetic stirring for 72 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, i.e., Nb2CT x MXene.

[0112] S2, the Nb2CT x MXene obtained in the above step S1 was first added into deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide was added into the deionized water to obtain a b solution; then, cobalt nitrate, nickel nitrate, platinum nitrate, ruthenium chloride and sodium citrate were dissolved in deionized water to obtain a c solution, and then the c solution was slowly added into the b solution; the reaction was carried out under the protection of nitrogen gas, in an oil bath at 100℃ and magnetic stirring for 24 hours; and then washing, filtering and freeze-drying were sequentially carried out to obtain a second reactant.

[0113] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment; the temperature was raised from room temperature to 500℃ at a rate of 3℃ / min under the protection of argon gas, and reacted at the temperature for 6 hours to obtain a Nb2CT x MXene supported high-entropy alloy nano-heterojunction catalyst (CoNiPtRuFeO x / Nb2CT x MXene).

[0114] Embodiment 16

[0115] This embodiment provides a sixteenth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0116] S1, 1g of LiF was added into 50mL of hydrofluoric acid and stirred to obtain a solution; then, 1g of Ta4AlC3 powder was added into the a solution, and the reaction was carried out under the condition of a 25℃ water bath and magnetic stirring for 96 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain a first reactant, i.e., Ta4C3T x MXene.

[0117] S2, the Ta4C3T xMXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours, and then washing, filtering and freeze-drying are sequentially carried out to obtain the second reactant.

[0118] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and the temperature is raised from room temperature to 600℃ at a rate of 8℃ / min in an argon protective gas, and reacted at this temperature for 4 hours to obtain Ta4C3T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuZnFeO x / Ta4C3T x MXene).

[0119] Example 17

[0120] The present embodiment provides a seventeenth kind of high-entropy alloy nanoheterojunction catalyst, and the preparation method is as follows:

[0121] S1, 1g of LiF is added to 50mL of hydrochloric acid and stirred to obtain solution a; then, 1g of Mo2Ga2C powder is added to solution a, and the reaction is carried out at 25℃ in a water bath for 48 hours, and then the product is washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and then the product is freeze-dried to obtain the first reactant, i.e., Mo2CT x MXene.

[0122] S2, the Mo2CT x MXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours, and then washing, filtering and freeze-drying are sequentially carried out to obtain the second reactant.

[0123] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and the temperature is raised from room temperature to 600℃ at a rate of 8℃ / min in an argon protective gas, and reacted at this temperature for 4 hours to obtain Ta4C3T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuZnFeO x / Mo2CT x MXene).

[0124] Embodiment 18

[0125] The embodiment provides an eighteenth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0126] S1, 1g of LiF was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Mo2AlTiC2 powder was added into the a solution, and the reaction was stirred under the condition of a 55℃ water bath for 80 hours; the product was washed and centrifuged with deionized water, and then washed and centrifuged with anhydrous ethanol and deionized water in sequence; the product was freeze-dried to obtain a first reactant, namely Mo2TiC2T x MXene.

[0127] S2, the Mo2CT x MXene obtained in the above step S1 was first added into deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide was added into the deionized water to obtain a b solution; then, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and sodium citrate were dissolved in deionized water to obtain a c solution, and then the c solution was slowly added into the b solution; the reaction was stirred under the condition of a 100℃ oil bath and nitrogen protection for 24 hours; and then washing, filtering and freeze-drying were sequentially performed to obtain a second reactant.

[0128] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment; the temperature was raised from room temperature to 600℃ at a temperature raising rate of 6℃ / min under the protection of argon gas, and the reaction was performed at the temperature for 6 hours to obtain a Mo2TiC2T x MXene supported high-entropy alloy nano-heterojunction catalyst (CoNiCuZnFeO x / Mo2TiC2T x MXene).

[0129] Embodiment 19

[0130] The embodiment provides a nineteenth high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0131] S1, 1g of LiF was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Mo2AlTiC2 powder was added into the a solution, and the reaction was stirred under the condition of a 55℃ water bath for 80 hours; the product was washed and centrifuged with deionized water, and then washed and centrifuged with anhydrous ethanol and deionized water in sequence; the product was freeze-dried to obtain a first reactant, namely Mo2TiC2T x MXene.

[0132] S2, the Mo2CT xMXene is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours under magnetic stirring, and then washing, filtering and freeze-drying are sequentially performed to obtain a second reactant,

[0133] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and the temperature is raised from room temperature to 500℃ at a rate of 5℃ / min under the protection of argon gas, and reacted at this temperature for 5 hours to obtain Ti3C2T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuZnMnFeO x / Ti3C2T x MXene).

[0134] Example 20

[0135] The present embodiment provides a twentieth high-entropy alloy nanoheterojunction catalyst, and the preparation method is as follows:

[0136] S1, 1g of LiF is added to 50mL of hydrochloric acid and stirred to obtain solution a; then, 1g of Ti3AlC2 powder is added to solution a, and the reaction is carried out under magnetic stirring at 45℃ water bath for 48 hours, the product is washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged, and the product is freeze-dried to obtain a first reactant, i.e., Ti3C2T x MXene.

[0137] S2, the Ti3C2T x MXene obtained in the above step S1 is first added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide is added to obtain solution b; then, cobalt nitrate, nickel nitrate, copper nitrate, aluminum nitrate, cadmium chloride, zinc nitrate and sodium citrate are dissolved in deionized water to obtain solution c, and then solution c is slowly added to solution b, and under the protection of nitrogen gas, the reaction is carried out at 100℃ in an oil bath for 24 hours under magnetic stirring, and then washing, filtering and freeze-drying are sequentially performed to obtain a second reactant.

[0138] S3, the second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment, and the temperature is raised from room temperature to 500℃ at a rate of 5℃ / min under the protection of argon gas, and reacted at this temperature for 5 hours to obtain Ti3C2T x MXene supported high-entropy alloy nanoheterojunction catalyst (CoNiCuZnAlCrFeO x / Ti3C2Tx MXene).

[0139] Embodiment 21

[0140] The embodiment provides a twenty-first high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0141] S1, 1g of LiF was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Ti3AlC2 powder was added into the a solution, and the reaction was stirred under the condition of a 45℃ water bath for 48 hours; the product was washed and centrifuged with deionized water, and then washed and centrifuged with anhydrous ethanol and deionized water in sequence; the product was freeze-dried to obtain a first reactant, i.e., Ti3C2T x MXene.

[0142] S2, the Ti3C2T x MXene obtained in the above step S1 was first added into deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide was added into the deionized water to obtain a b solution; then, cobalt nitrate, nickel nitrate, copper nitrate, palladium nitrate, cadmium sulfate, silver nitrate, sodium molybdate and sodium citrate were dissolved in deionized water to obtain a c solution; then, the c solution was slowly added into the b solution, and the reaction was stirred under the condition of a 100℃ oil bath and nitrogen protection for 24 hours; and then, the washing, filtration and freeze-drying treatment were sequentially performed to obtain a second reactant.

[0143] S3, the second reactant obtained in the step S2 was placed in a tube furnace for high-temperature heat treatment, and the temperature was increased from room temperature to 500℃ at a temperature increasing rate of 5℃ / min under the protection of argon gas, and the reaction was performed at the temperature for 5 hours to obtain a Ti3C2T x MXene supported high-entropy alloy nano-heterojunction catalyst (CoNiCuCrPdAgFeMoO x / Ti3C2T x MXene).

[0144] Embodiment 22

[0145] The embodiment provides a twenty-second high-entropy alloy nano-heterojunction catalyst, and a preparation method thereof is as follows:

[0146] S1, 1g of LiF was added into 50mL of hydrochloric acid and stirred to obtain a solution; then, 1g of Ti3AlC2 powder was added into the a solution, and the reaction was stirred under the condition of a 45℃ water bath for 48 hours; the product was washed and centrifuged with deionized water, and then washed and centrifuged with anhydrous ethanol and deionized water in sequence; the product was freeze-dried to obtain a first reactant, i.e., Ti3C2T x MXene.

[0147] S2, Take the Ti3C2T obtained in step S1 above... x MXene was first added to deionized water and ultrasonically dispersed evenly. Then, potassium ferricyanide was added to obtain solution b. Next, cobalt nitrate, nickel nitrate, copper nitrate, palladium nitrate, cadmium sulfate, silver nitrate, gold chloride, sodium tungstate, and sodium citrate were dissolved in deionized water to obtain solution c. Then, solution c was slowly added to solution b. The reaction was carried out under nitrogen protection in an oil bath at 100°C with magnetic stirring for 24 hours. Then, the mixture was washed, filtered, and freeze-dried to obtain the second reactant.

[0148] S3. The second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment. Under an argon protective gas atmosphere, the temperature is increased from room temperature to 500°C at a rate of 5°C / min, and the reaction is carried out at this temperature for 5 hours to obtain Ti3C2T. x MXene-supported high-entropy alloy nanoheterojunction catalyst (CoNiCuCrPdAgAuFeWO3) x / Ti3C2T x MXene).

[0149] Example 23

[0150] This embodiment provides the twenty-third type of high-entropy alloy nanoheterojunction catalyst, and its preparation method is as follows:

[0151] S1. Add 1g LiF to 50mL hydrochloric acid and stir to obtain solution a; then, add 1g Ti3AlC2 powder to solution a, and react magnetically at 45℃ for 24 hours. Wash the product with deionized water and centrifuge, then wash with anhydrous ethanol and deionized water successively and centrifuge. Freeze-dry the product to obtain the first reactant, namely Ti3C2T. x MXene.

[0152] S2, Take the Ti3C2T obtained in step S1 above... x MXene was first added to deionized water and ultrasonically dispersed evenly. Then, potassium ferricyanide was added to obtain solution b. Next, cobalt nitrate, nickel nitrate, copper nitrate, palladium nitrate, cadmium sulfate, silver nitrate, gold chloride, ruthenium chloride, iridium chloride, and sodium citrate were dissolved in deionized water to obtain solution c. Then, solution c was slowly added to solution b. The reaction was carried out under nitrogen protection in an oil bath at 100°C with magnetic stirring for 24 hours. Then, the mixture was washed, filtered, and freeze-dried to obtain the second reactant.

[0153] S3. The second reactant obtained in step S2 is placed in a tube furnace for high-temperature heat treatment. Under an argon protective gas atmosphere, the temperature is increased from room temperature to 500°C at a rate of 5°C / min, and the reaction is carried out at this temperature for 5 hours to obtain Ti3C2T. xMXene supported high-entropy alloy nanoheterostructure catalyst (CoNiCuCrPdAgAuRuIrFeO x / Ti3C2T x MXene).

[0154] Comparative Example 1

[0155] The present example provides a comparative example, which is prepared as follows:

[0156] S1, 1g of LiF was added to 50mL of hydrochloric acid and stirred to obtain solution a; then, 1g of Ti3AlC2 was added to solution a, and the reaction was stirred magnetically under a 45℃ water bath for 48 hours; the product was washed with deionized water and centrifuged, and then sequentially washed with anhydrous ethanol and deionized water and centrifuged; the product was freeze-dried to obtain the first reactant, i.e., Ti3C2T x MXene.

[0157] S2, the Ti3C2T x was obtained in the above step S1 was weighed and added to deionized water and ultrasonically dispersed uniformly, and then potassium ferricyanide was added thereto to obtain solution b; then, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and sodium citrate were dissolved in deionized water to obtain solution c, and then solution c was slowly added to solution b; under nitrogen protection gas, the reaction was stirred magnetically in an oil bath at 100℃ for 24 hours, and then sequentially washed, filtered and freeze-dried to obtain the second reactant;

[0158] S3, the second reactant obtained in step S2 was placed in a tube furnace for high-temperature heat treatment, and was heated from room temperature to 500℃ at a heating rate of 5℃ / min under oxygen protection gas, and reacted at this temperature for 5 hours.

[0159] The method of the comparative example cannot obtain Ti3C2T x MXene supported high-entropy alloy nanoheterostructure catalyst.

[0160] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0161] The above only describes the preferred embodiments of the present application, and does not limit the present application in any form, and any simple modification, equivalent change and modification made on the basis of the technical essence of the present application to the above embodiments all belong to the scope of the technical solutions of the present application.

Claims

1. A method for preparing a high-entropy alloy nanoheterojunction catalyst, characterized in that: Includes the following steps: S1. Fluoride is added to an acidic solution, followed by Mn+1AXn powder. The reaction is carried out under water bath conditions. The product is washed with deionized water and centrifuged, then washed with anhydrous ethanol and deionized water in sequence and centrifuged. The product is freeze-dried to obtain the first reactant. In Mn+1AXn, M is a transition metal element, A is a main group metal element, X is a main group nonmetal element, and n = 1, 2, 3. M in Mn+1AXn is selected from Y, Hf, Sc, W, Cr, Mo, Nb, Ti, V, Zr or Ta. The A is selected from Al, Si, P, Ga, Ge, As, In, or Sn; X is selected from C or N; S2. In a protective atmosphere, the first reactant is added to deionized water and inorganic salt a, and ultrasonically dispersed evenly. The metal salt and inorganic salt b are dissolved in deionized water and then added to the mixture. The reaction is carried out under oil bath conditions to obtain the second reactant. The inorganic salt a is selected from one or two of potassium ferrocyanide, potassium cobalt cyanide, sodium ferrocyanide, potassium ferrocyanide, potassium nickel cyanide, and potassium zinc cyanide. S3. Under a protective atmosphere, the second reactant is placed in a tube furnace for heat treatment to obtain the target product.

2. The preparation method according to claim 1, characterized in that: In step S1, the acidic solution is selected from one or two of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, oxalic acid, citric acid, perchloric acid, and hypochlorous acid.

3. The preparation method according to claim 1, characterized in that: The fluoride is selected from one or two of LiF, NaF, KF, RbF, CsF, NH4F, NaHF2, KHF2, NH4HF2, BaF2, ZnF2, MnF2, and BiF3.

4. The preparation method according to claim 1, characterized in that: The metal salts are selected from ferric sulfate, ferric nitrate, ferric acetate, ferric oxalate, ferric perchlorate, ferric chloride, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt perchlorate, cobalt chloride, nickel sulfate, nickel nitrate, nickel acetate, nickel oxalate, nickel perchlorate, nickel chloride, copper sulfate, copper nitrate, copper acetate, copper oxalate, copper perchlorate, copper chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxalate, zinc perchlorate, zinc chloride, manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, and high... The following are at least four of the following: manganese chlorate, manganese chloride, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum oxalate, aluminum perchlorate, aluminum chloride, cadmium sulfate, cadmium nitrate, cadmium acetate, cadmium oxalate, cadmium perchlorate, cadmium chloride, molybdenum chloride, sodium molybdate, molybdenum hexacarbonyl, tungsten chloride, sodium tungstate, tungsten hexacarbonyl, palladium sulfate, palladium nitrate, palladium chloride, platinum nitrate, chloroplatinic acid, ruthenium chloride, ammonium hexachlororuthenate, gold chloride, chloroauric acid, iridium chloride, chloroirinic acid, ammonium chloroirinate, silver nitrate, and silver acetate. The inorganic salt b is selected from one or two of sodium citrate, sodium salicylate, sodium fumarate, sodium sorbate, sodium laurate, sodium glycinate, sodium cinnamate, sodium oxalate, and sodium tartrate.

5. The preparation method according to claim 1, characterized in that: In step S1, the reaction temperature of the water bath is 20–100°C, and the reaction time is 1–120 hours.

6. The preparation method according to claim 1, characterized in that: In step S2, the reaction temperature of the oil bath is 80–300°C, and the reaction time is 1–120 hours.

7. The preparation method according to claim 1, characterized in that: In steps S2 and S3, the protective atmosphere is selected from either nitrogen or argon.

8. The preparation method according to claim 1, characterized in that: In step S3, the heat treatment temperature is 100-1200℃, the heating rate is 1-15℃ / min, and the heat treatment holding time is 0.5-48 hours.

9. A high-entropy alloy nanoheterojunction catalyst, characterized in that: Including high-entropy alloy nanoheterojunction catalysts obtained by the preparation method according to any one of claims 1 to 8.

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