Composite catalytic material and preparation method thereof, electrode and application thereof, and reactor for electrocatalytic hydrogen isotope separation

Abstract

This application relates to a composite catalytic material, a preparation method thereof, an electrode, its application, and a reactor for electrocatalytic hydrogen isotope separation. The composite catalytic material comprises a substrate, a nickel metal organic framework material layer, ruthenium particles, and a graphene layer. The nickel metal organic framework material layer is disposed on the surface of the substrate, the graphene layer is disposed on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are disposed between the nickel metal organic framework material layer and the graphene layer. This composite catalytic material is fabricated into an electrode for electrocatalytic hydrogen isotope separation, effectively regulating the diffusion rate of hydrogen and deuterium in a solution, thereby improving the efficiency of hydrogen-deuterium separation.

Description

Technical Field

[0001] The present application relates to the field of material technology, and in particular to a composite catalytic material and a preparation method thereof, an electrode and its application, and a reactor for electrocatalytic hydrogen isotope separation. Background Art

[0002] Traditional hydrogen isotope separation methods, including thermal diffusion and distillation, suffer from high energy consumption, low efficiency, and high costs, making them difficult to meet the needs of large-scale industrial applications. Electrochemical methods, as a green and controllable separation method, offer unique advantages in hydrogen isotope separation. However, traditional electrochemical separation of hydrogen isotopes is inefficient.

[0003] Therefore, it is necessary to improve the traditional technology. Summary of the Invention

[0004] Based on this, the present application provides a composite catalytic material and its preparation method, an electrode and its application, and a reactor for electrocatalytic hydrogen isotope separation that can effectively improve the efficiency of hydrogen isotope separation.

[0005] The technical solution of this application to solve the above technical problems is as follows.

[0006] On the one hand, the present application provides a composite catalytic material, including a substrate, a nickel metal organic framework material layer, ruthenium particles and a graphene layer, wherein the nickel metal organic framework material layer is arranged on the surface of the substrate, the graphene layer is arranged on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer.

[0007] In some embodiments, in the composite catalytic material, the graphene layer includes graphene and carbon dots mixed with each other; optionally, the mass ratio of the graphene to the carbon dots is 1:0.5~2.

[0008] In some embodiments, in the composite catalytic material, the metal-organic framework material layer includes a metal-organic framework material, and the metal-organic framework material includes nickel metal ions and organic ligands coordinated with the nickel metal ions; optionally, the organic ligands include terephthalic acid; optionally, the molar ratio of the nickel metal ions to the organic ligands is 0.4~0.8:1.

[0009] In some embodiments, in the composite catalytic material, the ratio of the amount of the ruthenium particles to the single side area of ​​the nickel metal organic framework material layer is 0.1 mmol / cm 2 ~0.2 mmol / cm 2 .

[0010] In some embodiments, in the composite catalytic material, the substrate includes at least one of foamed nickel, foamed copper, and carbon cloth.

[0011] On the one hand, the present application provides a method for preparing a composite catalytic material, comprising the following steps:

[0012] Disposing a nickel metal organic framework material layer on the surface of the substrate;

[0013] loading ruthenium particles on the surface of the nickel metal organic framework material layer away from the substrate to prepare a Ru-Ni material;

[0014] A graphene layer is provided on the surface of the Ru-Ni material, so that the ruthenium particles are provided between the nickel metal organic framework material layer and the graphene layer.

[0015] In some embodiments, in the method for preparing the composite catalytic material, the method for setting the nickel metal organic framework material layer includes a hydrothermal method; optionally, the hydrothermal solution used in the hydrothermal method includes an organic ligand, a nickel salt and a first solvent; optionally, the organic ligand includes terephthalic acid; optionally, the nickel salt includes at least one of nickel acetate, nickel nitrate and nickel chloride; optionally, the first solvent includes N,N-dimethylformamide; optionally, the first solvent also includes at least one of ethanol and water.

[0016] In some embodiments, in the method for preparing the composite catalytic material, providing the graphene layer comprises the following steps:

[0017] A graphene solution is placed on the surface of the Ru-Ni material and dried to form a graphene layer.

[0018] In some embodiments, in the method for preparing a composite catalytic material, the graphene solution includes graphene, carbon dots, a second solvent and a nafion solution; optionally, the second solvent includes at least one of water and isopropanol; optionally, the graphene solution includes 0.05 mg~0.2 mg of graphene, 0.05 mg~0.2 mg of carbon dots, 0.2 mL~1 mL of water, 0.2 mL~1 mL of isopropanol and 60 μL~100 μL of nafion solution.

[0019] On the one hand, the present application provides an electrode, comprising the above-mentioned composite catalytic material or the composite catalytic material prepared by the above-mentioned preparation method.

[0020] On the one hand, the present application provides the use of the above-mentioned electrode in electrocatalytic hydrogen isotope separation.

[0021] In some embodiments, in the application of the above-mentioned electrode in electrocatalytic hydrogen isotope separation, the cathode electrolyte of the electrocatalytic hydrogen isotope separation includes potassium hydroxide; optionally, the cathode electrolyte also includes at least one of heavy water and an alcohol solvent; optionally, the alcohol solvent includes at least one of methanol, ethanol, isopropanol and ethylene glycol.

[0022] In some embodiments, when the electrode is used in electrocatalytic hydrogen isotope separation, the reactor for performing the electrocatalytic hydrogen isotope separation includes one of a two-phase reactor and a three-phase reactor.

[0023] On the one hand, the present application provides a reactor for electrocatalytic hydrogen isotope separation, comprising a cathode electrolysis chamber, a cathode gas circulation chamber, an anode electrolysis chamber, a cathode arranged in the cathode electrolysis chamber, and an anode arranged in the anode electrolysis chamber, wherein the cathode adopts the above-mentioned electrode.

[0024] Compared with the prior art, the composite catalytic material of the present application has the following beneficial effects:

[0025] The composite catalytic material of the present application includes a substrate, a nickel metal organic framework material layer, ruthenium particles and a graphene layer. The nickel metal organic framework material layer is arranged on the surface of the substrate, the graphene layer is arranged on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer; the graphene serves as a hydrogen isotope screening layer, slowing down the contact between deuterium and the surface of the composite catalytic material, controlling the reaction rate, effectively improving the hydrogen isotope separation efficiency, and having good stability performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application and to more fully understand the present application and its beneficial effects, the following is a brief introduction to the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present application. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0027] Figure 1 This is a scanning electron microscope image of the Ni-MOF material prepared in step (2) of Example 1;

[0028] Figure 2 This is a scanning electron microscope image of the Ru-Ni material prepared in step (3) of Example 1;

[0029] Figure 3 This is a scanning electron microscope image of the Ru-NiC material prepared in step (4) of Example 1;

[0030] Figure 4 This is a transmission scanning electron micrograph of the Ru-NiC material prepared in step (4) of Example 1;

[0031] Figure 5 This is a scanning electron microscope image of the Pt-NiC material prepared in step (4) of Comparative Example 1;

[0032] Figure 6 TF-SIMS mapping of H and D of Ru-NiC electrode and Pt-NiC electrode;

[0033] Figure 7 is a graph of the D intensity depth profile of the Ru-NiC electrode and the Pt-NiC electrode;

[0034] Figure 8 It is a curve diagram of the linear sweep voltammetry test of Ru-NiC electrode in a three-electrode electrolytic cell;

[0035] Figure 9 is a curve diagram of the linear sweep voltammetry test of the Pt-NiC electrode in a three-electrode electrolytic cell;

[0036] Figure 10 It is a curve diagram of the linear sweep voltammetry test of NiF electrode in a three-electrode electrolytic cell;

[0037] Figure 11 This is a curve diagram of the linear sweep voltammetry test of the Ni-MOF electrode in a three-electrode electrolytic cell;

[0038] Figure 12 It is a curve diagram of the linear sweep voltammetry test of Ru-Ni electrode in a three-electrode electrolytic cell;

[0039] Figure 13 is the Tafel slope diagram of Ru-NiC electrode under different cathode electrolyte conditions;

[0040] Figure 14 is the Tafel slope diagram of Ru-NiC electrode under different cathode electrolyte conditions;

[0041] Figure 15 The graph of the kinetic isotope effect value of Ru-NiC electrode with and without isopropanol as a function of overpotential;

[0042] Figure 16 Schematic diagram of a two-phase hydrogen-deuterium separation reactor for hydrogen isotope separation testing;

[0043] Figure 17 Schematic diagram of a three-phase hydrogen-deuterium separation reactor for hydrogen isotope separation testing;

[0044] Figure 18 Schematic diagram of multi-stage electrolysis with 5 electrolytic cells of different electrode areas;

[0045] Figure 19 The mole fraction diagram of three generated gases at the outlet of Ru-NiC electrode when fed with electrolytes containing different deuterium contents with and without isopropanol;

[0046] Figure 20 Separation factor diagram of Ru-NiC electrode in constant current electrolysis of electrolyte with different deuterium contents for 7 hours with and without isopropanol;

[0047] Figure 21 The current curve of the deuterium (D) atomic fraction curve and the water separation factor during the five-stage electrolysis process of the deuterium (D) electrolyte;

[0048] Figure 22 Graph showing the deuterium (D) atomic fraction and water separation factor during long-term electrolytic hydrogen isotope separation in an electrolyte prepared from natural water. DETAILED DESCRIPTION

[0049] The present application will be further described in detail below in conjunction with the embodiments and examples. It should be understood that these embodiments and examples are only intended to illustrate the present application and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to provide a more thorough and comprehensive understanding of the disclosure of the present application.

[0050] It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various changes or modifications without violating the connotation of the present application, and the resulting equivalent forms also fall within the scope of protection of the present application. For example, features illustrated or described as part of one embodiment can be combined in a suitable manner in another embodiment to produce a new embodiment. In addition, in the description below, a large number of specific details are given in order to provide a more complete understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing embodiments and examples only and are not intended to limit this application.

[0052] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0053] In this application, "plurality", "multiple", "multiple times", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0054] As used herein, "combination thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0055] Herein, the “suitable” mentioned in “suitable combination”, “suitable method”, “any suitable method”, etc. shall be based on the ability to implement the technical solution of this application, solve the technical problems of this application, and achieve the expected technical effects of this application.

[0056] Herein, the terms "preferred," "better," "more preferred," and "suitable" are used solely to describe preferred implementations or examples and should not be construed as limiting the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0057] In this application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0058] In this application, the terms "optionally," "optional," and "optional" mean optional or dispensable, i.e., they refer to either option being selected from two parallel options: "with" or "without." If a technical solution contains multiple "optional" clauses, each "optional" clause is independent unless otherwise specified and there are no contradictions or constraints.

[0059] In this application, the terms "first," "second," "third," "fourth," etc. in "the first aspect," "the second aspect," "the third aspect," "the fourth aspect," etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor should they be understood as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc. serve only as non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0060] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0061] In this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. "Numerical interval" allows for a broad range of numerical interval types including percentage intervals, ratio intervals, and ratio intervals.

[0062] Unless otherwise specified, the temperature parameters in this application allow for both constant temperature treatment and temperature fluctuations within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the accuracy range of instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0063] In this application, the term "room temperature" or "normal temperature" generally refers to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0064] In this application, when referring to a range of units, if the unit is only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 3~5h means that the units of the left endpoint "3" and the right endpoint "5" are both hours.

[0065] All documents mentioned in this application are cited as references in this application, just as each document is cited as a reference individually. Unless they conflict with the invention purpose and / or technical solution of this application, the cited documents involved in this application are cited in their entirety and for all purposes. When cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When cited documents are involved in this application, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be adaptively amended according to the description in this application.

[0066] The mass or weight of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the proportional relationship of the mass or weight of each component. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass or weight described in the examples of this application may be units known in the chemical industry such as μg, mg, g, and kg.

[0067] The difficulty of HD exchange in water systems, as well as battery voltage and stability issues, lead to low efficiency of traditional electrochemical separation of hydrogen isotopes, and electrochemical hydrogen isotope separation has not been effectively applied.

[0068] One embodiment of the present application provides a composite catalytic material, including a substrate, a nickel metal organic framework material layer, ruthenium particles and a graphene layer. The nickel metal organic framework material layer is arranged on the surface of the substrate, the graphene layer is arranged on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer.

[0069] The composite catalytic material of the present application includes a substrate, a nickel metal organic framework material layer, ruthenium particles and a graphene layer. The nickel metal organic framework material layer is arranged on the surface of the substrate, the graphene layer is arranged on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer; the graphene acts as a hydrogen isotope screening layer, slowing down the contact between deuterium and the surface of the composite catalytic material, controlling the reaction rate, effectively improving the hydrogen isotope separation efficiency, and having good stability performance.

[0070] The composite catalytic material is made into electrodes for electrocatalytic hydrogen isotope separation, which can effectively regulate the diffusion rate of hydrogen and deuterium in the solution, thereby improving the hydrogen and deuterium separation efficiency.

[0071] It is understood that the ruthenium particles are loaded on the surface of the nickel metal organic framework material layer. It is further understood that in the composite catalytic material of the present application, the nickel metal organic framework material layer, ruthenium particles, and graphene layer are sequentially provided on the surface of the substrate. It is also understood that the nickel metal organic framework material layer is provided on at least one surface of the substrate, the graphene layer is provided on at least one surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are provided between the nickel metal organic framework material layer and the graphene layer.

[0072] In some of these examples, in the composite catalytic material, each surface of the substrate (especially the upper and lower surfaces) is provided with a nickel metal organic framework material layer, ruthenium particles and a graphene layer.

[0073] It can be understood that, viewed from all sides of the composite catalytic material, the nickel metal organic framework material layer is disposed on the surface of the substrate, the graphene layer is disposed on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are disposed between the nickel metal organic framework material layer and the graphene layer.

[0074] In some of these examples, the graphene layer in the composite catalytic material includes graphene and carbon dots mixed with each other.

[0075] Furthermore, the mass ratio of graphene to carbon dots is 1:0.5~2.

[0076] It can be understood that the mass ratio of graphene to carbon dots includes but is not limited to 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, and 1:2; in some examples, it can be within the range formed by any two of these point values ​​as end values, the same below.

[0077] Optionally, the mass ratio of graphene to carbon dots is 1:0.8-1.2. Further, the mass ratio of graphene to carbon dots is 1:1.

[0078] In some examples, in the composite catalytic material, the metal-organic framework material layer includes a metal-organic framework material, and the metal-organic framework material includes nickel metal ions and organic ligands coordinated with the nickel metal ions.

[0079] Further, the organic ligand includes terephthalic acid.

[0080] Furthermore, the molar ratio of the metal ion to the organic ligand is 0.4-0.8:1.

[0081] It is understood that the molar ratio of metal ion to organic ligand includes but is not limited to 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1

[0082] Optionally, the molar ratio of metal ion to organic ligand is 0.4-0.6:1.

[0083] In some of the examples, the ratio of the amount of ruthenium particles to the single-side area of ​​the nickel metal organic framework layer in the composite catalytic material is 0.1 mmol / cm 2 ~0.2 mmol / cm 2 .

[0084] It is understood that the ratio of the amount of ruthenium particles to the single-side area of ​​the nickel metal organic framework material layer includes but is not limited to 0.1 mmol / cm 2 , 0.11 mmol / cm 2, 0.12 mmol / cm 2 , 0.13 mmol / cm 2 , 0.14 mmol / cm 2 , 0.15mmol / cm 2 , 0.16 mmol / cm 2 , 0.17 mmol / cm 2 , 0.18 mmol / cm 2 , 0.19 mmol / cm 2 , 0.2 mmol / cm 2 .

[0085] Optionally, the ratio of the amount of ruthenium particles to the single-side area of ​​the nickel metal organic framework material layer is 0.1 mmol / cm 2 ~0.15 mmol / cm 2 .

[0086] In some examples, in the composite catalytic material, the substrate includes at least one of nickel foam, copper foam, and carbon cloth.

[0087] One embodiment of the present application provides a method for preparing a composite catalytic material, comprising the following steps:

[0088] Step S10: a nickel metal organic framework material layer is provided on the surface of the substrate to obtain a Ni-MOF material.

[0089] Ni-MOF refers to Nickel Metal-Organic Framework, a metal-organic framework material that is self-assembled by nickel ions and organic ligands through coordination bonds to form a crystalline material with a periodic network structure.

[0090] In some examples, in step S10 , the method of forming the nickel metal organic framework material layer includes a hydrothermal method.

[0091] It can be understood that the nickel metal organic framework material layer is in-situ grown on the substrate surface by the hydrothermal method. Further, the nickel metal organic framework material grows on the surface of the substrate including the outer surface and the pores of the substrate.

[0092] In some examples, in step S10 , the hydrothermal solution used in the hydrothermal method includes an organic ligand, a nickel salt, and a first solvent.

[0093] Optionally, the concentration of the organic ligand in the hydrothermal solution is 0.01 mol / L to 0.02 mol / L. Further, the concentration of the organic ligand in the hydrothermal solution is 0.01 mol / L.

[0094] Optionally, the concentration of the nickel salt in the hydrothermal solution is 0.02 mol / L to 0.04 mol / L. Further, the concentration of the nickel salt in the hydrothermal solution is 0.02 mol / L.

[0095] It can be understood that in the hydrothermal solution, when the concentration of the raw materials is determined, the concentration of each solute in the final hydrothermal solution can be controlled by controlling the addition amount of each raw material.

[0096] Optionally, the organic ligand comprises terephthalic acid.

[0097] Optionally, the nickel salt includes at least one of nickel acetate, nickel nitrate and nickel chloride.

[0098] In some examples, in step S10, the organic ligand is terephthalic acid, and the nickel salt is nickel acetate tetrahydrate; further, the mass ratio of terephthalic acid to nickel acetate tetrahydrate is 50~80:30~60; optionally, the mass ratio of terephthalic acid to nickel acetate tetrahydrate is 62:46.

[0099] Optionally, the first solvent includes N,N-dimethylformamide. Further, the first solvent also includes at least one of ethanol and water.

[0100] In some examples, in step S10, the first solvent includes N,N-dimethylformamide, ethanol, and water. Furthermore, the volume ratio of N,N-dimethylformamide to ethanol to water is 10-20:1-5:1-5. Alternatively, the volume ratio of N,N-dimethylformamide to ethanol to water is 16:1:1.

[0101] In some examples, in step S10, the preparation of the hydrothermal solution includes the following steps:

[0102] The organic ligand, the nickel salt, and the first solvent are mixed.

[0103] Furthermore, the organic ligand and the nickel salt are dissolved in the first solvent respectively to obtain an organic ligand solution and a nickel salt solution, and then the organic ligand solution and the nickel salt solution are mixed.

[0104] In some examples, in step S10, the hydrothermal method includes the following steps:

[0105] Immerse the substrate in the hydrothermal solution and keep it at 120℃~140℃ for 12 h~20 h.

[0106] It is understood that after the hydrothermal method is completed, the substrate on which the nickel metal-organic framework layer has been grown is removed for cleaning and drying. Furthermore, the cleaning agent includes an ethanol solution; the drying temperature is 60°C to 70°C, and the vacuum drying is performed for 12 to 15 hours.

[0107] In some examples, step S10 further includes a step of pre-treating the substrate before providing the nickel metal organic framework material layer on the surface of the substrate.

[0108] Furthermore, the pre-processing includes the following steps:

[0109] The front and back sides of the substrate are treated with plasma respectively, and then placed in an acid solution for ultrasonic treatment.

[0110] Optionally, the power of the plasma treatment is 100 W to 150 W, the gas flow rate is 3 sccm to 5 sccm, and the time is 5 min to 10 min; optionally, the acid solution includes a hydrochloric acid solution; further, the concentration of the acid solution is 1 mol / L to 3 mol / L; further, the ultrasonic treatment also includes cleaning and drying steps.

[0111] Pre-treating nickel foam with hydrochloric acid can remove impurities and oxides on its surface, regulate its pore structure to a certain extent, facilitate the penetration of liquid into its skeleton during hydrothermal treatment, and facilitate the subsequent growth of metal skeleton organic compounds.

[0112] Step S20: loading ruthenium particles on the surface of the nickel metal organic framework material layer prepared in step S10 away from the substrate to prepare a Ru-Ni material.

[0113] In some examples, in step S20, the Ni-MOF material prepared in step S10 is placed in a ruthenium precursor solution and allowed to stand. Furthermore, the ruthenium precursor solution includes a ruthenium precursor and a third solvent; further, the mass ratio of ruthenium trichloride trihydrate to water is 12 mg to 18 mg: 8 mL to 15 mL; further, the ruthenium precursor includes ruthenium trichloride trihydrate; further, the third solvent includes water; further, the mass ratio of ruthenium trichloride trihydrate to water is 12 mg: 8 mL. Furthermore, the standing time is 10 to 20 hours.

[0114] It can be understood that the ruthenium particles are loaded on the surface of the nickel metal organic framework material layer through a spontaneous replacement reaction; further, after standing, the material can be taken out, cleaned and dried.

[0115] Step S30: a graphene layer is provided on the surface of the Ru-Ni material prepared in step S20, so that the ruthenium particles are provided between the nickel metal organic framework material layer and the graphene layer.

[0116] It can be understood that the preparation method of the composite catalytic material provided in this application can produce the above-mentioned composite catalytic material, and the above-mentioned composite catalytic material can be produced by the preparation method of the composite catalytic material provided in this application, and the characteristics between the above-mentioned composite catalytic material and the preparation method of the composite catalytic material can be mutually applicable.

[0117] The composite catalytic material prepared by the preparation method of the composite catalytic material provided in the present application is applied as an electrode to hydrogen isotope separation, and has high separation efficiency and good stability.

[0118] It can be understood that in some of these examples, the graphene layer covers the Ru—Ni material.

[0119] In some examples, in step S30, providing the graphene layer includes the following steps:

[0120] A graphene solution is placed on the surface of the Ru-Ni material and dried to form a graphene layer.

[0121] In some examples, in step S30 , the graphene solution includes graphene, carbon dots, a second solvent, and a Nafion solution.

[0122] Optionally, the second solvent includes at least one of water and isopropyl alcohol.

[0123] In some examples, in step S30, the concentration of graphene in the graphene solution is 1 mg / L to 2 mg / L; further, the concentration of graphene in the graphene solution is 1 mg / L.

[0124] In some examples, in step S30, the graphene solution includes 0.05 mg to 0.2 mg of graphene, 0.05 mg to 0.2 mg of carbon dots, 0.2 mL to 1 mL of water, 0.2 mL to 1 mL of isopropanol, and 60 μL to 100 μL of nafion solution.

[0125] It can be understood that in the graphene solution, the mass of graphene includes but is not limited to 0.05 mg, 0.06 mg, 0.07 mg, 0.08 mg, 0.09 mg, 0.10 mg, 0.11 mg, 0.12 mg, 0.13 mg, 0.14 mg, 0.15 mg, 0.16 mg, 0.17 mg, 0.18 mg, 0.19 mg, and 0.20 mg; the mass of carbon dots includes but is not limited to 0.05 mg, 0.06 mg, 0.07 mg, 0.08 mg, 0.09 mg, 0.10 mg, 0.11 mg, 0.12 mg, 0.13 mg, 0.14 mg, 0.15 mg, 0.16 mg, 0.17 mg, 0.18 mg, 0.19 mg, and 0.20 mg; the volume of water includes but is not limited to 0.2 mL, 0.3 mL, 0.4 mL, 0.5 mL, 0.6 mL, 0.7 mL, 0.8 mL, 0.9 mL, 1 mL; the volume of isopropanol includes but is not limited to 0.2 mL, 0.3 mL, 0.4 mL, 0.5 mL, 0.6 mL, 0.7 mL, 0.8 mL, 0.9 mL, 1 mL; the volume of nafion solution includes but is not limited to 60 μL, 70 μL, 80 μL, 90 μL, 100 μL.

[0126] In some examples, in step S30, the graphene solution includes 0.08 mg to 0.12 mg of graphene, 0.08 mg to 0.12 mg of carbon dots, 0.3 mL to 0.8 mL of water, 0.3 mL to 0.8 mL of isopropanol, and 70 μL to 90 μL of nafion solution.

[0127] In some examples, in step S30, the graphene solution includes 0.1 mg of graphene, 0.1 mg of carbon dots, 0.5 mL of water, 0.5 mL of isopropanol, and 80 μL of nafion solution.

[0128] In some examples, in step S30 , a graphene solution is dropped onto the surface of the Ru—Ni material.

[0129] In some examples, in step S30 , the drying method includes drying by irradiation with an infrared lamp.

[0130] It is understood that the composite catalytic material preparation method provided in this application can be used to synthesize catalysts on a large scale on a substrate such as nickel foam, copper foam, or carbon cloth using a scaled-up flow electrolyzer. The scaled-up flow electrolyzer can be up to 12 cm x 5 cm.

[0131] One embodiment of the present application provides an electrode, comprising the above-mentioned composite catalytic material or the composite catalytic material prepared by the above-mentioned preparation method.

[0132] The electrode provided in this application is applied to electrochemical hydrogen isotope separation reactions. Graphene acts as a hydrogen isotope sieving layer between the electrode material and the electrolyte, regulating the rate at which hydrogen isotopes diffuse to the electrode surface to participate in the reaction.

[0133] In some examples, the electrodes have an area of ​​1 cm 2 ~60 cm 2 .

[0134] It is understood that the area of ​​the electrodes includes but is not limited to 1 cm², 2 cm², 3 cm², 4 cm², 5 cm², 6 cm², 7 cm², 8 cm², 9 cm², 10 cm², 11 cm², 12 cm², 13 cm², 14 cm², 15 cm², 16 cm², 17 cm², 18 cm², 19 cm², 20 cm², 21 cm², 22 cm², 23 cm², 24 cm², 25 cm², 26 cm², 27 cm², 28 cm², 29 cm², 30 cm², 31 cm², 32 cm², 33 cm², 34 cm², 35 cm², 36 cm², 37 cm², 38 cm², 39 cm², 40 cm², 41 cm², 42 cm², 43 cm², 44 cm², 45 cm², 46 cm², 47 cm², 48 cm², 49 cm², 50 cm² cm², 51 cm², 52 cm², 53 cm², 54 cm², 55 cm², 56 cm², 57 cm², 58 cm², 59 cm², 60 cm².

[0135] One embodiment of the present application provides the use of the above-mentioned electrode in electrocatalytic hydrogen isotope separation.

[0136] In some examples, the electrodes are used in electrocatalytic hydrogen isotope separation, wherein the catholyte for the electrocatalytic hydrogen isotope separation comprises potassium hydroxide.

[0137] In some of these examples, the concentration of potassium hydroxide in the catholyte is 0.1 mol / L to 1 mol / L.

[0138] It will be appreciated that the concentration of potassium hydroxide in the cathode electrolyte includes but is not limited to 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, and 1 mol / L.

[0139] In some examples, when the electrode is used in electrocatalytic hydrogen isotope separation, the cathode electrolyte further comprises at least one of heavy water and an alcohol solvent. Optionally, the alcohol solvent comprises at least one of methanol, ethanol, isopropanol, and ethylene glycol.

[0140] Optionally, the concentration of the alcohol solvent in the cathode electrolyte is 1 mol / L to 5 mol / L.

[0141] It is understood that the concentration of the alcohol solvent in the cathode electrolyte includes but is not limited to 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, and 5 mol / L.

[0142] In some examples, the electrodes are used in electrocatalytic hydrogen isotope separation, where the catholyte comprises potassium hydroxide and isopropyl alcohol.

[0143] The addition of isopropanol improved the isotope separation efficiency.

[0144] In some examples, the electrodes are used in electrocatalytic hydrogen isotope separation, where the catholyte further comprises potassium bifluoride.

[0145] In some examples, in the application of the above-mentioned electrode in electrocatalytic hydrogen isotope separation, the cathode electrolyte also includes heavy water; optionally, the volume fraction of heavy water in the cathode electrolyte is 1%~100%.

[0146] It will be appreciated that the volume fraction of heavy water in the cathode electrolyte includes, but is not limited to, 1%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100%.

[0147] It will be appreciated that the electrolyte comprises a cathode electrolyte and an anode electrolyte.

[0148] In some examples, in the application of the electrode for electrocatalytic hydrogen isotope separation, the anolyte comprises KOD. Furthermore, the concentration of potassium ions in the anolyte is 1 mol / L to 2 mol / L, and the solvent is deuterated water.

[0149] In some examples, the electrodes are used in electrocatalytic hydrogen isotope separation, and the reactor (electrolytic cell) for performing the electrocatalytic hydrogen isotope separation includes one of a two-phase reactor and a three-phase reactor.

[0150] In some examples, the electrodes are used in electrocatalytic hydrogen isotope separation, and the proton exchange membrane for electrocatalytic hydrogen isotope separation includes a speek membrane.

[0151] Using a flow electrolytic cell and the above electrodes, in the electrochemical hydrogen isotope separation reaction, the 2 , 10 mA / cm 2 , 2 mA / cm 2 , 1 mA / cm 2 , 0.5 mA / cm 2 The current density was stable for 432 hours.

[0152] One embodiment of the present application provides an electrochemical reactor, comprising the above-mentioned electrode.

[0153] Furthermore, the electrochemical reactor includes different electrolytic cells with different electrode areas. Furthermore, the electrochemical reactors with different electrode areas are used for different reaction stages of electrochemical hydrogen isotopes. Furthermore, the electrochemical reactor is connected to an external buffer bottle for separating reaction gas products.

[0154] One embodiment of the present application provides a reactor for electrocatalytic hydrogen isotope separation, comprising a cathode electrolysis chamber, an anode electrolysis chamber, a cathode disposed in the cathode electrolysis chamber, and an anode disposed in the anode electrolysis chamber, wherein the cathode adopts the above-mentioned electrode.

[0155] In some examples, the reactor for electrocatalytic hydrogen isotope separation further includes a cathode gas circulation chamber. It can be understood that this is a three-phase reactor.

[0156] The reactor comprises the above-mentioned electrodes and thus has at least the same advantages as the above-mentioned electrodes.

[0157] The present application will be described in further detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0158] Example 1

[0159] (1) Preparation of NiF materials

[0160] A 2 cm × 2 cm nickel foam substrate was treated with plasma on both sides for 5 min (150 W, 5 sccm), and then immersed in a 3 mol / L hydrochloric acid solution for ultrasonic treatment for 10 min. After the treatment, the nickel foam was ultrasonically cleaned with deionized water until neutral and then dried in an oven to obtain NiF material.

[0161] (2) Preparation of Ni-MOF materials

[0162] 62 mg of terephthalic acid and 46 mg of Ni(CH3COO)2·4H2O were dissolved in a mixed solvent (1 mL of ethanol + 1 mL of deionized water + 16 mL of N,N-dimethylformamide) and ultrasonicated until fully dissolved and dispersed to obtain a mixed solution. The mixed solution was transferred to a hydrothermal reactor, and the 2 cm×2 cm NiF material prepared in step (1) was immersed in the mixed solution and kept at 120°C for 12 h. After the reaction was completed, it was washed with ethanol solution and then vacuum dried at 60°C for 12 h to obtain Ni-MOF material. Its scanning electron microscope image is shown as follows: Figure 1 shown.

[0163] (3) Preparation of Ru-Ni materials

[0164] The Ni-MOF material prepared in step (2) was cut into 1 cm × 1 cm size and immersed in an aqueous solution of ruthenium trichloride trihydrate (12 mg ruthenium trichloride trihydrate + 8 mL deionized water). After soaking for 10 h, it was taken out, rinsed with deionized water and dried naturally to obtain Ru-Ni material. Its scanning electron microscope image is shown as follows: Figure 2 shown.

[0165] (4) Preparation of Ru-NiC materials

[0166] Graphene solution was added to both sides of the Ru-Ni material prepared in step (3) and dried by infrared light to obtain a graphene-wrapped ruthenium nickel composite material (Ru-NiC material). The graphene solution included 0.1 mg of graphene, 0.1 mg of carbon dots, 0.5 mL of deionized water, 0.5 mL of isopropanol, and 80 μL of Nafion solution. The scanning electron microscope image of the Ru-NiC material is shown in Figure 2. Figure 3 As shown, the transmission scanning electron microscope image of Ru-NiC material is as follows Figure 4 shown.

[0167] Comparative Example 1

[0168] The method is basically the same as Example 1, except that, in step (3), the Ni-MOF material prepared in step (2) is immersed in an aqueous solution of sodium hexachloroplatinate hexahydrate (12 mg sodium hexachloroplatinate hexahydrate + 8 mL deionized water), as follows:

[0169] (1) Preparation of NiF materials

[0170] A 2 cm × 2 cm nickel foam was treated with plasma on both the front and back sides for 5 min (150 W, 5 sccm), and then immersed in a 3 mol / L hydrochloric acid solution for ultrasonic treatment for 10 min. After the treatment, the nickel foam was ultrasonically cleaned with deionized water until neutral and then dried in an oven to obtain NiF material.

[0171] (2) Preparation of Ni-MOF materials

[0172] 62 mg of terephthalic acid and 46 mg of Ni(CH3COO)2·4H2O were dissolved in a mixed solvent (1 mL of ethanol + 1 mL of deionized water + 16 mL of N,N-dimethylformamide) and ultrasonicated until fully dissolved and dispersed to obtain a mixed solution; the mixed solution was transferred to a hydrothermal reactor, and the 2 cm×2 cm Ni material F prepared in step (1) was immersed in the mixed solution and maintained at 120°C for 12 h. After the reaction was completed, it was washed with ethanol solution and then vacuum dried at 60°C for 12 h to obtain Ni-MOF material.

[0173] (3) Preparation of Pt-Ni materials

[0174] The Ni-MOF material prepared in step (2) was cut into a size of 1 cm × 1 cm, immersed in an aqueous solution of ruthenium trichloride trihydrate and an aqueous solution of sodium hexachloroplatinate hexahydrate (12 mg sodium hexachloroplatinate hexahydrate + 8 mL deionized water), and taken out after soaking for 10 h. It was rinsed with deionized water and then dried naturally to obtain a Pt-Ni material.

[0175] (4) Preparation of Pt-NiC materials

[0176] Graphene solution was added to both sides of the Pt-Ni material prepared in step (3) and dried by infrared light to obtain a graphene-wrapped platinum-nickel composite material (Pt-NiC material). The graphene solution included 0.1 mg graphene, 0.1 mg carbon dots, 0.5 mL deionized water, 0.5 mL isopropanol, and 80 μL Nafion solution. The scanning electron microscope image of the Pt-NiC material is shown in Figure 2. Figure 5 shown.

[0177] Application Examples

[0178] The NiF material prepared in step (1) of Example 1 was used as a NiF electrode; the Ni-MOF material prepared in step (2) of Example 1 was used as a Ni-MOF electrode; the Ru-Ni material prepared in step (3) of Example 1 was used as a Ru-Ni electrode; the Ru-NiC material prepared in step (4) of Example 1 was used as a Ru-NiC electrode; and the Pt-NiC material prepared in step (4) of Comparative Example 1 was used as a Pt-NiC electrode.

[0179] Electrocatalytic hydrogen isotope separation tests were conducted using a flow cell. A NiF electrode (as comparative application example 2), a Ni-MOF electrode (as comparative application example 3), a Ru-Ni electrode (as comparative application example 4), a Ru-NiC electrode (as application example 1), and a Pt-NiC electrode (as comparative application example 1) were used as cathodes, platinum mesh was used as an anode, and a proton exchange membrane (speek) was used as a diaphragm between the cathode electrolyte and the anolyte to separate the cathode electrolysis chamber from the anode electrolyte chamber. The anolyte was located in the anode electrolyte chamber, and the anolyte was 1 mol / L KOD. The catholyte was located in the cathode electrolyte chamber, and the catholyte was 1M KOH, or different volume fractions of heavy water solutions and different organic additive solutions (including isopropyl alcohol and ethylene glycol, etc.) were additionally added to 1M KOH. The specific test results are as follows, where 1M refers to 1 mol / L and IPA is isopropyl alcohol.

[0180] Figure 6 TF-SIMS mapping images of H and D (deuterium) of Ru-NiC electrode and Pt-NiC electrode; Figure 7 The curves of D (deuterium) intensity depth profiles of Ru-NiC electrode and Pt-NiC electrode are shown in Figure 2. Figure 6 and Figure 7 It can be seen that the distribution of H on the surface and inside of the Ru-NiC electrode and the Pt-NiC electrode is uniform, with no significant difference; the content of D (deuterium) is less in the Ru-NiC electrode, while it is higher in the Pt-NiC electrode. There is a clear difference in the distribution of D (deuterium) between the two electrodes, indicating that the separation effect of D (deuterium) is limited in the Pt-NiC electrode, while D (deuterium) is effectively separated in the Ru-NiC electrode.

[0181] Figure 8 This is a curve diagram of the linear sweep voltammetry test of Ru-NiC electrode in a three-electrode electrolytic cell. Figure 9 The graph is a linear sweep voltammetry test of the Pt-NiC electrode in a three-electrode electrolytic cell. The cathode electrolytes are: No. 1 electrolyte, 1M KOH + 4M IPA ( Figure 8 Marked as Ru-NiC-IPA); No. 2 electrolyte, 1M KOH+4M IPA+5%D (the volume fraction of heavy water in the cathode electrolyte is 5%, Figure 8 Marked as Ru-NiC-IPA-5% D); No. 3 electrolyte, 1M KOH+4M IPA+50% D ( Figure 8 Marked as Ru-NiC-IPA-50% D); No. 4 electrolyte, 1M KOH+4M IPA+1M KOD ( Figure 8Marked as Ru-NiC-IPA+KOD); No. 5 electrolyte, 1M KOH. The rest are similar. Figure 8 and Figure 9 It can be seen that when the Ru-NiC electrode is used as the working electrode, the concentration change of heavy water and the addition of isopropyl alcohol (IPA) have a particularly obvious inhibitory trend on the current density, while when the Pt-NiC electrode is used as the working electrode, there is no such obvious difference, indicating that the Ru-NiC material has better isotope separation ability than the Pt-NiC material.

[0182] Figure 10 This is a graph of the linear sweep voltammetry test of NiF electrode in a three-electrode electrolytic cell. Figure 11 This is a curve diagram of the linear sweep voltammetry test of the Ni-MOF electrode in a three-electrode electrolytic cell. Figure 12 The graph is a linear sweep voltammetry test curve of Ru-Ni electrode in a three-electrode electrolytic cell; wherein, the cathode electrolytes are: No. 5 electrolyte, 1M KOH; No. 6 electrolyte, 1M KOH + 5% D (the volume fraction of heavy water in the cathode electrolyte is 5%); No. 7 electrolyte, 1M KOH + 5% D + 4M IPA. Figure 8 、 Figures 10 to 12 It can be seen that the current density of different types of electrodes (NiF electrode, Ni-MOF electrode, Ru-Ni electrode and Ru-NiC electrode) when reacting in electrolyte No. 7 containing isopropyl alcohol is suppressed to varying degrees. This inhibitory effect is most obvious when Ru-NiC material is used as the cathode; the higher the degree of suppression, the better the hydrogen isotope separation effect.

[0183] Figure 13 Figure 3 is the Tafel slope diagram of the Ru-NiC electrode under different cathode electrolyte conditions, where the cathode electrolytes are: No. 8 electrolyte, 1M KOH; No. 9 electrolyte, 1M KOD; No. 10 electrolyte, 4M IPA+1M KOH; No. 11 electrolyte, 4MIPA+1M KOD. Figure 14 The following are Tafel slope plots of the Ru-NiC electrode under different catholyte conditions: electrolyte 12, 4M EtOH (ethanol) + 1M KOH; electrolyte 13, 4M EtOH + 1M KOD; electrolyte 14, 4M EG (ethylene glycol) + 1M KOH; and electrolyte 15, 4M EG + 1M KOD. The KIE value is calculated based on the current density ratio of the pure H solution system to the pure deuterium solution system and the Tafel slope. For the same electrode, the current density ratio in the pure H solution system to the pure deuterium solution system is constant. A larger Tafel slope indicates a larger KIE value and better hydrogen isotope separation.

[0184] Depend on Figure 13 The kinetic isotope effect (KIE) value of Ru-NiC electrode in electrolyte without isopropanol and with 4M isopropanol as a function of overpotential is calculated as follows: Figure 15 As shown. Figure 15 It can be seen that the addition of isopropanol increases the KIE value from 149 to 10165 at an overpotential of 0.5 V vs. RHE, indicating that the addition of isopropanol improves the isotope separation efficiency.

[0185] It can be understood that Tafel is calculated based on the LSV data obtained from tests in different electrolytes, and the KIE value is then calculated based on the LSV and Tafel.

[0186] Figure 16 Schematic diagram of a two-phase hydrogen-deuterium separation reactor for hydrogen isotope separation testing; Figure 17 Schematic diagram of a three-phase hydrogen-deuterium separation reactor for hydrogen isotope separation testing; the results show that the isotope separation effect of the three-phase hydrogen-deuterium separation reactor is better than that of the two-phase hydrogen-deuterium separation reactor.

[0187] Figure 18 Schematic diagram of multi-stage electrolysis in 5 electrolytic cells with different electrode areas.

[0188] The molar fractions of the three generated gases (H2, D2, HD) at the outlet of the Ru-NiC electrode when fed with electrolytes containing different deuterium contents with and without isopropanol are as follows: Figure 19 As shown. Figure 19 It can be seen that under different feed deuterium contents, the deuterium (D) atomic fraction in the gas generated by the system containing isopropanol as the electrolyte is relatively low, indicating that the D element is effectively enriched in the solution.

[0189] The separation factor of Ru-NiC electrode in constant current electrolysis of electrolyte with different deuterium contents in the presence and absence of isopropanol for 7 hours is as follows Figure 20 As shown. Figure 20 It can be seen that the separation factor of the system containing isopropanol is higher than that of the system not containing isopropanol.

[0190] The deuterium (D) atomic fraction curve and the current curve of the water separation factor during the five-stage electrolysis of the electrolyte containing 1% D element by volume are shown in the figure below. Figure 21 As shown. Figure 21 It can be seen that after 17 days of multi-stage electrolysis reaction, the deuterium atomic fraction increased to 80%. In the long-term electrolysis separation process, the water separation factor of each stage increased with the increase of the time of each stage.

[0191] The curves of deuterium (D) atomic fraction and water separation factor during long-term electrolytic hydrogen isotope separation in electrolyte prepared from natural water are shown as follows: Figure 22As shown in a and b, the water separation factor in natural water also shows a trend of increasing in each stage.

[0192] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0193] The embodiments described above only express several implementation methods of the present application, which are convenient for understanding the technical solutions of the present application in a specific and detailed manner, but they cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several variations and improvements can be made, which all fall within the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A composite catalytic material, characterized in that: The invention comprises a substrate, a nickel metal organic framework material layer, ruthenium particles and a graphene layer, wherein the nickel metal organic framework material layer is arranged on the surface of the substrate, the graphene layer is arranged on the surface of the nickel metal organic framework material layer away from the substrate, and the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer; the nickel metal organic framework material layer comprises a metal organic framework material, the metal organic framework material comprises nickel metal ions and organic ligands coordinated with the nickel metal ions, and the organic ligands comprise terephthalic acid; the graphene layer comprises graphene and carbon dots mixed with each other.

2. The composite catalytic material according to claim 1, wherein The mass ratio of the graphene to the carbon dots is 1:0.5-2.

3. The composite catalytic material according to claim 1, wherein The molar ratio of the nickel metal ion to the organic ligand is 0.4-0.8:

1.

4. The composite catalytic material according to any one of claims 1 to 3, characterized in that: The composite catalytic material satisfies at least one of the following characteristics: (1) The ratio of the amount of the ruthenium particles to the single-side area of ​​the nickel metal organic framework material layer is 0.1 mmol / cm 2 ~0.2mmol / cm 2 ; (2) The substrate includes at least one of foamed nickel, foamed copper and carbon cloth.

5. A method for preparing a composite catalytic material according to any one of claims 1 to 4, characterized in that: The following steps are involved: A nickel metal organic framework material layer is provided on the surface of the substrate; the nickel metal organic framework material layer comprises a metal organic framework material, the metal organic framework material comprises nickel metal ions and an organic ligand coordinated with the nickel metal ions, and the organic ligand comprises terephthalic acid; loading ruthenium particles on the surface of the nickel metal organic framework material layer away from the substrate to prepare a Ru-Ni material; A graphene layer is provided on the surface of the Ru-Ni material, so that the ruthenium particles are provided between the nickel metal organic framework material layer and the graphene layer; the graphene layer includes mutually mixed graphene and carbon dots.

6. The method for preparing the composite catalytic material according to claim 5, wherein: The method for setting the nickel metal organic framework material layer is a hydrothermal method; the hydrothermal solution used in the hydrothermal method includes terephthalic acid, nickel salt and a first solvent.

7. The method for preparing the composite catalytic material according to claim 6, wherein: The nickel salt includes at least one of nickel acetate, nickel nitrate and nickel chloride.

8. The method for preparing the composite catalytic material according to claim 6, wherein: The first solvent includes N,N-dimethylformamide.

9. The method for preparing the composite catalytic material according to claim 8, wherein: The first solvent further comprises at least one of ethanol and water.

10. The method for preparing a composite catalytic material according to any one of claims 5 to 9, characterized in that: Providing the graphene layer comprises the following steps: A graphene solution is placed on the surface of the Ru-Ni material and dried to form a graphene layer; the graphene solution includes graphene, carbon dots, a second solvent and a nafion solution.

11. The method for preparing a composite catalytic material according to claim 10, wherein: The second solvent includes at least one of water and isopropyl alcohol.

12. The method for preparing a composite catalytic material according to claim 10, wherein: The graphene solution includes 0.05 mg to 0.2 mg of graphene, 0.05 mg to 0.2 mg of carbon dots, 0.2 mL to 1 mL of water, 0.2 mL to 1 mL of isopropyl alcohol, and 60 μL to 100 μL of nafion solution.

13. An electrode, characterized in that: The invention comprises the composite catalytic material according to any one of claims 1 to 4 or the composite catalytic material prepared by the preparation method according to any one of claims 5 to 12.

14. Use of the electrode according to claim 13 in electrocatalytic hydrogen isotope separation.

15. The use according to claim 14, characterized in that The cathode electrolyte for electrocatalytic hydrogen isotope separation comprises potassium hydroxide, heavy water and an alcohol solvent.

16. The use according to claim 15, characterized in that The alcohol solvent includes at least one of methanol, ethanol, isopropanol and ethylene glycol.

17. The use according to any one of claims 14 to 16, characterized in that: The reactor for performing the electrocatalytic hydrogen isotope separation includes one of a two-phase reactor and a three-phase reactor.

18. A reactor for electrocatalytic hydrogen isotope separation, characterized in that: It comprises a cathode electrolysis chamber, a cathode gas circulation chamber, an anode electrolysis chamber, a cathode arranged in the cathode electrolysis chamber, and an anode arranged in the anode electrolysis chamber, wherein the cathode adopts the electrode according to claim 13.

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