Nano carbon-ruthenium nickel composite catalytic material as well as preparation method and application thereof

Abstract

The invention discloses a nanocarbon-ruthenium nickel composite catalytic material and a preparation method and application thereof, and belongs to the technical field of catalytic materials.The preparation method of the nanocarbon-ruthenium nickel composite catalytic material.The preparation method of the nanocarbon-ruthenium nickel composite catalytic material comprises the following steps that ruthenium salt is added into a solvent and mixed to be uniform, and a solution A is obtained; adding nickel salt into the solvent, and uniformly mixing to obtain a solution B; adding the organic acid into the solvent, and uniformly mixing to obtain a solution C; adding nanocarbon into a solvent, and dispersing to obtain a mixed solution D; under the condition of continuous stirring, the solution A, the solution B and the solution C are synchronously dropwise added into the mixed solution D for a reaction, and a mixed solution E is obtained; performing centrifugal treatment on the mixed solution E to obtain a precursor F; and cleaning the precursor F, and carrying out vacuum drying to obtain the nano carbon-ruthenium nickel composite catalytic material. According to the invention, anchoring sites with a spatial confinement effect are provided for two metal precursors of ruthenium and nickel by using the anchoring sites and the porous structure on the surface of the nano carbon carrier.

Description

Technical Field

[0001] This invention relates to the field of catalytic materials technology, specifically to a nano-carbon-ruthenium-nickel composite catalytic material, its preparation method, and its application. Background Technology

[0002] Currently, the mainstream catalytic materials for seawater hydrogen production are divided into three categories: First, noble metal single-atom catalysts (such as Pt and Ru single atoms), which have high catalytic activity for the hydrogen evolution reaction (HER), but the number of single active sites is limited, and seawater is easily affected by Cl. - Oxidation or atomic aggregation leads to activity decay, and the use of precious metals is high and the cost is expensive; secondly, transition metal compound catalysts are cheaper, but their HER activity is far inferior to that of precious metals, and they are easily dissolved and corroded in alkaline or high-salt seawater environments, resulting in poor long-term stability; thirdly, nano-carbon-based supported catalysts (such as graphene-supported catalysts) have excellent conductivity and specific surface area, but the interaction between the support and the metal active sites is weak, which easily leads to metal shedding and insufficient resistance to seawater ion pollution.

[0003] Bimetallic catalysts have become a research hotspot in recent years due to the "synergistic effect of dual active sites." Catalytic performance can be enhanced by modulating the electronic effects of the two metal atoms. However, existing products are mostly designed for freshwater hydrogen production, failing to address corrosion and ion interference issues in seawater environments. Furthermore, their preparation processes are complex (e.g., high-temperature pyrolysis, atomic layer deposition), hindering large-scale application. Therefore, developing nano-carbon-based bimetallic catalysts with high catalytic activity, strong corrosion resistance, and low noble metal content has become crucial to overcoming these technological bottlenecks. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing nano-carbon-ruthenium-nickel composite catalytic materials to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0006] A method for preparing a nano-carbon-ruthenium-nickel composite catalytic material includes the following steps:

[0007] Add ruthenium salt to the solvent and mix well to obtain solution A;

[0008] Add the nickel salt to the solvent and mix thoroughly to obtain solution B;

[0009] The organic acid is added to the solvent and mixed thoroughly to obtain solution C;

[0010] Nano-carbon was added to a solvent for dispersion to obtain mixture D;

[0011] Under continuous stirring, solutions A, B, and C are simultaneously added dropwise to mixture D to react and obtain mixture E;

[0012] The mixture E was centrifuged to obtain precursor F;

[0013] After cleaning and vacuum drying the precursor F, nano-carbon-ruthenium nickel composite catalyst material was obtained.

[0014] Furthermore, the solvent is an organic solvent or a mixture of water and an organic solvent; the organic solvent is dichloromethane and / or ethylene glycol.

[0015] Furthermore, the concentration of ruthenium salt in solution A is 17-107 mg / mL; the concentration of nickel salt in solution B is 105-500 mg / mL; the concentration of organic acid in solution C is 50-150 mg / mL; and the concentration of nano-carbon in mixture D is 10-100 mg / mL.

[0016] Furthermore, the volume ratio of solution A, solution B, solution C and mixture D is (1-5):(1-2):(1-2):(2-3).

[0017] Furthermore, the ruthenium salt is one or more of ruthenium trichloride, ruthenium acetate, and ruthenium nitrate.

[0018] Furthermore, the nickel salt is one or more of nickel chloride, nickel nitrate, and nickel acetate.

[0019] Furthermore, the organic acid is one or more of citric acid, ascorbic acid, and formic acid.

[0020] Furthermore, the nano-carbon is in the form of powder or substrate supported, including one or more of graphene and carbon nanotubes.

[0021] Another objective of this invention is to provide a nano-carbon-ruthenium nickel composite catalytic material prepared by the above-described method.

[0022] Another objective of this invention is to provide an application of the above-mentioned nano-carbon-ruthenium nickel composite catalyst in hydrogen production by water electrolysis.

[0023] This invention provides a method for preparing a nano-carbon-ruthenium-nickel composite catalytic material. By utilizing the anchoring sites and porous structure on the surface of the nano-carbon support, spatially confined anchoring sites are provided for the ruthenium and nickel precursors. In this unique support environment, ruthenium and nickel atoms can undergo directional co-reduction and synergistic nucleation, forming bimetallic clusters with specific coordination structures. This preparation method effectively overcomes the technical challenges commonly encountered in traditional impregnation-pyrolysis processes, such as uneven metal particle distribution, size runaway, and phase separation of bimetallic components. Experiments show that the nano-carbon-ruthenium-nickel composite catalytic material prepared by this invention maintains stable catalytic activity even under high current density conditions, demonstrating broad prospects for industrial application. Compared to traditional ruthenium-based or nickel-based catalysts, this nano-carbon-ruthenium-nickel composite catalytic material achieves a synergistic improvement in the activity, selectivity, and stability of the hydrogen evolution reaction through the unique synergistic effect between the bimetallic cluster structure and the nano-carbon support. Under industrial-grade high current density conditions, this nano-carbon-ruthenium-nickel composite catalyst material can still maintain a low overpotential and excellent durability, while exhibiting good corrosion resistance, effectively ensuring continuous and efficient hydrogen production, and providing a reliable material basis for promoting the industrial application of water electrolysis hydrogen production technology. Attached Figure Description

[0024] Figure 1 SEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 1;

[0025] Figure 2 The image shows the HAADF-STEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 1.

[0026] Figure 3 The linear polarization curve of the nano-carbon-ruthenium nickel composite catalytic material prepared in Example 1 is shown.

[0027] Figure 4 SEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 2;

[0028] Figure 5 The linear polarization curve of the nano-carbon-ruthenium nickel composite catalytic material prepared in Example 2 is shown.

[0029] Figure 6 SEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 3;

[0030] Figure 7 Linear polarization curve of the nano-carbon-ruthenium-nickel composite catalytic material prepared in Example 3;

[0031] Figure 8 SEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 4;

[0032] Figure 9 The linear polarization curve of the nano-carbon-ruthenium-nickel composite catalytic material prepared in Example 4 is shown.

[0033] Figure 10 This is a SEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 5;

[0034] Figure 11 The linear polarization curve of the nano-carbon-ruthenium-nickel composite catalytic material prepared in Example 5 is shown.

[0035] Figure 12 SEM image of the nano-carbon-ruthenium nickel composite catalyst prepared in Example 6;

[0036] Figure 13 The image shows the linear polarization curve of the nano-carbon-ruthenium-nickel composite catalytic material prepared in Example 6. Detailed Implementation

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0038] To address the current technical bottleneck in the atomically precise synthesis of bimetallic catalysts for hydrogen production via water electrolysis, this invention develops a method for the controllable assembly of ruthenium-nickel (RuNi) bimetallic clusters on a functionalized nanocarbon substrate. This method solves the technical problems of existing seawater hydrogen production catalysts, such as low catalytic activity, weak resistance to seawater corrosion, poor long-term cycle stability, and high cost due to the high amount of precious metals used. It also overcomes the susceptibility of catalysts to Cl- in seawater. - Mg 2+ Ca 2+ This method overcomes the performance degradation caused by plasma interference, enabling efficient, stable, and low-cost seawater electrolysis for hydrogen production.

[0039] Specifically, in one embodiment of the present invention, a method for preparing a nano-carbon-ruthenium nickel composite catalytic material is provided, comprising the following steps:

[0040] S1. Add ruthenium salt to the solvent and mix well to obtain solution A with a concentration of 17-107 mg / mL;

[0041] S2. Add the nickel salt to the solvent and mix well to obtain solution B with a concentration of 105-500 mg / mL;

[0042] S3. Add the organic acid to the solvent and mix well to obtain a solution C with a concentration of 50-150 mg / mL;

[0043] S4. Add the nano-carbon to the solvent for dispersion to obtain a mixed solution D with a concentration of 10-100 mg / mL;

[0044] S5. Under continuous stirring, solutions A, B, and C are simultaneously added dropwise to mixture D to react and obtain mixture E, so that ruthenium and nickel are uniformly loaded on the surface of nano-carbon.

[0045] S6. Centrifuge the mixture E to obtain precursor F and remove free impurities;

[0046] S7. After cleaning and vacuum drying the precursor F, nano-carbon-ruthenium nickel composite catalyst material is obtained.

[0047] Preferably, the solvent is an organic solvent or a mixture of water and an organic solvent; the organic solvent is dichloromethane and / or ethylene glycol to ensure the dispersibility of ruthenium salt, nickel salt, and nano-carbon. The volume ratio of solution A, solution B, solution C, and mixture D is (1-5):(1-2):(1-2):(2-3). The ruthenium salt is one or more of ruthenium trichloride, ruthenium acetate, and ruthenium nitrate. The nickel salt is one or more of nickel chloride, nickel nitrate, and nickel acetate. The organic acid is one or more of citric acid, ascorbic acid, and formic acid, which can enhance the coordination bonding of ruthenium, nickel, and the nano-carbon support. The nano-carbon is in powder or substrate-supported form, including one or more of graphene and carbon nanotubes. The cleaning solution used is a mixture of anhydrous ethanol and hydrochloric acid.

[0048] Example 1: This example provides a method for preparing a nano-carbon-ruthenium nickel composite catalytic material, including the following steps:

[0049] S1. Add ruthenium trichloride to ethylene glycol, mix well, and stir magnetically for 10 minutes to dissolve it completely, to obtain solution A with a concentration of 17 mg / mL;

[0050] S2. Add anhydrous nickel chloride to ethylene glycol, mix well, and ultrasonically disperse for 5 minutes to obtain solution B with a concentration of 105 mg / mL;

[0051] S3. Add ascorbic acid to ethylene glycol, mix well, and stir for 15 minutes until completely clear to obtain solution C with a concentration of 50 mg / mL;

[0052] S4. Add the substrate-supported carbon nanotubes to ethylene glycol and ultrasonically disperse for 30 minutes to obtain a mixed solution D with a concentration of 50 mg / mL;

[0053] S5. Under continuous stirring at 300 r / min, 1 mL of solution A, 1 mL of solution B, and 1 mL of solution C are simultaneously added dropwise to 2 mL of mixed solution D through a three-channel funnel at a dropping rate of 1 mL / min to ensure uniform mixing. Then, the mixture is placed in a reaction vessel and the temperature is controlled at 150℃ for 12 h to allow ruthenium and nickel to be uniformly loaded on the surface of nano-carbon, resulting in mixed solution E.

[0054] S6. Transfer the mixture E into a high-speed centrifuge, set the speed to 10,000 rpm and centrifuge for 10 minutes to separate the precursor F and remove free impurities.

[0055] S7. The precursor F is repeatedly washed with a mixture of anhydrous ethanol and hydrochloric acid in a volume ratio of 5:1 to remove residual salts; then it is placed in a vacuum drying oven and dried at 50°C for 2 hours, and then naturally cooled to room temperature to obtain the nano-carbon-ruthenium nickel composite catalyst.

[0056] The nano-carbon-ruthenium-nickel composite catalytic material prepared in Example 1 was characterized by scanning electron microscopy (SEM) and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), as shown below. Figures 1-2 As shown, the results indicate that the prepared nano-carbon-ruthenium-nickel composite catalyst possesses an uneven, porous, and rough surface structure; HAADF-STEM images confirm that RuNi clusters are uniformly loaded on the nano-carbon. Furthermore, the electrolysis performance of the nano-carbon-ruthenium-nickel composite catalyst prepared in Example 1 for hydrogen production from water in an electrolyte of 1 M KOH and 0.5 M NaCl was evaluated. The data were not iR compensated. Figure 3 As shown in the figure, the nano-carbon-ruthenium-nickel composite catalyst exhibits a flux density of 0.846 A·cm⁻¹ at an applied potential of -0.6 V. -2 The current density indicates excellent hydrogen production performance.

[0057] Example 2: This example provides a method for preparing a nano-carbon-ruthenium nickel composite catalytic material, including the following steps:

[0058] S1. Add ruthenium trichloride to ethylene glycol, mix well, and stir magnetically for 10 minutes to fully dissolve it, to obtain solution A with a concentration of 50 mg / mL;

[0059] S2. Add anhydrous nickel chloride to ethylene glycol, mix well, and ultrasonically disperse for 5 minutes to obtain solution B with a concentration of 315 mg / mL;

[0060] S3. Add ascorbic acid to ethylene glycol, mix well, and stir for 15 minutes until completely clear to obtain solution C with a concentration of 100 mg / mL;

[0061] S4. Add the substrate-supported carbon nanotubes to ethylene glycol and ultrasonically disperse for 30 minutes to obtain a mixed solution D with a concentration of 50 mg / mL;

[0062] S5. Under continuous stirring at 300 r / min, 5 mL of solution A, 1 mL of solution B, and 1 mL of solution C are simultaneously added dropwise to 2 mL of mixed solution D through a three-channel funnel at a dropping rate of 1 mL / min to ensure uniform mixing. Then, the mixture is placed in a reaction vessel and the temperature is controlled at 50℃ for 24 h to allow ruthenium and nickel to be uniformly loaded on the surface of nano-carbon, resulting in mixed solution E.

[0063] S6. Transfer the mixture E into a high-speed centrifuge, set the speed to 10,000 rpm and centrifuge for 10 minutes to separate the precursor F and remove free impurities.

[0064] S7. The precursor F is repeatedly washed with a mixture of anhydrous ethanol and hydrochloric acid in a volume ratio of 5:1 to remove residual salts; then it is placed in a vacuum drying oven and dried at 50°C for 2 hours, and then naturally cooled to room temperature to obtain the nano-carbon-ruthenium nickel composite catalyst.

[0065] The high-resolution scanning electron microscope images and linear polarization curves of the nano-carbon-ruthenium-nickel composite catalyst prepared in Example 2 are shown below. Figures 4-5 As shown in the figure, this nano-carbon-ruthenium-nickel composite catalyst exhibits a flux density of 0.870 A·cm⁻¹ at an applied potential of -0.6 V. -2 The current density indicates excellent hydrogen production performance.

[0066] Example 3: This example provides a method for preparing a nano-carbon-ruthenium nickel composite catalytic material, including the following steps:

[0067] S1. Add ruthenium trichloride to ethylene glycol, mix well, and stir magnetically for 10 minutes to dissolve it completely, to obtain solution A with a concentration of 107 mg / mL;

[0068] S2. Add anhydrous nickel chloride to ethylene glycol, mix well, and ultrasonically disperse for 5 minutes to obtain solution B with a concentration of 500 mg / mL;

[0069] S3. Add ascorbic acid to ethylene glycol, mix well, and stir for 15 minutes until completely clear to obtain solution C with a concentration of 120 mg / mL;

[0070] S4. Add the substrate-supported carbon nanotubes to ethylene glycol and ultrasonically disperse for 30 minutes to obtain a mixed solution D with a concentration of 50 mg / mL;

[0071] S5. Under continuous stirring at 300 r / min, 1 mL of solution A, 1 mL of solution B, and 1 mL of solution C are simultaneously added dropwise to 2 mL of mixed solution D through a three-channel funnel at a dropping rate of 1 mL / min to ensure uniform mixing. Then, the mixture is placed in a reaction vessel and the temperature is controlled at 150℃ for 12 h to allow ruthenium and nickel to be uniformly loaded on the surface of nano-carbon, resulting in mixed solution E.

[0072] S6. Transfer the mixture E into a high-speed centrifuge, set the speed to 10,000 rpm and centrifuge for 10 minutes to separate the precursor F and remove free impurities.

[0073] S7. The precursor F is repeatedly washed with a mixture of anhydrous ethanol and hydrochloric acid in a volume ratio of 5:1 to remove residual salts; then it is placed in a vacuum drying oven and dried at 50°C for 2 hours, and then naturally cooled to room temperature to obtain the nano-carbon-ruthenium nickel composite catalyst.

[0074] The high-resolution scanning electron microscope images and linear polarization curves of the nano-carbon-ruthenium-nickel composite catalyst prepared in Example 3 are shown below. Figures 6-7 As shown in the figure, this nano-carbon-ruthenium-nickel composite catalyst exhibits a flux density of 0.866 A·cm⁻¹ at an applied potential of -0.6 V. -2 The current density indicates excellent hydrogen production performance.

[0075] Example 4: This example provides a method for preparing a nano-carbon-ruthenium nickel composite catalytic material, including the following steps:

[0076] S1. Add ruthenium acetate to ethylene glycol, mix well, and stir magnetically for 10 minutes to fully dissolve it, to obtain solution A with a concentration of 17 mg / mL;

[0077] S2. Add nickel acetate to ethylene glycol, mix well, and ultrasonically disperse for 5 minutes to obtain solution B with a concentration of 105 mg / mL;

[0078] S3. Add formic acid to ethylene glycol, mix well, and stir for 15 minutes until completely clear to obtain solution C with a concentration of 50 mg / mL;

[0079] S4. Add the substrate-supported carbon nanotubes to ethylene glycol and ultrasonically disperse for 30 minutes to obtain a mixed solution D with a concentration of 50 mg / mL;

[0080] S5. Under continuous stirring at 300 r / min, 1 mL of solution A, 1 mL of solution B, and 1 mL of solution C are simultaneously added dropwise to 2 mL of mixed solution D through a three-channel funnel at a dropping rate of 1 mL / min to ensure uniform mixing. Then, the mixture is placed in a reaction vessel and the temperature is controlled at 150℃ for 12 h to allow ruthenium and nickel to be uniformly loaded on the surface of nano-carbon, resulting in mixed solution E.

[0081] S6. Transfer the mixture E into a high-speed centrifuge, set the speed to 10,000 rpm and centrifuge for 10 minutes to separate the precursor F and remove free impurities.

[0082] S7. The precursor F is repeatedly washed with a mixture of anhydrous ethanol and hydrochloric acid in a volume ratio of 5:1 to remove residual salts; then it is placed in a vacuum drying oven and dried at 50°C for 2 hours, and then naturally cooled to room temperature to obtain the nano-carbon-ruthenium nickel composite catalyst.

[0083] The high-resolution scanning electron microscope images and linear polarization curves of the nano-carbon-ruthenium-nickel composite catalyst prepared in Example 4 are shown below. Figures 8-9 As shown in the figure, this nano-carbon-ruthenium-nickel composite catalyst exhibits a flux density of 0.883 A·cm⁻¹ at an applied potential of -0.6 V. -2 The current density indicates excellent hydrogen production performance.

[0084] Example 5: This example provides a method for preparing a nano-carbon-ruthenium nickel composite catalytic material, including the following steps:

[0085] S1. Add ruthenium trichloride to ethylene glycol, mix well, and stir magnetically for 10 minutes to dissolve it completely, to obtain solution A with a concentration of 30 mg / mL;

[0086] S2. Add anhydrous nickel chloride to ethylene glycol, mix well, and ultrasonically disperse for 5 minutes to obtain solution B with a concentration of 200 mg / mL;

[0087] S3. Add ascorbic acid to ethylene glycol, mix well, and stir for 15 minutes until completely clear to obtain solution C with a concentration of 150 mg / mL;

[0088] S4. Add the substrate-supported carbon nanotubes to ethylene glycol and ultrasonically disperse for 30 minutes to obtain a mixed solution D with a concentration of 50 mg / mL;

[0089] S5. Under continuous stirring at 300 r / min, 3 mL of solution A, 2 mL of solution B, and 2 mL of solution C are simultaneously added dropwise to 3 mL of mixed solution D through a three-channel funnel at a dropping rate of 1 mL / min to ensure uniform mixing. Then, the mixture is placed in a reaction vessel and the temperature is controlled at 120℃ for 18 h to allow ruthenium and nickel to be uniformly loaded on the surface of nano-carbon, resulting in mixed solution E.

[0090] S6. Transfer the mixture E into a high-speed centrifuge, set the speed to 10,000 rpm and centrifuge for 10 minutes to separate the precursor F and remove free impurities.

[0091] S7. The precursor F is repeatedly washed with a mixture of anhydrous ethanol and hydrochloric acid in a volume ratio of 5:1 to remove residual salts; then it is placed in a vacuum drying oven and dried at 50°C for 3 hours, and then naturally cooled to room temperature to obtain the nano-carbon-ruthenium nickel composite catalyst.

[0092] The high-resolution scanning electron microscope images and linear polarization curves of the nano-carbon-ruthenium-nickel composite catalyst prepared in Example 5 are shown below. Figures 10-11 As shown in the figure, this nano-carbon-ruthenium-nickel composite catalyst exhibits a flux density of 0.883 A·cm⁻¹ at an applied potential of -0.6 V. -2 The current density indicates excellent hydrogen production performance.

[0093] Example 6: This example provides a method for preparing a nano-carbon-ruthenium nickel composite catalytic material, including the following steps:

[0094] S1. Add ruthenium nitrate to ethylene glycol, mix well, and stir magnetically for 10 minutes to fully dissolve it, to obtain solution A with a concentration of 25 mg / mL;

[0095] S2. Add nickel nitrate to ethylene glycol, mix well, and sonicate for 5 minutes to obtain solution B with a concentration of 180 mg / mL;

[0096] S3. Add citric acid to ethylene glycol, mix well, and stir for 15 minutes until completely clear to obtain solution C with a concentration of 50 mg / mL;

[0097] S4. Add the substrate-supported carbon nanotubes to ethylene glycol and ultrasonically disperse for 30 minutes to obtain a mixed solution D with a concentration of 50 mg / mL;

[0098] S5. Under continuous stirring at 300 r / min, 2 mL of solution A, 1 mL of solution B, and 1 mL of solution C are simultaneously added dropwise to 2 mL of mixed solution D through a three-channel funnel at a dropping rate of 1 mL / min to ensure uniform mixing. Then, the mixture is placed in a reaction vessel and the temperature is controlled at 100℃ for 30 h to allow ruthenium and nickel to be uniformly loaded on the surface of nano-carbon, resulting in mixed solution E.

[0099] S6. Transfer the mixture E into a high-speed centrifuge, set the speed to 10,000 rpm and centrifuge for 10 minutes to separate the precursor F and remove free impurities.

[0100] S7. The precursor F is repeatedly washed with a mixture of anhydrous ethanol and hydrochloric acid in a volume ratio of 5:1 to remove residual salts; then it is placed in a vacuum drying oven and dried at 50°C for 3 hours, and then naturally cooled to room temperature to obtain the nano-carbon-ruthenium nickel composite catalyst.

[0101] The high-resolution scanning electron microscope images and linear polarization curves of the nano-carbon-ruthenium-nickel composite catalyst prepared in Example 6 are shown below. Figures 12-13 As shown in the figure, this nano-carbon-ruthenium-nickel composite catalyst exhibits a flux density of 0.870 A·cm⁻¹ at an applied potential of -0.6 V. -2 The current density indicates excellent hydrogen production performance.

[0102] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification.

Claims

1. A method for preparing a nano-carbon-ruthenium-nickel composite catalytic material, characterized in that, Includes the following steps: Add ruthenium salt to the solvent and mix well to obtain solution A; Add the nickel salt to the solvent and mix thoroughly to obtain solution B; The organic acid is added to the solvent and mixed thoroughly to obtain solution C; Nano-carbon was added to a solvent for dispersion to obtain mixture D; Under continuous stirring, solutions A, B, and C are simultaneously added dropwise to mixture D to react and obtain mixture E; The mixture E was centrifuged to obtain precursor F; After cleaning and vacuum drying the precursor F, nano-carbon-ruthenium nickel composite catalyst material was obtained.

2. The preparation method of the nano-carbon-ruthenium nickel composite catalytic material according to claim 1, characterized in that, The solvent is an organic solvent or a mixture of water and an organic solvent; the organic solvent is dichloromethane and / or ethylene glycol.

3. The preparation method of the nano-carbon-ruthenium nickel composite catalytic material according to claim 1, characterized in that, The concentration of ruthenium salt in solution A is 17-107 mg / mL; the concentration of nickel salt in solution B is 105-500 mg / mL; the concentration of organic acid in solution C is 50-150 mg / mL; and the concentration of nano-carbon in mixture D is 10-100 mg / mL.

4. The preparation method of the nano-carbon-ruthenium nickel composite catalytic material according to claim 3, characterized in that, The volume ratio of solution A, solution B, solution C and mixture D is (1-5):(1-2):(1-2):(2-3).

5. The preparation method of the nano-carbon-ruthenium nickel composite catalytic material according to claim 1, characterized in that, The ruthenium salt is one or more of ruthenium trichloride, ruthenium acetate, and ruthenium nitrate.

6. The preparation method of the nano-carbon-ruthenium nickel composite catalytic material according to claim 1, characterized in that, The nickel salt is one or more of nickel chloride, nickel nitrate, and nickel acetate.

7. The method for preparing the nano-carbon-ruthenium nickel composite catalytic material according to claim 1, characterized in that, The organic acid is one or more of citric acid, ascorbic acid, and formic acid.

8. The method for preparing the nano-carbon-ruthenium nickel composite catalytic material according to claim 1, characterized in that, The nano-carbon is in the form of powder or substrate supported, including one or more of graphene and carbon nanotubes.

9. A nano-carbon-ruthenium-nickel composite catalytic material prepared by any one of the preparation methods described in claims 1-8.

10. The application of the nano-carbon-ruthenium-nickel composite catalytic material as described in claim 9 in hydrogen production by water electrolysis.

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