Double transition metal doped graphene catalyst and application thereof

Abstract

The invention discloses a double transition metal doped graphene catalyst and application thereof, the double transition metal doped graphene catalyst is of a hexagonal crystal system structure, and the space group is P6 / mmm; the composition form of the active center is Cu2C3N3, Nb2C3N3, Ta2C3N3, Rh2C6, Rh2C3N3 and Rh2N6, the hydrogen evolution free energy of the active center is-0.03 eV,-0.09 eV, 0.10 eV, 0.12 eV,-0.21 eV and 0.06 eV respectively, the metal binding energy of the active center is-4.53 eV,-8.60 eV,-8.03 eV,-6.13 eV,-7.11 eV and-5.62 eV respectively, the metal forming energy of the active center is-0.54 eV,-1.94 eV,-0.06 eV,-0.64 eV,-1.62 eV and-0.13 eV respectively, and the active center has good catalytic activity, structural stability and preparation feasibility and is used for

Description

Technical Field

[0001] The present invention relates to the technical field of electrocatalytic reduction hydrogen production, and in particular to a double transition metal doped graphene catalyst and application thereof. Background Art

[0002] Environmental pollution, global warming, and energy crisis caused by the burning of large amounts of fossil fuels have always been the focus of world attention. Hydrogen, as an environmentally friendly, renewable, and high-density energy source, is one of the most promising energy sources to replace fossil fuels [1,2]. So far, there are three main methods for producing hydrogen: producing hydrogen from fossil energy, producing hydrogen from bioenergy, and producing hydrogen from water electrolysis.

[0003] The hydrogen production reaction from fossil fuels involves a strong endothermic reaction. The reaction process consumes a lot of energy, and its fuel cost accounts for more than 50% of the production cost [3]. In addition, the reaction process will also produce substances that pollute the air and water, which is not in line with the concept of green energy. Biomass gasification is a widely used method for hydrogen production. This method can promote the benign cycle of materials in nature and thus protect the ecological environment [4]. However, the cost of using oxygen is too high, and the energy consumption of water vapor is too high. Although air gasification is the most widely used, the calorific value of air is low. The development of corresponding catalysts is the key to the gasification hydrogen production process. Therefore, sustainable production of hydrogen by water electrolysis is a promising method to alleviate the current energy crisis and alleviate pollution. The catalysts currently available on the market for large-scale hydrogen production are precious metal platinum (Pt) and its alloys. Their high cost and general shortage of supply have weakened the advantages of water electrolysis for hydrogen production [4]. Therefore, the development of cheap and abundant catalysts with special hydrogen evolution activity has become a research hotspot.

[0004] References

[0005] [1]W.Zhong,W.Tu,Z.Wang,Z.Lin,B.Xiao,Ultralow-temperature assistedsynthesis of single platinum atoms anchored on carbon nanotubes for efficient electrocatalytic acidic hydrogen evolution,J.Energy.Chem.2020,51,280.

[0006] [2] R.Gao,J.Wang,Z.-F.Huang,R.Zhang,W.Wang,L.Pan,J.Zhang,W.Zhu,X.Zhang,C.Shi,J.Lim,J.-J.Zou,Nat.Energy2021,6,614.

[0007] [3] Wang, H., & Zhao, Y. Hydrogen production from fossil fuels: A review of technologies and processes. Int. J. Hydrogen Energy, 2017, 42, 12596–12608.

[0008] [4] Zhou, Y., et al. Biomass gasification for hydrogen production: A review of recent advances. Renewable and Sustainable Energy Reviews, 2018, 81, 418–431. Summary of the invention

[0009] In view of the shortcomings of the fossil fuel hydrogen production reaction in the prior art involving a strongly endothermic reaction, the reaction process has high energy consumption, and its fuel cost accounts for more than 50% of the production cost, the reaction process also produces substances that pollute the air and water, the cost of using oxygen is too high, the energy consumption of water vapor is too high, the calorific value of air is low, and the precious metal platinum (Pt) and its alloys are expensive and generally in short supply. The purpose of the present invention is to provide a double transition metal doped graphene catalyst and its application, which makes it possible to produce efficient hydrogen at normal temperature and pressure and low electrode potential.

[0010] In order to solve the problems of the prior art, the technical solution adopted by the present invention is:

[0011] A double transition metal doped graphene catalyst, wherein the double transition metal doped graphene catalyst has a hexagonal crystal structure, a structural space group of P6 / mmm configuration, and a high degree of symmetry; wherein the transition metal is one or more of the third period elements, fourth period elements, and fifth period elements in the periodic table;

[0012] The third period element is one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc;

[0013] The fourth period element is one or more of yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium and silver;

[0014] The fifth period element is one or more of hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.

[0015] As an improvement, the transition metal is one or more of copper, niobium, rhodium and tantalum; the double transition metal doped graphene catalyst is copper atom pair doped graphene, niobium atom pair doped graphene, rhodium atom pair doped graphene or tantalum atom pair doped graphene.

[0016] The present application also discloses the use of any of the above-mentioned double transition metal doped graphene catalysts in electrocatalytic reduction to produce hydrogen, and the double transition metal doped graphene catalyst is electrocatalytically reduced to produce hydrogen in an electrolytic cell.

[0017] As an improvement, the electrolytic cell comprises a double transition metal doped graphene catalyst, a cathode, an anode, an electrolyte solution and at least one proton source; wherein the anode and the cathode are in two different compartments or in the same compartment; wherein the electrolyte solution is an aqueous electrolyte solution, and the aqueous electrolyte solution is composed of one or more of a soluble salt, an alkali metal, an alkaline earth metal oxide, an organic acid, an inorganic acid, an organic solvent, and an organic solvent miscible with water;

[0018] Among them, the reaction formula is:

[0019] 2H++2e – →H2.

[0020] As an improvement, the proton source is one or more of protons in an acidic medium, protons decomposed from water in a neutral environment, and protons decomposed from water in an alkaline environment.

[0021] A further improvement is that the temperature for producing hydrogen by electrocatalytic reduction is 0°C to 50°C.

[0022] As an improvement, the electrocatalytic reduction hydrogen production is carried out under atmospheric pressure.

[0023] As a further improvement, the electrolyte solution is an acidic, neutral or alkaline aqueous electrolyte solution.

[0024] As a further improvement, the electrolyte solution in the electrolytic cell is an acidic electrolyte solution, and protons and electrons combine to produce hydrogen; the electrolyte solution in the electrolytic cell is a neutral or alkaline aqueous electrolyte solution, and water decomposition occurs to produce hydrogen.

[0025] Beneficial effects:

[0026] Compared with the prior art, the double transition metal doped graphene catalyst and its application in the present invention have the following beneficial effects:

[0027] 1. The catalyst can produce hydrogen by hydrolysis under strong adsorption, and its adsorption effect is generally better than that of single-atom catalysts with the same structural components, such as platinum catalysts;

[0028] 2. The graphene material designed in this application has excellent electrical, thermal and mechanical properties. Its huge specific surface area and pore structure are the key to being a hydrogen storage material. It is currently widely used in batteries and energy storage.

[0029] 3. Double transition metal doped functional graphene hydrogen evolution catalysts meet the requirements of cheap and abundant catalysts with special hydrogen evolution activity. This application confirms six double transition metal doped active centers, whose hydrogen evolution performance is comparable to that of platinum-based catalysts, or even better than that of platinum-based materials, and is expected to be put into application;

[0030] 4. This application study confirms that graphene doped with transition metal elements can reduce protons to hydrogen under strong adsorption at ambient temperature and pressure;

[0031] 5. Given the environmental friendliness of hydrogen, especially in automotive, public transportation and stationary power generation, and the energy-intensive and environmentally unfavorable conditions typically used during its manufacture, the present invention has significant applicability in a variety of industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The atomic model diagram of the double transition metal doped graphene catalyst of the present application, wherein Type I is the transition metal elements doping different sides of the graphene, and Type II is the transition metal elements doping the same side of the graphene;

[0033] Figure 2 The metal binding energy E of double transition metal doped graphene catalyst for this application b and metal formation energy E f Figure 2, where (a) is the metal binding energy E b Figure 2, (b) is the metal formation energy E f picture;

[0034] Figure 3 The hydrogen adsorption configuration and hydrogen evolution free energy distribution diagram of the double transition metal doped graphene catalyst of this application, where (a) is the hydrogen adsorption configuration diagram and (b) is |ΔG H |≤0.3eV, the hydrogen evolution free energy distribution diagram of TM2C3N3 with top adsorption configuration, (c) is |ΔG H |≤0.3eV, the hydrogen evolution free energy distribution diagram of TM2C3N3 adsorbed at the bridge position. DETAILED DESCRIPTION

[0035] Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings. These examples are provided to further understand the present invention rather than to limit its scope.

[0036] In the following description, a series of steps are described. Those skilled in the art will appreciate that the order of the steps is not critical to the resulting construction and its effects unless the context requires. Furthermore, it will be apparent to those skilled in the art that, regardless of the order of the steps, the presence or absence of a time delay between steps may exist between some or all of the steps.

[0037] As used herein, including in the claims, unless the context indicates otherwise, terms in the singular should be construed to include the plural forms as well, and vice versa. Thus, it should be noted that, as used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly indicates otherwise.

[0038] Throughout the specification and claims, the terms “comprises,” “comprising,” “having,” and “containing” and variations thereof should be understood to mean “including but not limited to,” and are not intended to exclude other components / ingredients.

[0039] When these terms, features, values ​​and ranges are used in conjunction with terms such as "about", "around", "generally", "substantially", "essentially", "at least", etc., the present invention also covers the precise terms, features, values ​​and ranges, etc. (i.e., "about 3" should also precisely cover 3, or "substantially constant" should also precisely cover constant).

[0040] The term "at least one" should be understood to mean "one or more", and thus includes embodiments containing one or more components / ingredients. In addition, dependent claims referring to independent claims that use "at least one" to describe features have the same meaning when the features are referred to as "the" and "at least one".

[0041] It should be understood that the foregoing embodiments of the present invention may be modified while still falling within the scope of the present invention. Unless otherwise specified, the features disclosed in the specification may be replaced by alternative features for the same, equivalent or similar purposes. Therefore, unless otherwise specified, the disclosed model is only an example of a series of equivalent or similar features.

[0042] The use of exemplary language (e.g., "such as", "for example", "such as") is only intended to better illustrate the present invention, and does not limit the scope of the present invention, unless otherwise specified. Any steps described in the specification can be implemented in any order or simultaneously, unless the context clearly indicates otherwise.

[0043] All features and / or steps disclosed in the specification can be combined in any combination, except combinations in which at least some features and / or steps are mutually exclusive. Specifically, the preferred features of the present invention are applicable to all aspects of the present invention and can be used in any combination.

[0044] This application study confirms that graphene doped with transition metal elements can reduce protons to hydrogen under strong adsorption at ambient temperature and pressure.

[0045] Given the environmental friendliness of hydrogen, particularly in automotive, public transportation and stationary power generation, and the energy-intensive and environmentally hostile conditions typically used during its manufacture, the present invention has significant applicability across a variety of industries.

[0046] Therefore, the present invention provides a double transition metal doped graphene catalyst for producing hydrogen at ambient temperature and pressure. In the application of the double transition metal doped graphene catalyst of the present invention in the electrocatalytic reduction of hydrogen, an electrolytic cell is used, which can be any one of a series of conventional commercially available suitable and feasible electrolytic cell designs that can accommodate the special purpose cathode of the present invention. Therefore, in some embodiments, the electrolytic cell and system have one or more cathode units and one or more anode units.

[0047] An electrolytic cell in the present context is an electrochemical cell that undergoes a redox reaction when electrical energy is applied to the cell.

[0048] The proton donor may be any suitable substance capable of providing protons in the electrolytic cell. The proton donor may be an acid, for example, any suitable organic or inorganic acid. The proton donor may be provided in an acidic, neutral or alkaline aqueous solution.

[0049] The electrolytic cell comprises a double transition metal doped graphene catalyst, a cathode, an anode, an electrolyte solution and at least one proton source; wherein the cathode reaction equation is:

[0050] 2H++2e – →H2

[0051] The reaction mechanism can be shown in the following equation describing the so-called distal association mechanism:

[0052] Volmer step:H + +e – +*→H*

[0053] Different parts / portions or components / ingredients may be provided in separate containers, or they may be provided in a single container. Thus, the anode and cathode may be placed in the same compartment of the electrolytic cell of the present invention, but in other embodiments, the anode is in one compartment and the cathode is in another compartment. The electrolyte solution may be an aqueous solution in which ions are dissolved. The aqueous solution may be a neutral, alkaline or acidic solution. In some embodiments, the aqueous solution is an acidic solution. The electrolyte in the electrolyte solution may also be a molten salt, such as a sodium chloride salt.

[0054] Generally speaking, the catalyst on the electrode surface should ideally have the following properties: it should be chemically stable; it should not be oxidized or otherwise consumed during the electrolysis process; it should promote the formation of hydrogen; and the production cost of the catalyst should be less than that of catalysts such as the precious metal Pt. As will be further described, the double transition metal doped graphene catalyst of the present invention meets these properties, especially the Cu2C3N3 catalyst, which is the material with the best catalytic activity, and its production cost is relatively low.

[0055] The catalyst in the cathode catalytic layer of the electrolytic cell should have the following characteristics: it should be able to promote hydrogen reduction reaction; it should have good electrical conductivity; it should have a large specific surface area; it should be chemically stable and resistant to poisoning; the double transition metal doped graphene catalyst of the present invention meets the above characteristics. In addition, in order to increase the stability and conductivity of the cathode material, a layer of cathode support is usually coated on the surface of the cathode material. The cathode support can be a porous material, such as carbon fiber cloth, carbon fiber paper, graphite, etc., which is used to increase the surface area of ​​the cathode material and provide an electron conduction channel. In addition, a metal mesh, conductive paper or conductive support rod is required as a cathode current collector, which is tightly connected to the cathode material and the cathode support to collect electrons and conduct them to the conductive element of the external circuit.

[0056] The anode material of the electrolytic cell device described in the method is composed of a substrate composed of stainless steel, titanium or aluminum, a catalyst layer and a reaction layer. Among them, the commonly used catalyst materials for the catalyst layer include platinum, platinum alloys, cobalt oxides, etc., and the present invention can use a double transition metal doped graphene catalyst as the catalyst layer. The reaction layer is also called an adsorption layer, which is often used to enhance the adsorption of gas or improve the efficiency of the electrolytic reaction.

[0057] The electrolyte, which conducts current and maintains ion flow, can be acidic, neutral, or alkaline, depending on the application and reaction requirements of the electrolytic cell.

[0058] The electrochemical properties of double transition metal doped graphene catalysts are studied in this application. Graphene can be used as a catalyst substrate due to its high conductivity and huge specific surface area, thereby reducing the dependence on rare metal catalysts to achieve green catalysis. Here, the chemical stability and electrocatalytic performance of double transition metal doped graphene catalysts are studied in this application. Based on this, it is determined that double transition metal atom / nitrogen co-doping is an effective activation method, among which copper, niobium, rhodium, and tantalum can effectively activate defective graphene.

[0059] Example 1

[0060] A double transition metal doped graphene catalyst, the double transition metal doped graphene catalyst has a hexagonal structure, a structural space group of P6 / mmm configuration, and is highly symmetrical; two configurations are considered in the present application, Type I is that double transition metal elements are doped on different sides of graphene respectively, and Type II is that double transition metal elements are doped on the same side of graphene at the same time, denoted as TM2C6, TM2C3N3, TM2N6, wherein the transition metal is one or more of the third period elements, fourth period elements, and fifth period elements in the periodic table;

[0061] The third period element is one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc;

[0062] The fourth period element is one or more of yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium and silver;

[0063] The fifth period element is one or more of hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.

[0064] Chemical stability analysis of double transition metal doped graphene catalysts, Figure 1 The atomic model diagram of the double transition metal doped graphene catalyst of the present application, wherein Type I is the transition metal elements doping different sides of the graphene, and Type II is the transition metal elements doping the same side of the graphene;

[0065] Figure 2 The metal binding energy E of double transition metal doped graphene catalyst for this application b and metal formation energy E f Figure 2, where (a) is the metal binding energy E b Figure 2, (b) is the metal formation energy E fFigure 2 shows the parameters of binding energy and formation energy, which can be used to evaluate the thermodynamic stability and synthetic feasibility of the material. The more negative the binding energy, the stronger the interaction between the dopant and its coordination, while the more negative the formation energy, the higher the feasibility of the experimental synthesis process. The binding energy ranges from 9.64 to 0.88 eV, reflecting the strong chemical bond between the transition metal atoms and the substrate, which will provide sufficient anti-aggregation. Finally, the two configurations were compared and only the more stable ones were selected for catalytic activity analysis. Finally, 37 types were screened out, including 7 TM2C6: Sc2C6, Ti2C6, Y2C6, Zr2C6, Nb2C6, Rh2C6 and Pd2C6; 19 TM2C3N3: Sc2C3N3, Ti2C 3N3, V2C3N3, Mn2C3N3, Fe2C3N3, Co2C3N3, Ni2C3N3, Cu2C3N3, Zn2C3N3, Y2C3N3, Zr2C3N3, Nb2C3N3, Mo2C3N3, Ru2C3N3, Rh2C3N3, Pd2C3N3, Ag2C3N3, Hf2C3N3 and Ta2C3N3; 11 TM2N6: Sc2N6, Ti2N6, Co2N6, Zn2N6, Y2N6, Zr2N6, Nb2N6, Rh2N6, Pd2N6, Ag2N6 and Hf2N6.

[0066] Regardless of the coordination environment, the metallic bonds of Sc, Ti, Y, Zr, Nb, Rh and Pd form a stable structure. It is worth mentioning that ScC3N3 and YC3N3 have been synthesized in experiments, and Fe2N6 has been partially prepared experimentally. Therefore, the theoretical candidates of this application are expected to be synthesized.

[0067] Example 2

[0068] Analysis of catalytic activity of double transition metal / tri-nitrogen co-doped graphene catalysts:

[0069] Due to the high symmetry of graphene, two possible hydrogen adsorption sites are considered: type I, where hydrogen atoms are adsorbed on top of a single transition metal atom, and type II, where hydrogen atoms are adsorbed on pairs of transition metal atoms.

[0070] The catalytic activities discussed in this study are based on the following formula.

[0071] Under standard conditions, the Gibbs free energy of hydrogen adsorption is ΔG H The calculation formula is:

[0072] ΔG H =ΔE H –ΔE ZPE –TΔS H

[0073] Where, ΔEH is the energy calculated using DFT, ΔE ZPE represents the zero-point energy difference between the adsorption state and the gas phase of hydrogen obtained by vibration frequency calculation, T represents the temperature (here 298.15K), ΔS H It is the entropy difference due to hydrogen adsorption.

[0074] Figure 3 The hydrogen adsorption configuration and hydrogen evolution free energy distribution diagram of the double transition metal doped graphene catalyst of this application, where (a) is the hydrogen adsorption configuration diagram and (b) is |ΔG H |≤0.3eV, the hydrogen evolution free energy distribution diagram of TM2C3N3 with top adsorption configuration, (c) is |ΔG H |≤0.3eV, the hydrogen evolution free energy distribution diagram of TM2C3N3 adsorbed at the bridge position.

[0075] Figure 3 (a) shows two possible hydrogen adsorption sites, type I is hydrogen adsorbed on the top of a single transition metal atom, and type II is hydrogen adsorbed on a transition metal atom pair. The hydrogen adsorption free energy is a key parameter that determines the catalytic performance. The optimal hydrogen adsorption free energy of 0.0 eV indicates the thermal neutral state of adsorbed hydrogen. Specifically, a high positive value indicates a strong interaction between the proton and the catalyst, while a high negative value generally indicates a strong binding with the adsorbed hydrogen atom. A hydrogen evolution Gibbs free energy value within ±0.3 eV indicates good hydrogen evolution activity, which has been experimentally confirmed.

[0076] Figure 3 (b) and Figure 3(c) shows the Gibbs free energy distribution diagram of double transition metal / tri-nitrogen doped graphene. After screening, 11 candidate materials stand out, 8 of which have hydrogen adsorption as bridge site adsorption and 3 as top adsorption. The bridge site adsorption includes: V2C3N3, Mn2C3N3, Co2C3N3, Ni2C3N3, Cu2C3N3, Nb2C3N3, Mo2C3N3, Ta2C3N3, and the Gibbs free energies are: -0.21, -0.20, -0.19, -0.14, -0.03, -0.09, 0.17, 0.10 eV respectively; the top adsorption includes: Zn2C3N3, Rh2C3N3, Pd2C3N3, and the Gibbs free energies are: -0.13, -0.21, -0.15 eV respectively. Among them, Cu2C3N3, Nb2C3N3, and Ta2C3N3 have better hydrogen evolution performance than platinum-based materials. The corresponding binding energy and adsorption energy are listed in Table 1. The binding energy and formation energy of Cu2C3N3 are -4.53 and -0.54 eV, respectively, the binding energy and formation energy of Nb2C3N3 are -8.60 and -1.94 eV, respectively, and the binding energy and formation energy of Ta2C3N3 are -8.03 and -0.06 eV, respectively, that is, these three candidate materials have high catalytic activity and strong structural stability.

[0077] Example 3

[0078] Analysis of catalytic activity of bimetallic Rh2-doped graphene:

[0079] Table 1 gives the values ​​of Gibbs free energy, metal binding energy and formation energy of bimetallic Rh2-doped graphene. H is adsorbed at the top position in Rh2N6, and the corresponding Gibbs free energy is 0.06eV. It has been experimentally confirmed that the absolute value of the Gibbs free energy of hydrogen evolution is between 0.1, which means excellent hydrogen evolution activity. Therefore, Rh2N6 material has good hydrogen evolution performance, even exceeding platinum-based materials. The binding energy and formation energy of Rh2N6 are -5.62 and -0.13eV respectively, which are within a reasonable range. In addition, according to the data shown in Table 1, the hydrogen evolution Gibbs free energy of Rh2C6 is 0.12eV, the binding energy is -6.13eV, and the formation energy is -0.64eV. In Example 2, the Gibbs free energy of Rh2C3N3 is -0.21 eV, and the binding energy and formation energy are -7.11 and -1.62 eV, respectively. Therefore, the bimetallic Rh2 active center has excellent catalytic activity in hydrogen evolution electrocatalysis and is easy to prepare.

[0080] Table 1 Binding energy E b , Formation Energy E f , hydrogen adsorption free energy ΔG H . (E b 、E f and ΔGH , in eV)

[0081]

[0082] Example 4

[0083] Application of double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production, double transition metal doped graphene catalyst electrocatalytic reduction hydrogen production in an electrolytic cell, the electrolytic cell comprises double transition metal doped graphene catalyst, cathode, anode, electrolyte solution and at least one proton source; wherein the anode and cathode are in two different compartments or in the same compartment; wherein the electrolyte solution is an aqueous electrolyte solution, and the aqueous electrolyte solution is composed of one or more of soluble salts, alkali metals, alkaline earth metal oxides, organic acids, inorganic acids, organic solvents, and organic solvents miscible with water. The electrolyte solution is an acidic, neutral or alkaline aqueous electrolyte solution.

[0084] The proton source is one or more of protons in an acidic medium, protons from water decomposition in a neutral environment, and protons from water decomposition in an alkaline environment.

[0085] The temperature of electrocatalytic reduction hydrogen production is 0°C to 50°C, and the electrocatalytic reduction hydrogen production is carried out under atmospheric pressure.

[0086] The electrolyte solution in the electrolytic cell is an acidic electrolyte solution, and protons and electrons combine to produce hydrogen; the electrolyte solution in the electrolytic cell is a neutral or alkaline aqueous electrolyte solution, and water decomposition occurs to produce hydrogen.

[0087] The present invention and its embodiments are described schematically above, and the description is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. Therefore, if a person skilled in the art is inspired by it and designs a structural method and an embodiment similar to the technical solution without creativity without departing from the purpose of the invention, they shall all fall within the protection scope of the present invention.

Claims

1. A double transition metal doped graphene catalyst, characterized in that: The double transition metal doped graphene catalyst has a hexagonal crystal structure, a structural space group of P6 / mmm configuration, and a high degree of symmetry; wherein the transition metal is one or more of the third period elements, fourth period elements, and fifth period elements in the periodic table; The third period element is one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc; The fourth period element is one or more of yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium and silver; The fifth period element is one or more of hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.

2. A double transition metal doped graphene catalyst according to claim 1, characterized in that: The transition metal is one or more of copper, niobium, rhodium and tantalum; the double transition metal doped graphene catalyst is copper atom pair doped graphene, niobium atom pair doped graphene, rhodium atom pair doped graphene or tantalum atom pair doped graphene.

3. An application of the double transition metal doped graphene catalyst according to claim 1 or 2 in electrocatalytic reduction hydrogen production, characterized in that: Double transition metal doped graphene catalysts for electrocatalytic reduction of hydrogen in electrolytic cells.

4. The use of the double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production according to claim 3, characterized in that: The electrolytic cell comprises a double transition metal doped graphene catalyst, a cathode, an anode, an electrolyte solution and at least one proton source; wherein the anode and the cathode are in two different compartments or in the same compartment; wherein the electrolyte solution is an aqueous electrolyte solution, and the aqueous electrolyte solution is composed of one or more of a soluble salt, an alkali metal, an alkaline earth metal oxide, an organic acid, an inorganic acid, an organic solvent, and an organic solvent miscible with water; Among them, the cathode reaction equation is: <h2 style=";text-align:left;direction:ltr">2H++2e<h2 style=";text-align:left;direction:ltr"> – <h2 style=";text-align:left;direction:ltr"> →H2。 5. The use of the double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production according to claim 4, characterized in that: The proton source is one or more of protons in an acidic medium, protons from water decomposition in a neutral environment, and protons from water decomposition in an alkaline environment.

6. The use of the double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production according to claim 3, characterized in that: The temperature for electrocatalytic reduction hydrogen production is 0°C to 50°C.

7. The use of the double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production according to claim 3, characterized in that: The electrocatalytic reduction of hydrogen is carried out at atmospheric pressure.

8. The use of the double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production according to claim 4, characterized in that: The electrolyte solution is an acidic, neutral or alkaline aqueous electrolyte solution.

9. The use of the double transition metal doped graphene catalyst in electrocatalytic reduction hydrogen production according to claim 8, characterized in that: The electrolyte solution in the electrolytic cell is an acidic electrolyte solution, and protons and electrons combine to produce hydrogen; the electrolyte solution in the electrolytic cell is a neutral or alkaline aqueous electrolyte solution, and water decomposition occurs to produce hydrogen.

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