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

Abstract

The invention relates to a composite catalytic material and a preparation method thereof, an electrode and application thereof, 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 arranged on the surface of the substrate, the graphene layer is arranged on the surface, away from the substrate, of the nickel metal organic framework material layer, and the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer. The composite catalytic material is prepared into an electrode for electrocatalytic hydrogen isotope separation, and the diffusion rate of hydrogen and deuterium in a solution can be effectively regulated and controlled, so that the hydrogen and deuterium separation efficiency is improved.

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 include thermal diffusion and distillation, which have problems such as high energy consumption, low efficiency, and high cost, making it difficult to meet the needs of large-scale industrial applications. As a green and controllable separation method, electrochemical methods have shown unique advantages in the field of hydrogen isotope separation. However, the efficiency of traditional electrochemical separation of hydrogen isotopes is low.

[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 a preparation method thereof, 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 of the 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 of the 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 of the 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 arranged on the surface of the Ru-Ni material, so that the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer.

[0015] In some of the embodiments, in the method for preparing the composite catalytic material, the method for setting the nickel metal organic framework material layer comprises a hydrothermal method; optionally, the hydrothermal solution used in the hydrothermal method comprises an organic ligand, a nickel salt and a first solvent; optionally, the organic ligand comprises terephthalic acid; optionally, the nickel salt comprises at least one of nickel acetate, nickel nitrate and nickel chloride; optionally, the first solvent comprises N,N-dimethylformamide; optionally, the first solvent also comprises 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 of the 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 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 of the 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 of the embodiments, in the application of the electrode in electrocatalytic hydrogen isotope separation, the reactor for performing the electrocatalytic hydrogen isotope separation comprises one of a two-phase reactor and a three-phase reactor.

[0023] On 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 acts as a hydrogen isotope screening layer to slow down the contact between deuterium and the surface of the composite catalytic material, control the reaction rate, effectively improve the hydrogen isotope separation efficiency, and has 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 completely understand the present application and its beneficial effects, the following is a brief introduction to the drawings required for the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings without creative work.

[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 microscope image 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 system electrolytic cell;

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

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

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

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

[0039] Fig.13 Tafel slope diagram of Ru-NiC electrode under different cathode electrolyte conditions;

[0040] Fig.14 Tafel slope diagram of Ru-NiC electrode under different cathode electrolyte conditions;

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

[0042] Fig.16 Schematic diagram of a hydrogen-deuterium separation two-phase reactor for conducting hydrogen isotope separation tests;

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

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

[0045] Fig.19 The graphs of the mole fractions of three generated gases at the outlet of Ru-NiC electrode when the electrolyte with different deuterium contents is fed with and without isopropanol;

[0046] Fig. 20 The separation factor diagram of Ru-NiC electrode in constant current electrolysis of electrolyte with different deuterium content in the presence and absence of isopropanol for 7 hours;

[0047] Fig.21 It is a current curve of the deuterium (D) atomic fraction curve and the water separation factor during the five-stage electrolysis of the deuterium (D) electrolyte;

[0048] Fig. 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 used to illustrate the present application and are not used to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[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 equivalent forms obtained also fall within the scope of protection of the present application. For example, the features illustrated or described as part of one embodiment can be combined in another embodiment in a suitable manner 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 comprehensive 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 belongs. The terms used herein in the specification of this application are only for the purpose of describing implementation modes and embodiments 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 the present application, "plurality", "multiple", "multiple times", etc., unless otherwise specified, refer to a number greater than 2 or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0054] As used herein, "combination thereof", "any combination thereof", "any combination thereof" etc. 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, "preferred", "better", "more preferred", and "suitable" are only used to describe implementation methods or examples with better effects, and it should be understood that they do not constitute a limitation on the scope of protection of this application. If multiple "preferred" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "preferred" item is independent.

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

[0058] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

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

[0060] In the present 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 the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0062] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[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 the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 3~5 h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0065] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the invention purpose and / or technical solution of this application, the cited documents involved in this application are cited with all contents and all purposes. When the 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 the cited documents are involved in this application, the examples and preferred methods of the cited relevant technical features can also be incorporated into this application as references, but are limited to the implementation of 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 modified adaptively according to the description of this application.

[0066] The mass or weight of the relevant components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also indicate the proportional relationship of the mass or weight between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the specification of the embodiments of the present application, it is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass or weight described in the specification of the embodiments of the present 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, result in low efficiency of traditional electrochemical separation of hydrogen isotopes, which means that 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, wherein 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.

[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 to slow down the contact between deuterium and the surface of the composite catalytic material, control the reaction rate, effectively improve the hydrogen isotope separation efficiency, and has good stability performance.

[0070] The composite catalytic material is made into an electrode 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 can be understood that the ruthenium particles are loaded on the surface of the nickel metal organic framework material layer. It can be further understood that in the composite catalytic material of the present application, the surface of the substrate is provided with a nickel metal organic framework material layer, ruthenium particles and a graphene layer in sequence; it can also be 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 the 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 from all sides of the composite catalytic material, 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.

[0074] In some of these examples, in the composite catalytic material, the graphene layer 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, 1:2; in some examples, any two of these point values ​​can be used as end values ​​within the range, 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 of the 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 metal ions to organic ligands is 0.4-0.8:1.

[0081] It is understood that the molar ratio of metal ions to organic ligands 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 ions to organic ligands 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 material layer in the composite catalyst 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 the 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 foamed nickel, foamed copper, and carbon cloth.

[0087] An 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, which is a metal-organic framework material. It is a crystalline material with a periodic network structure formed by self-assembly of nickel ions and organic ligands through coordination bonds.

[0090] In some of the examples, in step S10, the method of providing 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 of the 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 of the 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. Further, the volume ratio of N,N-dimethylformamide, ethanol and water is 10-20:1-5:1-5. Optionally, the volume ratio of N,N-dimethylformamide, ethanol and 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 material layer is 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 h to 15 h.

[0107] In some of the examples, in step S10, before the step of providing the nickel metal organic framework material layer on the surface of the substrate, the step of pre-treating the substrate is also included.

[0108] Further, the pre-processing comprises 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~150 W, the gas flow rate is 3 sccm~5 sccm, and the time is 5 min~10 min; optionally, the acid solution includes a hydrochloric acid solution; further, the concentration of the acid solution is 1 mol / L~3 mol / L; further, the ultrasonic treatment also includes the steps of cleaning and drying.

[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 of the examples, in step S20, the Ni-MOF material prepared in step S10 is placed in a ruthenium precursor solution and allowed to stand. Further, 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~18 mg:8 mL~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. Further, the standing time is 10 h~20 h.

[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 particles can be taken out, cleaned and dried.

[0115] Step S30: a graphene layer is disposed on the surface of the Ru-Ni material prepared in step S20, so that the ruthenium particles are disposed 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 the present application can produce the above-mentioned composite catalytic material, the above-mentioned composite catalytic material can be produced by the preparation method of the composite catalytic material provided in the present 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] The 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 isopropanol.

[0123] In some of the 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 of the examples, in step S30, 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.

[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, 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, 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 of the 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 of the 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 of the 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 infrared light irradiation.

[0130] It can be understood that the composite catalytic material preparation method provided in the present application can be used to synthesize catalysts on a large scale on a large-area substrate such as foamed nickel, foamed copper, or carbon cloth by using an enlarged flow electrolyzer. The enlarged flow electrolyzer can reach 12 cm×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 the present application is applied to the electrochemical hydrogen isotope separation reaction, and 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 of these examples, the electrode area is 1 cm 2 ~60 cm 2 .

[0134] It is understood that the area of ​​the electrode 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, 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 electrode is used in electrocatalytic hydrogen isotope separation, wherein the catholyte of 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~1 mol / L.

[0138] It is understood 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 of the examples, in the application of the electrode 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 of these examples, the electrodes are used in electrocatalytic hydrogen isotope separation, where the catholyte comprises potassium hydroxide and isopropanol.

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

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

[0145] In some of the 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 includes a cathode electrolyte and an anode electrolyte.

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

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

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

[0151] Using the 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 stably maintained for 432 hours.

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

[0153] Further, the electrochemical reactor comprises different electrolytic cells with different electrode areas. Further, the electrochemical reactors with different electrode areas are applied to different reaction stages of electrochemical hydrogen isotopes. Further, the electrochemical reactor is connected to a buffer bottle for separation of reaction gas products.

[0154] An embodiment of the present application provides a reactor for electrocatalytic hydrogen isotope separation, including a cathode electrolysis 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.

[0155] In some of the 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 electrode and thus has at least the same advantages as the above-mentioned electrode.

[0157] The present application is further described in 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] The 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 it was neutral and then placed in an oven for drying 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) respectively, 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 a Ni-MOF material, whose scanning electron microscope image is shown in the figure. 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, immersed in an aqueous solution of ruthenium trichloride trihydrate (12 mg ruthenium trichloride trihydrate + 8 mL deionized water), and taken out after soaking for 10 h. It was rinsed with deionized water and dried naturally to obtain a Ru-Ni material. Its scanning electron microscope image is shown in FIG. 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 then 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] The 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 it was neutral and then placed in an oven for drying 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) respectively, 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 a 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. The material 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), wherein 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 FIG. Figure 5 shown.

[0177] Application Examples.

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

[0179] A flow cell was used to carry out an electrocatalytic hydrogen isotope separation test, wherein a NiF electrode (as application comparative example 2), a Ni-MOF electrode (as application comparative example 3), a Ru-Ni electrode (as application comparative example 4), a Ru-NiC electrode (as application example 1) and a Pt-NiC electrode (as application comparative example 1) were respectively used as cathodes, a platinum mesh was used as an anode, a proton exchange membrane (speek) was used as a diaphragm between a cathode electrolyte and an anode electrolyte to separate the cathode electrolyte chamber from the anode electrolyte chamber, an anode electrolyte was provided in the anode electrolyte chamber, and the anode electrolyte was 1 mol / L KOD, a cathode electrolyte was provided in the cathode electrolyte chamber, and the cathode electrolyte was 1M KOH, or different volume fractions of a heavy water solution and different organic additive solutions (including isopropanol and ethylene glycol, etc.) were additionally added to 1M KOH, and the specific test results were as follows, wherein 1M refers to 1 mol / L, and IPA is isopropanol.

[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. 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 significant difference in the distribution of D (deuterium) in the two electrodes, indicating that the separation effect of D (deuterium) in the Pt-NiC electrode is limited, while D (deuterium) is effectively separated in the Ru-NiC electrode.

[0181] Figure 8 It is the curve diagram of the linear sweep voltammetry test of Ru-NiC electrode in the three-electrode electrolytic cell. Fig. 9 The curve diagram of the linear sweep voltammetry test of the Pt-NiC electrode in the three-electrode system 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 in the figure); No. 5 electrolyte, 1M KOH. The rest are similar. Figure 8 and Fig. 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 compared with the Pt-NiC material, the Ru-NiC material has better isotope separation ability.

[0182] Fig.10 This is a curve diagram of the linear sweep voltammetry test of NiF electrode in a three-electrode electrolytic cell. Fig.11 This is a curve diagram of the linear sweep voltammetry test of the Ni-MOF electrode in a three-electrode electrolytic cell. Fig.12 The graph is a linear sweep voltammetric test curve of Ru-Ni electrode in a three-electrode electrolytic cell; 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 , Figure 10~Figure 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 isopropanol is inhibited to varying degrees. This inhibitory effect is most obvious when Ru-NiC material is used as the cathode; the higher the degree of inhibition, the better the hydrogen isotope separation effect.

[0183] Fig.13 It is the Tafel slope diagram of 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. Fig.14 The Tafel slope diagram of Ru-NiC electrode under different cathode electrolyte conditions, where the cathode electrolytes are: No. 12 electrolyte, 4M EtOH (ethanol) + 1M KOH; No. 13 electrolyte, 4M EtOH + 1M KOD; No. 14 electrolyte, 4M EG (ethylene glycol) + 1M KOH; No. 15 electrolyte, 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. The current density ratio of the same electrode in the pure H solution system to the pure deuterium solution system is certain. The larger the Tafel slope, the larger the KIE value, and the better the hydrogen isotope separation effect.

[0184] Depend on Fig.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 shown in Figure 2. Fig.15 As shown. Fig.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 LSV data obtained from tests in different electrolytes, and the KIE value is then calculated based on LSV and Tafel.

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

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

[0188] The molar fractions of the three gases (H2, D2, HD) at the outlet of the Ru-NiC electrode when the electrolyte with different deuterium contents is fed with and without isopropanol are shown in Figure 2. Fig.19 As shown. Fig.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 for 7 hours with and without isopropanol is as follows Fig. 20 As shown. Fig. 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 an electrolyte containing 1% D by volume are shown in Figure 2. Fig.21 As shown. Fig.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 in 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 electrolysis of hydrogen isotope separation in electrolyte prepared from natural water are shown in Figure 2. Fig. 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-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it 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 modifications and improvements can be made, which all belong to 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: It includes 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.

2. The composite catalytic material according to claim 1, characterized in that 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.

3. The composite catalytic material according to claim 1, characterized in that: 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.

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 ~0.2 mmol / 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, characterized in that: The following steps are involved: Disposing a nickel metal organic framework material layer on the surface of the substrate; 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 arranged on the surface of the Ru-Ni material, so that the ruthenium particles are arranged between the nickel metal organic framework material layer and the graphene layer.

6. The method for preparing the composite catalytic material according to claim 5, characterized in that: The preparation method meets at least one of the following characteristics: (1) The method for setting the nickel metal organic framework material layer comprises a hydrothermal method; optionally, the hydrothermal solution used in the hydrothermal method comprises an organic ligand, a nickel salt and a first solvent; optionally, the organic ligand comprises terephthalic acid; optionally, the nickel salt comprises at least one of nickel acetate, nickel nitrate and nickel chloride; optionally, the first solvent comprises N,N-dimethylformamide; optionally, the first solvent further comprises at least one of ethanol and water; (2) Providing the graphene layer comprises the following steps: Placing a graphene solution on the surface of the Ru-Ni material and forming a graphene layer after drying; Optionally, the graphene solution comprises graphene, carbon dots, a second solvent and a nafion solution; optionally, the second solvent comprises at least one of water and isopropanol; optionally, the graphene solution comprises 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.

7. An electrode, characterized in that: It includes the composite catalytic material as described in any one of claims 1 to 4 or the composite catalytic material prepared by the preparation method as described in any one of claims 5 to 6.

8. Use of the electrode as claimed in claim 7 in electrocatalytic hydrogen isotope separation.

9. The use according to claim 8, characterized in that The application satisfies at least one of the following characteristics: (1) The cathode electrolyte for 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; (2) The reactor for performing the electrocatalytic hydrogen isotope separation includes one of a two-phase reactor and a three-phase reactor.

10. 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 7.

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