Medium-high-entropy metal carbide material for hydrogen evolution reaction as well as preparation method and application of medium-high-entropy metal carbide material

Abstract

The invention belongs to the technical field of materials, and relates to a medium-high-entropy metal carbide material for hydrogen evolution reaction and a preparation method thereof.The medium-high-entropy metal carbide material comprises a carbon carrier and medium-high-entropy metal carbide loaded on the carbon carrier, and metal in the medium-high-entropy metal carbide comprises precious metal A and transition metal B; based on the total weight of the medium-and-high-entropy metal carbide material, the mass percentage of metal is 0.1%-70%. The preparation process of the medium-high-entropy metal carbide material comprises the following steps: uniformly mixing a metal precursor and a carbon-containing precursor, carrying out high-temperature roasting, and cooling to room temperature to obtain the medium-high-entropy metal carbide material. Compared with the prior art, the method has the advantages that the microstructure and electron distribution are effectively adjusted through various metal components in the medium-high-entropy metal carbide, so that the adsorption energy between a hydrogen intermediate and an active site is optimized, the catalytic activity of a hydrogen evolution reaction is improved, and the problem that transition metal carbide is prone to oxidation is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of materials, and in particular relates to a high entropy metal carbide material for hydrogen evolution reverse application and a preparation method thereof. Background Art

[0002] With the exhaustion of fossil energy, finding new green and efficient energy sources has become a top priority. The hydrogen evolution reaction (HER) from water electrolysis is a promising method for storing hydrogen energy, and the key lies in the efficiency of the electrocatalyst. Hydrogen evolution reaction catalysts mainly include platinum-based metal catalysts, transition metal-based electrocatalysts, high entropy alloys (HEAs), high entropy oxides (HEOs) and high entropy carbides (HECs). Emerging high-entropy materials constrain multiple main elements in a lattice, providing great possibilities for designing high-performance hydrogen evolution reaction catalysts (High-Entropy Alloy Nanosheets for Fine-Tuning Hydrogen Evolution [J]. ACS Catalysis 2022, 12 (19), 11955-11959).

[0003] High-entropy alloys and their derived carbides, nitrides, sulfides and phosphides are considered to be a new generation of energy conversion catalysts due to their high entropy, lattice distortion, hysteresis diffusion and "cocktail" effect (High-entropy metal carbide nanowires [J]. Cell Reports Physical Science 2022, 3 (4), 100839). Medium- and high-entropy metal carbide materials have metastable states and more lattice distortions. At the same time, amorphous materials have a higher defect site density and unique electronic structure than crystalline materials, thus having a large number of active sites and higher intrinsic catalytic ability, which makes them have lower reaction energy barriers in many catalytic reactions. However, there are currently no reports on disordered metal carbides and their preparation methods.

[0004] In addition, electrocatalysis requires a sufficient number of active sites, and the resulting medium-high entropy metal carbide materials are usually submicron or even micron-sized, and their particles are too large for electrocatalytic applications. The synthesis of medium-high entropy metal carbide nanomaterials is a huge challenge (Electrical Discharge Induced Bulk-to-Nanoparticle Transformation: Nano High-Entropy Carbide as Catalysts for Hydrogen Evolution Reaction[J]. Advanced Functional Materials 2022, 32(35), 2203787). Moreover, transition metal carbides, such as Mo2C, are prone to forming an inert oxide layer on their surface. The formation of this oxide thin layer will significantly reduce the conductivity of the carbide material, and also reduce its catalytic activity as a hydrogen evolution reaction.

[0005] Therefore, how to further regulate the particle size and electron distribution of medium-high entropy metal carbide materials, prepare amorphous medium-high entropy carbide materials, enhance their intrinsic catalytic ability, slow down the oxidation of transition metal carbides, maintain stability, and extend the service life of carbide catalysts remains a difficult problem. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and to provide a high entropy metal carbide material and a preparation method thereof in hydrogen evolution reaction application, by effectively adjusting the microstructure and electron distribution through multiple metal components in amorphous high entropy metal carbide, thereby improving the electrochemical hydrogen evolution performance of the metal carbide material.

[0007] The purpose of the present invention can be achieved by the following technical solutions:

[0008] The invention provides a medium-high entropy metal carbide material for hydrogen evolution reaction application. The medium-high entropy metal carbide material comprises a carbon carrier and a medium-high entropy metal carbide loaded on the carbon carrier, wherein the metal in the medium-high entropy metal carbide on the carbon carrier comprises a noble metal A and a transition metal B; based on the total weight of the medium-high entropy metal carbide material, the mass percentage of the metal in the medium-high entropy metal carbide on the carbon carrier is 0.1% to 70%; based on the total weight of the metal in the medium-high entropy metal carbide on the carbon carrier, the mass percentage of each noble metal A element is 5% to 40%, and the mass percentage of each transition metal B element is 5% to 40%.

[0009] Furthermore, the medium-high entropy metal carbide material includes one or two precious metals A and at least two transition metals B.

[0010] Furthermore, the precious metal A is selected from one or two of Pt, Ru, Ir or Rh; and the transition metal B is selected from two or more of Mo, W, V, Zr, Fe, Co, Ni, Cu or Cr.

[0011] On the other hand, the present invention also provides a method for preparing a medium-high entropy metal carbide material as any of the above-mentioned ones, comprising the following steps: mixing a metal precursor and a carbon-containing precursor evenly, subjecting the mixture to a high-temperature roasting process, and then cooling the mixture to room temperature to obtain a medium-high entropy metal carbide material for hydrogen evolution reaction.

[0012] Furthermore, the metal precursor is selected from any one of metal sulfates, metal chlorides, metal acetates, metal nitrates, metal ammonium salts, metal carbonyl compounds or metal oxides; the carbon-containing precursor is selected from any one of natural carbon materials, artificial carbon materials, various derived carbon materials or carbon-containing organic matter, such as Ketjenblack EC-600JD, Vulcan XC-72, glucose (C6H 12 O6) etc.

[0013] Furthermore, the metal precursor and the carbon-containing precursor are mixed uniformly by at least one of a grinding method, an impregnation method, an ultrasonic mixing method or a rotary evaporation method.

[0014] Furthermore, the solvent used in the immersion method, ultrasonic mixing method or rotary evaporation method is selected from at least any one of water, ethanol, methanol, acetone, ethylene glycol or isopropanol.

[0015] Furthermore, the conditions of the high temperature calcination process are: calcination at 400° C. to 1200° C. for 0.5 h to 48 h in a specific atmosphere.

[0016] Further, the specific atmosphere is selected from any one of argon, nitrogen, helium, hydrogen-nitrogen mixture, hydrogen-argon mixture, hydrogen-helium mixture, carbon monoxide-nitrogen mixture, carbon monoxide-helium mixture, hydrogen or carbon monoxide;

[0017] The volume concentration of hydrogen or carbon monoxide in the mixed gas is 0.1% to 30%.

[0018] Furthermore, the cooling to room temperature adopts any one of natural cooling, rapid cooling or programmed cooling; wherein the cooling rate of the rapid cooling method is 30°C / min to 60°C / min; the cooling rate of the programmed cooling method is 0.5°C / min to 20°C / min.

[0019] In a third aspect, the present invention also provides a use of any of the above-mentioned medium-high entropy metal carbide materials in electrochemical hydrogen evolution.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The present invention provides a high-entropy metal carbide material for hydrogen evolution reaction application and a preparation method thereof. Precious metals and transition metals that are easy to form carbides are selected to react with a carbon-containing precursor at high temperature to obtain a medium-high entropy metal carbide supported on a carbon carrier. The microstructure and electron distribution are effectively adjusted by multiple metal components in the medium-high entropy metal carbide to optimize the adsorption energy between hydrogen intermediates and active sites. The medium-high entropy metal carbide material has a metastable state and more lattice distortion, and is also amorphous. Amorphous materials have a higher defect site density and a unique electronic structure than crystalline materials, so they have a large number of active sites and a higher intrinsic catalytic ability, which makes them have a lower reaction energy barrier in many catalytic reactions, improves their intrinsic catalytic ability and catalytic activity, and reduces the demand for precious metals.

[0022] (2) The present invention provides a high-entropy metal carbide material for hydrogen evolution reaction application and a preparation method thereof, which fixes multiple metal elements in a lattice to form an amorphous medium-high entropy metal carbide material, thereby slowing down the oxidation rate of the material, thereby improving the material's oxidation resistance and stability, extending the material's service life, and improving the easy oxidation problem of transition metal carbides.

[0023] (3) The present invention provides a high entropy metal carbide material for hydrogen evolution reaction application and a preparation method thereof, which uses a lower precious metal loading to achieve a significant improvement in electrochemical performance and has good practical production value. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The RuMoWVZrC prepared in Example 1 of the present invention x / C XRD pattern;

[0025] Figure 2 The RuMoWVZrC prepared in Example 1 of the present invention x HAADF-STEM image of / C;

[0026] Figure 3 The RuMoWVZrC prepared in Example 1 of the present invention x Polarization curves of different metal carbides prepared by / C and Comparative Examples 1-5;

[0027] Figure 4 The RuMoWVZrC prepared in Example 1 of the present invention x / C electrochemical polarization curves before and after 5000 cycles of CV experiment;

[0028] Figure 5 The RuMoWVZrC prepared in Example 1 of the present inventionx Electrochemical polarization curves of / C before and after the antioxidant test;

[0029] Figure 6 This is the XRD pattern of Mo2C / C prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0031] The present invention provides a high-entropy metal carbide material for hydrogen evolution reaction application, the medium-high entropy metal carbide material comprises a carbon carrier and a medium-high entropy metal carbide loaded on the carbon carrier, the metal in the medium-high entropy metal carbide comprises a noble metal A and a transition metal B; based on the total weight of the medium-high entropy metal carbide material, the mass percentage of the metal in the medium-high entropy metal carbide on the carbon carrier is 0.1% to 70%; based on the total weight of the metal in the medium-high entropy metal carbide on the carbon carrier, the mass percentage of each noble metal A element is 5% to 40%, and the mass percentage of each transition metal B element is 5% to 40%. The medium-high entropy metal carbide material comprises one or two noble metals A, and at least two transition metals B.

[0032] In some specific embodiments, the precious metal A is selected from one or two of Pt, Ru, Ir or Rh; the transition metal B is selected from two or more of Mo, W, V, Zr, Fe, Co, Ni, Cu or Cr.

[0033] The above-mentioned medium-high entropy metal carbide material is prepared by the following method: after the metal precursor and the carbon-containing precursor are evenly mixed, they are roasted at 400°C to 1200°C in a specific atmosphere for 0.5h to 48h, and then cooled to room temperature to obtain the high entropy carbide material in the hydrogen evolution reaction. The metal precursor is selected from any one of metal sulfates, metal chlorides, metal acetates, metal nitrates, metal ammonium salts, metal carbonyl compounds or metal oxides; the carbon-containing precursor is selected from any one of natural carbon materials, artificial carbon materials, various derivative carbon materials or carbon-containing organic matter, such as Ketjenblack EC-600JD, Vulcan XC-72, glucose (C6H 12 O6) etc.

[0034] In some specific embodiments, the metal precursor and the carbon-containing precursor are mixed uniformly by at least one of grinding, impregnation, ultrasonic mixing or rotary evaporation.

[0035] In some specific embodiments, the solvent used in the immersion method, ultrasonic mixing method or rotary evaporation method is selected from at least any one of water, ethanol, methanol, acetone, ethylene glycol or isopropanol.

[0036] In some specific embodiments, the specific atmosphere is selected from any one of argon, nitrogen, helium, hydrogen-nitrogen mixture, hydrogen-argon mixture, hydrogen-helium mixture, carbon monoxide-nitrogen mixture, carbon monoxide-helium mixture, hydrogen or carbon monoxide; the volume concentration of hydrogen or carbon monoxide in the mixture is 0.1% to 30%.

[0037] In some specific embodiments, the cooling to room temperature is carried out by any one of natural cooling, rapid cooling or programmed cooling; wherein the cooling rate of the rapid cooling method is 30°C / min to 60°C / min; the cooling rate of the programmed cooling method is 0.5°C / min to 20°C / min.

[0038] The above-mentioned medium-high entropy carbide materials can be applied in the field of electrochemical hydrogen evolution.

[0039] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0040] Example 1

[0041] This embodiment provides a medium-high entropy metal carbide material RuMoWVZrC x / C, the specific preparation method is as follows:

[0042] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0082g molybdenum pentachloride (MoCl5), 0.0078g ruthenium trichloride (RuCl3·3H2O), 0.0119g tungsten hexachloride (WCl6), 0.0047 vanadium trichloride (VCl3), and 0.0070g zirconium tetrachloride (ZrCl4) in 1.6mL of anhydrous ethanol solution, mix ultrasonically for 2h, and place the obtained viscous mixture sample in a vacuum oven at 70℃ and dry for 12h to obtain a solid mixture. Grind the solid mixture into powder, and calcine it at 800℃ for 2h in a tube furnace under argon atmosphere at a heating rate of 10℃ / min. When the temperature naturally drops to room temperature, a solid powder of RuMoWVZrC is obtained. x / C material.

[0043] like Figure 1 As shown, Figure 1 The RuMoWVZrC prepared in this example x XRD spectrum of / C material, from Figure 1It can be found that there are no diffraction peaks, which is consistent with the disordered structure of high entropy carbides.

[0044] like Figure 2 As shown, Figure 2 The RuMoWVZrC prepared in this example x TEM images of / C materials, from Figure 2 It can be seen that the prepared RuMoWVZrC x The size of the / C nanoparticles is 3nm-5nm, indicating that the particle size of the medium-high entropy carbide material of the present invention reaches the nanometer level.

[0045] The above results show that RuMoWVZrC x / C materials were successfully prepared.

[0046] Example 2

[0047] This embodiment provides a medium-high entropy carbide material RuMoWVFeC x / C, the specific preparation method is as follows:

[0048] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0082g molybdenum pentachloride (MoCl5), 0.0078g ruthenium trichloride (RuCl3·3H2O), 0.0119g tungsten hexachloride (WCl6), 0.0047 vanadium trichloride (VCl3), and 0.0049g ferric chloride (FeCl3) in 1.6mL of anhydrous ethanol solution, mix ultrasonically for 2h, and place the obtained viscous mixture sample in a vacuum oven at 70℃ and dry for 12h to obtain a solid mixture. Grind the solid mixture into powder, calcine it at 800℃ for 5h in a tube furnace under argon, and the heating rate is 10℃ / min. When the temperature drops to room temperature naturally, the solid powder RuMoWVFeC x / C material.

[0049] Example 3

[0050] This embodiment provides a medium-high entropy carbide material RuMoWVCoC x / C, the specific preparation method is as follows:

[0051] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0082g molybdenum pentachloride (MoCl5), 0.0078g ruthenium trichloride (RuCl3·3H2O), 0.0119g tungsten hexachloride (WCl6), 0.0047 vanadium trichloride (VCl3), 0.0087g cobalt nitrate (Co(NO3)2·6H2O) in 1.6mL of anhydrous ethanol solution, mix by ultrasonic for 2h, and place the obtained viscous mixture sample in a vacuum oven at 70℃ and dry for 12h to obtain a solid mixture. Grind the solid mixture into powder, calcine at 800℃ for 2h in a tube furnace under argon atmosphere, and heat at a rate of 10℃ / min. When the temperature drops to room temperature naturally, the solid powder RuMoWVCoC is obtained. x / C material.

[0052] Comparative Example 1

[0053] This comparative example provides a Mo2C / C material, and the specific preparation steps are as follows:

[0054] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0410g molybdenum pentachloride (MoCl5) in 1.6mL anhydrous ethanol solution, and mix ultrasonically for 2h. The viscous mixture sample is placed in a vacuum oven at 70℃ and dried for 12h to obtain a solid mixture. The solid mixture is ground into powder and calcined at 800℃ for 2h in a tube furnace under argon atmosphere with a heating rate of 10℃ / min. When the temperature naturally drops to room temperature, the solid powder obtained is Mo2C / C material.

[0055] like Figure 6 As shown, Figure 6 is the XRD pattern of Mo2C / C prepared in this comparative example. Figure 6 It can be found that the diffraction peaks of 34.3°, 37.9° and 39.3° appear in the range of 30° to 40°, corresponding to the (100), (002) and (101) crystal planes of molybdenum carbide, respectively, which indicates that the Mo2C / C material was successfully prepared in this comparative example.

[0056] Comparative Example 2

[0057] This comparative example provides a WC / C material, and the specific preparation steps are as follows:

[0058] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0595g tungsten hexachloride (WCl6) in 1.6mL anhydrous ethanol solution, and mix ultrasonically for 2h. The viscous mixture sample is placed in a vacuum oven at 70℃ and dried for 12h to obtain a solid mixture. The solid mixture is ground into powder and calcined at 800℃ for 2h in a tubular furnace under argon atmosphere with a heating rate of 10℃ / min. When the temperature naturally drops to room temperature, the solid powder obtained is WC / C material.

[0059] Comparative Example 3

[0060] This comparative example provides a VC / C material, and the specific preparation steps are as follows:

[0061] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0236 vanadium trichloride (VCl3) in 1.6mL anhydrous ethanol solution, and mix ultrasonically for 2h. The viscous mixture sample is placed in a vacuum oven at 70℃ and dried for 12h to obtain a solid mixture. The solid mixture is ground into powder and calcined at 800℃ for 2h in a tubular furnace under argon atmosphere with a heating rate of 10℃ / min. When the temperature naturally drops to room temperature, the solid powder obtained is VC / C material.

[0062] Comparative Example 4

[0063] This comparative example provides a Zr3C2 / C material, and the specific preparation steps are as follows:

[0064] Take 0.05g Ketjenblack EC-600JD in a 20ml sample bottle, dissolve 0.0350g zirconium tetrachloride (ZrCl4) in 1.6mL anhydrous ethanol solution, and mix ultrasonically for 2h. The viscous mixture sample is placed in a vacuum oven at 70℃ and dried for 12h to obtain a solid mixture. The solid mixture is ground into powder and calcined at 800℃ for 2h in a tube furnace under argon atmosphere with a heating rate of 10℃ / min. When the temperature naturally drops to room temperature, the solid powder obtained is Zr3C2 / C material.

[0065] Comparative Example 5

[0066] This comparative example provides a Ru@C material, and the specific preparation steps are as follows:

[0067] 0.05 g of Ketjenblack EC-600JD was put into a 20 ml sample bottle, 0.0392 g of ruthenium trichloride (RuCl3·3H2O) was dissolved in 1.6 mL of anhydrous ethanol solution, and ultrasonically mixed for 2 h. The obtained viscous mixture sample was placed in a vacuum oven and dried at 70 ° C for 12 h to obtain a solid mixture. The solid mixture was ground into powder and calcined at 800 ° C for 2 h in a tube furnace under argon atmosphere with a heating rate of 10 ° C / min. When the temperature naturally dropped to room temperature, the solid powder obtained was Ru@C material.

[0068] According to the calculation based on the feed ratio, the component contents of the carbide materials obtained in Comparative Examples 1-5 and Examples 1-3 are shown in Table 1 and Table 2.

[0069] Table 1 Component contents of carbide materials obtained in Comparative Examples 1-5 and Examples 1-3 (based on the total weight of the medium-high entropy metal carbide material)

[0070]

[0071]

[0072] Table 2 Component contents of carbide materials obtained in Comparative Examples 1-5 and Examples 1-3 (based on the total weight of metals in the medium-high entropy metal carbides on the carbon carrier)

[0073]

[0074] The materials obtained in Example 1 and Comparative Examples 1-5 were tested as follows:

[0075] A three-electrode test system was used, the electrolyte was 1M KOH solution, and the CHI-760E electrochemical station was used at room temperature. Platinum foil was used as the counter electrode and Hg / HgO was used as the reference electrode. The catalyst slurry was prepared using ultrapure water and ethanol (v / v = 50:950) and a certain amount of 5wt% Nafion solution. 20μL of the catalyst slurry was placed on a glassy carbon electrode (d = 5mm, with a geometric electrode area of ​​0.196cm 2 ) and dried in air to prepare the working electrode. The ink concentration of the catalyst was 5 mg mL -1 20 μL was dropped onto the glassy carbon electrode. The polarization curve of hydrogen evolution reaction was obtained by linear sweep voltammetry (LSV) with a scan rate of 5 mVs -1 .

[0076] In the evaluation of the catalytic activity of hydrogen evolution reaction catalysts, the current density is generally 10 mA cm -2 The overpotential at which the catalyst is reacted is used to characterize and compare the performance of the catalyst. The standard potential of the hydrogen evolution reaction is 0 V, so the current density is 10 mA cm -2The potential at which the catalyst reacts is called the overpotential. The smaller the overpotential, the better the hydrogen evolution reaction performance of the catalyst.

[0077] In Example 1, RuMoWVZrC x The polarization curves of different metal carbides in / C and Comparative Examples 1-5 are shown in Figure 3 As shown, according to Figure 3 The middle curve data shows that when Mo2C, WC, VC, Zr3C2, and Ru@C in Comparative Examples 1-5 are used for hydrogen evolution reaction at a current density of 10 mA cm -2 The overpotentials at the locations reached 134mV, 251mV, 596mV, 590mV, and 58mV. x For / C material, this value is only 32 mV, which indicates that medium- and high-entropy carbide materials have good electrochemical hydrogen evolution performance in an alkaline environment.

[0078] In addition, the RuMoWVZrC x The stability and antioxidant properties of the / C material were tested. The test system, equipment, and electrode preparation were the same as those in the above test. The stability test was performed using a 5000-cycle cyclic voltammetry (CV) aging experiment with a CV test voltage range of -100mV to 100mV and a scan rate of 50mV s -1 After 5000 cycles of CV aging, the hydrogen evolution reaction polarization curve was tested again, and the test conditions were the same as above.

[0079] Example 1 RuMoWVZrC x The electrochemical polarization curves of the / C material before and after 5000 cycles of CV experiment are shown in Figure 4 As shown, according to Figure 4 Data in the aging experiment, RuMoWVZrC x / C material at a current density of 10mAcm -2 The overpotential at is still 32 mV, the same as the starting potential.

[0080] The above results show that the present invention forms an amorphous medium-high entropy carbide material by fixing multiple metal elements in a lattice. The material has the characteristics of high entropy and amorphism, and can effectively adjust the microstructure and electron distribution through multiple metal components in the medium-high entropy metal carbide to optimize the adsorption energy between hydrogen intermediates and active sites. The medium-high entropy carbide material has a metastable state and more lattice distortion, and is amorphous. Therefore, it has a higher defect site density and a unique electronic structure than crystalline materials, thereby having a large number of active sites and a higher intrinsic catalytic ability, so that it has a lower reaction energy barrier in many catalytic reactions, thereby improving its intrinsic catalytic ability and catalytic activity.

[0081] The carbide material easily forms a thin layer of oxide on its surface in the air, and the formation of the oxide thin layer will significantly reduce the conductivity of the carbide material, and also reduce its catalytic activity as a catalyst for hydrogen evolution reaction. However, due to the different atomic radii of the elements in the medium-high entropy carbide material of the present invention, the diffusion resistance of various atoms increases, making the diffusion slow, providing a structural basis for the material's oxidation resistance and stability, and helping to improve the stability of the catalyst during the catalytic process. In addition, we used a water washing operation to simulate the accelerated oxidation process of the material in the air, and tested the RuMoWVZrC after 24 hours of water washing. x / C materials' hydrogen evolution properties.

[0082] RuMoWVZrC prepared in Example 1 x The electrochemical polarization curves of / C before and after the antioxidant test are shown in Figure 5 As shown, according to Figure 5 Middle curve data, RuMoWVZrC x After the / C material is washed with water, the current density is 10mAcm -2 The overpotential at the RuMoWVZrC increased from 32mV to 35mV, with a small increase. x The formation rate of the oxide layer on the surface of / C material is slow. The above results show that the medium-high entropy metal carbide material forms an amorphous medium-high entropy metal carbide material by fixing multiple metal elements in a lattice. Its "high entropy effect" enhances the mutual solubility between elements, reduces the Gibbs free energy of solid solution formation, promotes the formation of single-phase solid solution, and makes the medium-high entropy material have stronger acid and alkali resistance and oxidation resistance, significantly improves catalytic stability, effectively slows down the formation of the oxide layer on the surface of the carbide, slows down the oxidation rate of the material, improves the oxidation resistance and stability of the material, prolongs the service life of the material, and improves the easy oxidation problem of transition metal carbides.

[0083] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A high entropy metal carbide material for hydrogen evolution reaction application, characterized in that: The medium-high entropy metal carbide material comprises a carbon carrier and a medium-high entropy metal carbide loaded on the carbon carrier, wherein the metal in the medium-high entropy metal carbide comprises a noble metal A and a transition metal B; The mass percentage of the metal is 0.1% to 70% based on the total weight of the medium-high entropy metal carbide material; Calculated by the total weight of metals in the medium- and high-entropy metal carbides on the carbon carrier, the mass percentage of each precious metal A element is 5% to 40%, and the mass percentage of each transition metal B element is 5% to 40%.

2. The high entropy metal carbide material in hydrogen evolution reaction application according to claim 1, characterized in that: The medium-high entropy metal carbide material includes one or two precious metals A and at least two transition metals B.

3. The high entropy metal carbide material in hydrogen evolution reverse application according to claim 2, characterized in that: The precious metal A is selected from one or two of Pt, Ru, Ir or Rh; the transition metal B is selected from two or more of Mo, W, V, Zr, Fe, Co, Ni, Cu or Cr.

4. A method for preparing a high entropy metal carbide material for hydrogen evolution reaction application as claimed in any one of claims 1 to 3, characterized in that: The method comprises the following steps: uniformly mixing a metal precursor and a carbon-containing precursor, subjecting the mixture to a high-temperature calcination process, and then cooling the mixture to room temperature to obtain a high-entropy metal carbide material for hydrogen evolution reaction.

5. The method for preparing a high entropy metal carbide material in a hydrogen evolution reaction application according to claim 4, characterized in that: The metal precursor is selected from any one of metal sulfates, metal chlorides, metal acetates, metal nitrates, metal ammonium salts, metal carbonyl compounds or metal oxides; The carbon-containing precursor is selected from any one of natural carbon materials, artificial carbon materials, various derived carbon materials or carbon-containing organic matter.

6. The method for preparing a high entropy metal carbide material in a hydrogen evolution reaction application according to claim 4, characterized in that: The method of uniformly mixing the metal precursor and the carbon-containing precursor is at least one of a grinding method, an impregnation method, an ultrasonic mixing method or a rotary evaporation method.

7. The method for preparing a high entropy metal carbide material in hydrogen evolution reaction application according to claim 6, characterized in that: The solvent used in the immersion method, ultrasonic mixing method or rotary evaporation method is selected from at least any one of water, ethanol, methanol, acetone, ethylene glycol or isopropanol.

8. The method for preparing a high entropy metal carbide material in hydrogen evolution reaction application according to claim 4, characterized in that: The conditions of the high temperature calcination process are: calcination at 400°C to 1200°C for 0.5h to 48h in a specific atmosphere.

9. The method for preparing a high entropy metal carbide material in hydrogen evolution reaction application according to claim 8, characterized in that: The specific atmosphere is selected from any one of argon, nitrogen, helium, hydrogen-nitrogen mixture, hydrogen-argon mixture, hydrogen-helium mixture, carbon monoxide-nitrogen mixture, carbon monoxide-helium mixture, hydrogen or carbon monoxide; The volume concentration of hydrogen or carbon monoxide in the mixed gas is 0.1% to 30%.

10. Use of the medium-high entropy metal carbide material according to any one of claims 1 to 3 in electrochemical hydrogen evolution.

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