Ruthenium-doped inverse perovskite nitride nanosheets and their use as water electrolysis catalysts
By loading ruthenium-doped anti-perovskite nitride nanosheets onto a nickel foam support, the problem of slow hydrogen evolution kinetics in water electrolysis was solved, achieving efficient and low-energy-consumption hydrogen production through water electrolysis.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-23
- Publication Date
- 2026-06-16
AI Technical Summary
In existing water electrolysis technologies, the hydrogen evolution reaction at the cathode and the oxygen evolution reaction at the anode are slow, resulting in high overpotentials and high electricity costs, which limits the widespread application of water electrolysis for hydrogen production.
Ruthenium-doped anti-perovskite nitride nanosheets were used as a catalyst for water electrolysis. By loading ruthenium-doped anti-perovskite nitride CuNCo3 onto a nickel foam support, the electronic structure was modulated and active sites were increased, thereby optimizing the material's conductivity and mass transfer process.
It significantly reduces the overpotential for hydrogen evolution in water electrolysis, improves electrocatalytic activity, and reduces energy consumption. It is superior to commercial Pt/C catalysts and is suitable for high-current industrial electrolysis scenarios.
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Figure CN122214913A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to ruthenium-doped anti-perovskite nitride nanosheets and their application as a catalyst for water electrolysis, belonging to the field of water electrolysis catalysis technology. Background Technology
[0002] Water electrolysis involves two half-cell reactions: the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode. During the electrolysis process, water at the cathode undergoes reduction to produce hydrogen, while water at the anode undergoes oxidation to produce oxygen. The OER reaction at the anode is a multi-step, four-electron process. Because the HER and OER reactions are kinetic and require significant overpotentials to maintain their operation, the high electricity costs prevent the widespread application of water electrolysis technology. Therefore, developing efficient, stable, and hydrogen-evolving electrocatalysts is of great significance for the promotion of hydrogen production through water electrolysis.
[0003] Noble metals are considered state-of-the-art catalysts for HER or OER due to their high catalytic activity; however, their scarcity and high cost limit their industrial application in the electrochemical splitting of water. Ruthenium, among noble metals, possesses electronic properties similar to platinum, but at only one-fifth the cost, offering a potential solution for improving the efficiency of electrocatalytic reactions. Summary of the Invention
[0004] In view of the above-mentioned prior art, the present invention provides a ruthenium-doped anti-perovskite nitride nanosheet and its application as a catalyst for water electrolysis.
[0005] This invention is achieved through the following technical solution: A ruthenium-doped anti-perovskite nitride nanosheet is composed of a support and ruthenium-doped anti-perovskite nitride loaded on the support. The support is nickel foam, and the structure of the anti-perovskite nitride is CuNCo3. The loading amount of the ruthenium-doped anti-perovskite nitride is 2-5%, preferably 3.64%, and the doping amount of ruthenium in the anti-perovskite nitride is 1-3%, preferably 1.61%.
[0006] The preparation method of the ruthenium-doped anti-perovskite nitride nanosheets includes the following steps: (1) Place the nickel foam in the initial mixed solution and react at 100-150°C for 10-15 hours; wash and dry the reaction product to obtain the copper-cobalt bimetallic hydroxide (CoCu-LDH) nanosheet precursor. The initial mixed solution is composed of cobalt salt, copper salt, urea and water. (2) The copper-cobalt bimetallic hydroxide nanosheet precursor was placed in a ruthenium trichloride solution with a concentration of 0.5-2.5 mg / mL and soaked for 1-6 hours; then removed, washed and dried to obtain ruthenium-doped copper-cobalt bimetallic hydroxide (Ru-CoCu-LDH) nanosheet precursor; (3) The ruthenium-doped copper-cobalt bimetallic hydroxide nanosheet precursor is heated to 400-450°C (preferably 420°C) and kept at the temperature for 2-3 hours under an ammonia atmosphere to perform nitriding treatment, thereby obtaining ruthenium-doped anti-perovskite nitride nanosheets, wherein the structure of the anti-perovskite nitride is CuNCo3.
[0007] Furthermore, in step (1), the nickel foam is pretreated to remove surface oxides and oil stains. The pretreatment method is as follows: ultrasonic cleaning with hydrochloric acid, deionized water and ethanol in sequence, followed by vacuum drying.
[0008] Furthermore, in step (1), the cobalt salt is selected from cobalt nitrate; the copper salt is selected from copper nitrate.
[0009] Further, in step (1), the concentration of cobalt salt is 0.051 mol / L, the concentration of copper salt is 0.017 mol / L, and the concentration of urea is 0.221 mol / L.
[0010] Applications of the ruthenium-doped anti-perovskite nitride nanosheets in the preparation of water electrolysis catalysts, applications in water electrolysis catalysis, and applications in hydrogen evolution through water electrolysis.
[0011] Furthermore, in specific applications, the water electrolysis catalytic device includes an anode electrode, a cathode electrode, and an electrolyte. The cathode electrode is a ruthenium-doped anti-perovskite nitride nanosheet, the cathode electrode is a copper-cobalt bimetallic hydroxide nanosheet precursor, and the electrolyte is a KOH solution.
[0012] Furthermore, in specific applications, the water electrolysis hydrogen production device includes a working electrode, a reference electrode, a counter electrode, and an electrolyte. The working electrode is a ruthenium-doped anti-perovskite nitride nanosheet, the reference electrode is an Ag / AgCl electrode, the counter electrode is a carbon rod, and the electrolyte is a KOH solution.
[0013] The ruthenium-doped anti-perovskite nitride nanosheets of the present invention incorporate the noble metal ruthenium into the anti-perovskite nitride CuNCo3. By adjusting the amount of ruthenium doping, the electronic structure of the anti-perovskite nitride can be effectively controlled, optimizing the conductivity of the material and increasing the number of available active sites. Furthermore, the addition of ruthenium microscopically affects the morphology of the material, giving it a larger contact area with the electrolyte, accelerating the mass transfer process, and effectively improving electrocatalytic activity. When used as a catalyst, it can greatly reduce the energy consumption of water electrolysis. Attached Figure Description
[0014] Figure 1 Scanning electron microscope image of ruthenium-doped anti-perovskite nitride nanosheets.
[0015] Figure 2 Transmission electron microscopy image of ruthenium-doped anti-perovskite nitride nanosheets.
[0016] Figure 3 Linear voltammetric curves of hydrogen evolution reaction in water electrolysis of ruthenium-doped anti-perovskite nitride nanosheets.
[0017] Figure 4 Linear voltammetric curves of the total hydrolysis reaction of ruthenium-doped anti-perovskite nitride nanosheets. Detailed Implementation
[0018] The present invention will be further described below with reference to embodiments. However, the scope of the present invention is not limited to the following embodiments. Those skilled in the art will understand that various changes and modifications can be made to the present invention without departing from the spirit and scope thereof.
[0019] Unless otherwise specified, the instruments, reagents, and materials used in the following embodiments are all conventional instruments, reagents, and materials already available in the prior art and can be obtained through legitimate commercial channels. Unless otherwise specified, the experimental methods and detection methods used in the following embodiments are all conventional experimental methods and detection methods already available in the prior art.
[0020] Example 1: Preparation of Ruthenium-doped anti-perovskite nitride nanosheets The steps are as follows: (1) The nickel foam (2 cm × 4 cm) was pretreated to remove surface oxides and oil stains. The pretreatment method was as follows: ultrasonic cleaning with hydrochloric acid (concentration 3.0 mol / L), deionized water and ethanol in sequence, with a cleaning time of 15 minutes / time; and then placed in a vacuum drying oven and vacuum dried at 60℃ for 8 hours.
[0021] (2) Dissolve 0.873 g cobalt nitrate hexahydrate, 0.296 g copper nitrate hexahydrate and 0.9 g urea in 35 ml of deionized water and stir magnetically until fully mixed to obtain the initial mixed solution.
[0022] (3) The pretreated nickel foam was placed in the initial mixed solution and transferred to a polytetrafluoroethylene reactor. The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction product was washed three times with deionized water and then three times with ethanol. It was then dried in a vacuum drying oven for 6 hours to obtain the CoCu-LDH nanosheet precursor (size 2 cm × 4 cm, mass 164 mg).
[0023] (4) Dissolve 0.02 g RuCl3·3H2O in 10 mL of deionized water and stir for 10 min to obtain a ruthenium trichloride solution. Place the CoCu-LDH nanosheet precursor in the ruthenium trichloride solution and soak at room temperature for 3 hours. Remove it, wash it 3 times with deionized water, then wash it 3 times with ethanol, and dry it in a vacuum drying oven for 6 hours to obtain the Ru-CoCu-LDH nanosheet precursor.
[0024] (5) The Ru-CoCu-LDH nanosheet precursor was placed in a quartz tube and placed in a muffle furnace. It was heated to 420°C at a rate of 5°C / min under an argon atmosphere, and then switched to an ammonia atmosphere and held at that temperature for 2 hours for nitriding treatment. The reaction product was washed three times with deionized water and then three times with ethanol. It was then dried in a vacuum drying oven for 6 hours to obtain ruthenium-doped anti-perovskite nitride nanosheets (2 cm × 4 cm), i.e., Ru-CuNCo3 nanosheets. The mass of Ru-CuNCo3 nanosheets was 170.2 mg, the mass of ruthenium-doped anti-perovskite nitride was 6.2 mg, and the mass of ruthenium was 0.1 mg. That is, the loading of ruthenium-doped anti-perovskite nitride was 3.64%, and the doping amount of ruthenium in anti-perovskite nitride was 1.61%.
[0025] Scanning electron microscope image of ruthenium-doped anti-perovskite nitride nanosheets as shown below Figure 1 As shown, the transmission electron microscope image of ruthenium-doped anti-perovskite nitride nanosheets is as follows. Figure 2 As shown. From Figure 1 Its microstructure can be observed to be: nanosheets with a thickness of 3–15 nm, stacked in a petal-like shape, exhibiting a petal-shaped mesoporous heterostructure nanosheet morphology. From Figure 2 As can be seen, its surface is uniformly distributed with many mesopores with an average diameter of about 4 nm.
[0026] Experiment 1 Catalytic activity of ruthenium-doped anti-perovskite nitride nanosheets The catalytic activity of ruthenium-doped anti-perovskite nitride nanosheets in the hydrogen evolution reaction of water electrolysis was tested using a three-electrode system. The apparatus for hydrogen production by water electrolysis included a working electrode, a reference electrode, a counter electrode, and an electrolyte. The working electrode was ruthenium-doped anti-perovskite nitride nanosheets (prepared in Example 1), and five experimental groups were set up with the following mass values of ruthenium-doped anti-perovskite nitride nanosheets: 0.01 g, 0.015 g, 0.02 g, 0.025 g, and 0.03 g, respectively. The reference electrode was an Hg / HgO electrode, the counter electrode was a graphite rod, and the electrolyte was a 1 M KOH solution.
[0027] The linear voltammetric curve of the hydrogen evolution reaction in water electrolysis is as follows: Figure 3 As shown, during the electrolysis of water to produce hydrogen, at 10 mA·cm⁻¹ -2At the specified current density, the hydrogen evolution overpotential is only 23 mV. Compared with the commercial Pt / C catalyst (30 mV), this represents a reduction of 7 mV, and the overpotential optimization improves by 23.33%. This indicates that the ruthenium-doped anti-perovskite nitride nanosheets of this invention possess excellent water electrolysis catalytic performance, significantly superior to that of commercial Pt / C catalysts.
[0028] Experiment 2: Catalytic activity of ruthenium-doped anti-perovskite nitride nanosheets for total hydrolysis The catalytic activity of ruthenium-doped anti-perovskite nitride nanosheets for total hydrolysis was tested using a dual-electrode system. Five experimental groups were set up with ruthenium-doped anti-perovskite nitride nanosheets (prepared in Example 1) as the cathode electrode, and the masses of ruthenium-doped anti-perovskite nitride nanosheets were 0.01 g, 0.015 g, 0.02 g, 0.025 g, and 0.03 g, respectively. Cobalt-copper bimetallic hydroxide nanosheet precursor (prepared in Example 1) was used as the anode electrode, Ag / AgCl electrode was used as the reference electrode, and 1M KOH solution was used as the electrolyte.
[0029] The linear voltammetric curve of the total hydrolysis reaction is as follows: Figure 4 As shown, compared to commercial Pt / C catalysts, the Tafel slope is optimized by approximately 27%–33%, indicating that the hydrogen evolution reaction kinetics of the ruthenium-doped anti-perovskite nitride nanosheets of this invention are far superior to those of commercial Pt / C catalysts. The additional overpotential required for increasing current density is significantly reduced, making it more suitable for high-current industrial electrolysis scenarios.
[0030] Example 2: Preparation of Ruthenium-doped anti-perovskite nitride nanosheets The steps are as follows: (1) Dissolve 0.01 g RuCl3·3H2O in 10 mL of deionized water and stir for 10 min to obtain a ruthenium trichloride solution. Place the CoCu-LDH nanosheet precursor (prepared in Example 1) in the ruthenium trichloride solution and soak at room temperature for 5 hours. Remove it, wash it 3 times with deionized water, then wash it 3 times with ethanol, and dry it in a vacuum drying oven for 6 hours to obtain the Ru-CoCu-LDH nanosheet precursor.
[0031] (2) The Ru-CoCu-LDH nanosheet precursor was placed in a quartz tube and placed in a muffle furnace. It was heated to 420°C at a rate of 5°C / min under an argon atmosphere, and then switched to an ammonia atmosphere and kept at the temperature for 2 hours for nitriding treatment. The reaction product was washed three times with deionized water and then three times with ethanol. It was then dried in a vacuum drying oven for 6 hours to obtain ruthenium-doped anti-perovskite nitride nanosheets.
[0032] Example 3: Preparation of Ruthenium-doped anti-perovskite nitride nanosheets The steps are as follows: (1) Dissolve 0.02 g RuCl3·3H2O in 10 mL of deionized water and stir for 10 min to obtain a ruthenium trichloride solution. Place the CoCu-LDH nanosheet precursor (prepared in Example 1) in the ruthenium trichloride solution and soak at room temperature for 4 hours. Remove it, wash it 3 times with deionized water, then wash it 3 times with ethanol, and dry it in a vacuum drying oven for 6 hours to obtain the Ru-CoCu-LDH nanosheet precursor.
[0033] (2) The Ru-CoCu-LDH nanosheet precursor was placed in a quartz tube and placed in a muffle furnace. It was heated to 420°C at a rate of 5°C / min under an argon atmosphere, and then switched to an ammonia atmosphere and kept at the temperature for 2 hours for nitriding treatment. The reaction product was washed three times with deionized water and then three times with ethanol. It was then dried in a vacuum drying oven for 6 hours to obtain ruthenium-doped anti-perovskite nitride nanosheets.
[0034] Example 4: Preparation of Ruthenium-doped anti-perovskite nitride nanosheets The steps are as follows: (1) Dissolve 0.01 g RuCl3·3H2O in 10 mL of deionized water and stir for 10 min to obtain a ruthenium trichloride solution. Place the CoCu-LDH nanosheet precursor (prepared in Example 1) in the ruthenium trichloride solution and soak it at room temperature for 5 hours. Take it out, wash it 3 times with deionized water, then wash it 3 times with ethanol, and dry it in a vacuum drying oven for 6 hours to obtain the Ru-CoCu-LDH nanosheet precursor.
[0035] (2) The Ru-CoCu-LDH nanosheet precursor was placed in a quartz tube and placed in a muffle furnace. It was heated to 420°C at a rate of 5°C / min under an argon atmosphere, and then switched to an ammonia atmosphere and kept at the temperature for 2 hours for nitriding treatment. The reaction product was washed three times with deionized water and then three times with ethanol. It was then dried in a vacuum drying oven for 6 hours to obtain ruthenium-doped anti-perovskite nitride nanosheets.
[0036] The above embodiments are provided to those skilled in the art to fully disclose and describe how the claimed implementations can be carried out and used, and are not intended to limit the scope of the disclosure herein. Modifications that will be obvious to those skilled in the art will be within the scope of the appended claims.
Claims
1. A ruthenium-doped anti-perovskite nitride nanosheet, characterized in that: It is composed of a support and a ruthenium-doped anti-perovskite nitride loaded on the support. The support is nickel foam, the structure of the anti-perovskite nitride is CuNCo3, the loading amount of the ruthenium-doped anti-perovskite nitride is 2-5%, and the doping amount of ruthenium in the anti-perovskite nitride is 1-3%.
2. The ruthenium-doped anti-perovskite nitride nanosheet according to claim 1, characterized in that, It is prepared by the following method: (1) Place the nickel foam in the initial mixed solution and react at 100-150°C for 10-15 hours; wash and dry the reaction product to obtain the copper-cobalt bimetallic hydroxide nanosheet precursor; the initial mixed solution is composed of cobalt salt, copper salt, urea and water; (2) The copper-cobalt bimetallic hydroxide nanosheet precursor was placed in a ruthenium trichloride solution with a concentration of 0.5–2.5 mg / mL and soaked for 1–6 hours; then removed, washed, and dried to obtain the ruthenium-doped copper-cobalt bimetallic hydroxide nanosheet precursor. (3) The ruthenium-doped copper-cobalt bimetallic hydroxide nanosheet precursor is heated to 400-450°C and kept at the temperature for 2-3 hours under an ammonia atmosphere to perform nitriding treatment to obtain ruthenium-doped anti-perovskite nitride nanosheets, wherein the structure of the anti-perovskite nitride is CuNCo3.
3. The ruthenium-doped anti-perovskite nitride nanosheet according to claim 2, characterized in that: In step (1), the nickel foam is pretreated by sequentially ultrasonically cleaning with hydrochloric acid, deionized water, and ethanol, followed by vacuum drying.
4. The ruthenium-doped anti-perovskite nitride nanosheet according to claim 2, characterized in that: In step (1), the cobalt salt is selected from cobalt nitrate; the copper salt is selected from copper nitrate.
5. The ruthenium-doped anti-perovskite nitride nanosheet according to claim 2, characterized in that: In step (1), the concentration of cobalt salt is 0.051 mol / L, the concentration of copper salt is 0.017 mol / L, and the concentration of urea is 0.221 mol / L.
6. The ruthenium-doped anti-perovskite nitride nanosheet according to claim 1, characterized in that: The ruthenium-doped anti-perovskite nitride has a loading of 3.64%, and the doping amount of ruthenium in the anti-perovskite nitride is 1.61%.
7. The method for preparing ruthenium-doped anti-perovskite nitride nanosheets according to any one of claims 1 to 6, characterized in that, Includes the following steps: (1) Place the nickel foam in the initial mixed solution and react at 100-150°C for 10-15 hours; wash and dry the reaction product to obtain the copper-cobalt bimetallic hydroxide nanosheet precursor; the initial mixed solution is composed of cobalt salt, copper salt, urea and water; (2) The copper-cobalt bimetallic hydroxide nanosheet precursor was placed in a ruthenium trichloride solution with a concentration of 0.5–2.5 mg / mL and soaked for 1–6 hours; then removed, washed, and dried to obtain the ruthenium-doped copper-cobalt bimetallic hydroxide nanosheet precursor. (3) The ruthenium-doped copper-cobalt bimetallic hydroxide nanosheet precursor is heated to 400-450°C and kept at the temperature for 2-3 hours under an ammonia atmosphere to perform nitriding treatment to obtain ruthenium-doped anti-perovskite nitride nanosheets, wherein the structure of the anti-perovskite nitride is CuNCo3.
8. The use of the ruthenium-doped anti-perovskite nitride nanosheets according to any one of claims 1 to 6 in the preparation of a water electrolysis catalyst, or in the catalysis of water electrolysis, or in the hydrogen evolution process of water electrolysis.
9. The application according to claim 8, characterized in that: In practical applications, the water electrolysis catalytic device includes an anode electrode, a cathode electrode, and an electrolyte. The cathode electrode is a ruthenium-doped anti-perovskite nitride nanosheet, the cathode electrode is a copper-cobalt bimetallic hydroxide nanosheet precursor, and the electrolyte is a KOH solution.
10. The application according to claim 8, characterized in that: In practical applications, the water electrolysis hydrogen production device includes a working electrode, a reference electrode, a counter electrode, and an electrolyte. The working electrode is a ruthenium-doped anti-perovskite nitride nanosheet, the reference electrode is an Ag / AgCl electrode, the counter electrode is a carbon rod, and the electrolyte is a KOH solution.