A method for preparing a ruthenium-doped transition metal carbide nano-catalyst based on Ru catalytic carbonization and its application
Patent Information
- Application Number
- CN202611052785.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-15
- Publication Date
- 2026-08-28
AI Technical Summary
然而，传统碳化方法通常需要高温处理，易导致纳米颗粒团聚、活性位点减少以及结构不可控等问题，从而影响催化性能
本发明提供了一种基于Ru催化碳化辅助制备钌掺杂过渡金属碳化物纳米催化剂的方法及其应用，通过构建含Ru的过渡金属有机框架（MOFs）前驱体，在惰性气氛下进行热处理，利用Ru在碳化过程中的催化作用，提高碳化效率并改善材料结构，实现碳化过程的协同调控，从而获得结构稳定、分散性良好、导电性优异的钌掺杂过渡金属碳化物材料。本发明具有原料廉价易得、制备工艺简单、可控性强等优点。本发明所得催化剂在高电流密度条件下电解水析氢反应中表现出优异的催化活性和电化学稳定性，具有良好的工业应用前景。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrocatalytic materials and energy conversion technology, and provides a method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru catalytic carbonization and its application. Background Technology
[0002] With the continued depletion of fossil fuels and the increasing prominence of environmental problems, the development of clean and efficient energy conversion technologies has become a research hotspot. Hydrogen energy, as a clean energy carrier, has advantages such as high energy density and environmental friendliness. Among these, water electrolysis for hydrogen production is considered an important pathway to achieving green hydrogen production.
[0003] In the hydrogen evolution reaction (HER) of water electrolysis, the performance of the catalyst directly determines the reaction efficiency. Although noble metal catalysts (such as Pt) have excellent activity, their high cost limits their large-scale application. Therefore, the development of low-cost, high-performance non-noble metal catalysts is of great significance.
[0004] Transition metal carbides are considered potential alternative materials due to their electronic structure similar to that of noble metals. However, traditional carbonization methods typically require high-temperature processing, which can lead to problems such as nanoparticle aggregation, reduction of active sites, and uncontrollable structure, thereby affecting catalytic performance.
[0005] Therefore, it is of great significance to develop a low-temperature controllable, structurally stable carbonization method that can suppress agglomeration. Summary of the Invention
[0006] In view of this, the purpose of this invention is to provide a method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization and its application.
[0007] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve the transition metal salt, ruthenium salt and organic ligand in a mixed solvent to form a homogeneous solution; (2) Then add an organic base to the solution, stir to react, and obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heat-treated under inert gas protection and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0008] Preferably, in step (1), the transition metal salt is selected from any one or more salts of Ni, Co, and Fe; the ruthenium salt is ruthenium trichloride; and the organic ligand is selected from any one or more of terephthalic acid, phthalic acid, p-hydroxyterephthalic acid, or 4,4'-biphenyl.
[0009] Preferably, in steps (1) and (2), the ratio of transition metal salt, ruthenium salt, organic ligand, mixed solvent, and organic base is 0.5–1.5 mmol: 0.01–0.05 mmol: 0.3–1 mmol: 16–55 mL: 1–5 mL; the mixed solvent is obtained by mixing N,N'-dimethylformamide (DMF) and deionized water in a volume ratio of 15–50: 1–5; the organic base is triethylamine or tetramethylammonium hydroxide.
[0010] Preferably, in step (2), the stirring reaction conditions are: stirring reaction at room temperature for 2 to 6 hours.
[0011] Preferably, in step (4), the inert gas is argon or nitrogen.
[0012] Preferably, in step (4), the heat treatment conditions are: heating to 400-800℃ at 2-5℃ / min and holding for 2-4 hours.
[0013] A ruthenium-doped transition metal carbide nanocatalyst was prepared by the aforementioned method.
[0014] The aforementioned application of a ruthenium-doped transition metal carbide nanocatalyst in the hydrogen evolution reaction of water electrolysis.
[0015] Preferably, the hydrogen evolution reaction of water electrolysis is carried out at a current density ≥ 500 mA / cm². 2 Under the conditions.
[0016] The beneficial effects of this invention are: This invention provides a method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization and its application. By constructing a Ru-containing transition metal-organic framework (MOF) precursor and performing heat treatment under an inert atmosphere, the catalytic effect of Ru during carbonization is utilized to improve carbonization efficiency and material structure, achieving synergistic regulation of the carbonization process. This results in ruthenium-doped transition metal carbide materials with stable structure, good dispersibility, and excellent conductivity. This invention has advantages such as inexpensive and readily available raw materials, simple preparation process, and strong controllability. The catalyst obtained by this invention exhibits excellent catalytic activity and electrochemical stability in the hydrogen evolution reaction of water electrolysis under high current density conditions, showing promising prospects for industrial application.
[0017] This invention has the following advantages: (1) Lowering the carbonization temperature: Ru plays a catalytic role in the pyrolysis process, which lowers the energy barrier of the carbonization reaction; (2) Inhibit particle aggregation: effectively maintain the nanostructure and increase the specific surface area; (3) Controllable structure: It can form a core-shell structure or a multi-level structure; (4) Improved conductivity: enhances electron transport capability; (5) Excellent high current performance: It remains stable even under industrial-grade current density conditions; (6) The method is universal: it is applicable to a variety of systems such as Ni, Fe, and Co.
[0018] Other advantages, objectives, and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination, or may be learned from practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Attached Figure Description
[0019] To make the objectives, technical solutions, and advantages of the present invention clearer, the preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein: Figure 1 The thermogravimetric (TGA) curves of the ruthenium-doped metal framework in reference control group 1 and the non-ruthenium-doped metal framework in reference control group 2 are shown.
[0020] Figure 2 The X-ray diffraction patterns of the ruthenium-doped metal-organic frameworks in reference control group 1 and the non-ruthenium-doped metal-organic frameworks in reference control group 2 are obtained at 350 °C.
[0021] Figure 3 The Raman spectra of the ruthenium-doped metal-organic frameworks in reference control group 1 and the non-ruthenium-doped metal-organic frameworks in reference control group 2 were obtained at 350 °C.
[0022] Figure 4 The transmission electron microscope (TEM) image of the sample obtained at 350 °C for reference control group 2, which is a non-ruthenium-doped metal-organic framework.
[0023] Figure 5 The transmission electron microscope (TEM) image of the ruthenium-doped metal-organic framework sample obtained at 350 °C is shown in reference control group 1.
[0024] Figure 6 The X-ray diffraction patterns of the ruthenium-doped and reference control group 3 non-ruthenium-doped metal-organic frameworks obtained at 400 °C in Example 1 are shown.
[0025] Figure 7 The images shown are field emission electron microscope (FET) and aberration transmission scanning electron microscope (SEM) images of the ruthenium-doped metal-organic framework sample obtained at 400 °C in Example 1.
[0026] Figure 8 The figures show the hydrogen evolution performance of the ruthenium-doped nickel catalyst Ru&Ni obtained in Example 1 at 400 °C and the ruthenium-doped nickel catalyst Ru&Ni obtained in Comparative Example 4 at 350 °C in 1M KOH.
[0027] Figure 9 The image shows the long-term stability of the ruthenium-doped nickel carbide / nickel core-shell catalyst obtained from the ruthenium-doped metal-organic framework in Example 1 at 400 °C in an anion exchange membrane electrolyzer.
[0028] Figure 10 The graph shows the hydrogen evolution performance of the ruthenium-doped iron catalyst obtained by the ruthenium-doped metal-organic framework in Example 2 at 600 °C in 1M KOH.
[0029] Figure 11 The graph shows the hydrogen evolution performance of the ruthenium-doped nickel catalyst obtained in Example 3 at 400 °C in 1M KOH.
[0030] Figure 12 The graph shows the hydrogen evolution performance of the ruthenium-doped nickel catalyst obtained in Example 4 at 800 °C in 1M KOH.
[0031] Figure 13 The graph shows the hydrogen evolution performance of the ruthenium-nickel catalyst obtained by the reduction method of activated carbon supported on ruthenium-nickel metal at 400 °C in 1M KOH.
[0032] Figure 14 The graph shows the hydrogen evolution performance of the platinum-doped nickel catalyst obtained by the platinum-doped metal-organic framework in Comparative Example 2 at 400 °C in 1M KOH.
[0033] Figure 15 The figure shows the hydrogen evolution performance of the ruthenium-doped nickel catalyst obtained in Comparative Example 3 at 800 °C in 1M KOH. Detailed Implementation
[0034] The present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that the following description is only for explaining the present invention and does not limit its content.
[0035] Example 1
[0036] A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and terephthalic acid (150 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add triethylamine (1 mL) to the solution and stir at room temperature for 3 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 400°C at 2°C / min under nitrogen protection. It is held for 2 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0037] Reference control group 1 Ruthenium-doped metal frameworks were prepared at 350 °C according to the method in Example 1, except that in step (4), the temperature was raised to 350 °C and held.
[0038] Reference control group 2 The non-ruthenium-doped metal framework was prepared according to the method of Example 1 at 350°C, except that ruthenium trichloride was omitted and step (4) was heated to 350°C and held at that temperature.
[0039] Reference control group 3 A non-ruthenium-doped metal framework was prepared at 400°C according to the method in Example 1, except that ruthenium trichloride was omitted.
[0040] Figure 1 The thermogravimetric (TGA) curves are shown for the ruthenium-doped metal framework in reference control group 1 and the unruthenium-doped metal framework in reference control group 2. Figure 1 It can be seen that the introduction of ruthenium significantly advanced the weight loss curve, proving that ruthenium played a catalytic role in the carbonization process.
[0041] Figure 2 X-ray diffraction patterns of ruthenium-doped metal-organic frameworks (reference control group 1) and non-ruthenium-doped metal-organic frameworks (reference control group 2) obtained at 350 °C are shown. Figure 2 It can be seen that both organic frameworks first form a homogeneous nickel carbide phase at low temperatures.
[0042] Figure 3 Raman spectra of ruthenium-doped metal-organic frameworks (MOFs) from reference control group 1 and non-ruthenium-doped MFOs from reference control group 2, obtained at 350 °C. Figure 3 It can be seen that a graphitic carbon layer has been formed on the surface of Ru and Ni at 350 °C, proving the catalytic carbonization effect of ruthenium.
[0043] Figure 4 The image shown is a transmission scanning electron microscope (SEM) image of the non-ruthenium-doped metal-organic framework sample obtained at 350 °C, serving as a reference control group 2. Figure 4 It can be seen that Ni 350 ℃ is composed of Ni3C of various shapes and sizes, and is not covered by an outer carbon layer.
[0044] Figure 5 The image shown is a transmission scanning electron microscope (SEM) image of the ruthenium-doped metal-organic framework sample obtained at 350 °C in control group 1. Figure 5 It can be seen that Ru&Ni 350 ℃ is composed of uniform Ni3C particles, with an outer layer of obvious carbon coating, proving that ruthenium catalyzes the carbonization process and forms a carbon layer at low temperature.
[0045] Figure 6 The X-ray diffraction patterns are those of the ruthenium-doped metal-organic frameworks in Example 1 and the non-ruthenium-doped reference control group 3, obtained at 400 °C. Figure 6 It can be seen that when the temperature rises to 400 ℃, due to the protection of the carbon layer generated by ruthenium catalytic carbonization, Ni3C in Ru&Ni at 400 ℃ is not completely decomposed, while Ni at 400 ℃ has completely decomposed, forming a homogeneous Ni phase.
[0046] Figure 7 These are field emission electron microscope (FET) and aberration transmission electron microscope (TEM) images of the ruthenium-doped metal-organic framework sample obtained at 400 °C in Example 1. Figure 7 It can be seen that Ru & Ni at 400 °C is composed of uniformly dispersed nanoparticles, and its microstructure is a core-shell structure of nickel carbide coated with carbon as the outer layer and nickel as the core. This proves that the carbide layer formed by ruthenium-catalyzed carbide can effectively protect the carbides during high-temperature processes.
[0047] Electrochemical testing Catalyst (2 mg): Ruthenium-doped nickel carbide nanoparticles prepared in Example 1 were loaded onto 1×1 cm carbon paper, and the hydrogen evolution performance of the three-dimensional electrode was tested. The results are as follows: Figure 8 As shown. By Figure 8 It can be seen that the performance of the ruthenium-doped nickel carbide (Ru & Ni 400 ℃) electrode prepared in Example 1 is better than that of the electrode prepared with commercial Pt / C catalyst (purchased from Shanghai Hesen Electric Co., Ltd.) at high current density, indicating that the catalyst material prepared in this invention has good prospects in replacing noble metal hydrogen evolution catalysts.
[0048] The hydrogen evolution performance was tested as follows: A slurry was prepared by mixing 1 mg of the catalyst prepared in Example 1 with 5 μL of Nafin solution (5 wt%), 100 μL of ethanol, and 100 μL of deionized water, and sonicated for 30 min. The slurry was then uniformly coated onto 1×1 cm carbon paper to prepare a test sample. The hydrogen evolution performance was tested in 1 M KOH electrolyte using a three-electrode system, where the prepared carbon paper served as the working electrode, the carbon rod as the counter electrode, and Hg / HgO as the reference electrode. The testing equipment was a Shanghai Chenhua Electrochemical Workstation 760E. The LSV scan rate was 5 mV / s.
[0049] Figure 8The hydrogen evolution performance of the ruthenium-doped nickel catalyst Ru&Ni 400 ℃ in 1M KOH is shown in the figure. The obtained ruthenium-doped nickel catalyst Ru&Ni 400 ℃ exhibits excellent catalytic performance.
[0050] Figure 9 This is a graph showing the long-term stability of the ruthenium-doped metal-organic framework in Example 1 at 400 °C in an anion exchange membrane electrolyzer. Figure 9 It can be seen that the electrolyzer assembled with the obtained catalyst can achieve a high current density of 2 A / cm². -2 It has maintained stable operation for a long period of time, proving its feasibility in actual catalytic production.
[0051] Example 2
[0052] A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve ferric chloride (120 mg, 0.74 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and terephthalic acid (150 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add triethylamine (1-5 mL) to the solution and stir at room temperature for 4 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 600°C at 5°C / min under nitrogen protection. It is held for 4 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0053] Figure 10 This is a graph showing the hydrogen evolution performance of the ruthenium-doped iron catalyst obtained at 600 °C from the ruthenium-doped metal-organic framework in Example 2 in 1M KOH. Figure 10 It can be seen that the performance of the obtained ruthenium-doped iron catalyst Ru&Fe 600 ℃ at high current density far exceeds that of commercial platinum carbon, which proves its superior position in hydrogen evolution catalysis.
[0054] Example 3
[0055] A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and terephthalic acid (150 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add tetramethylammonium hydroxide (1.5 mL) to the solution and stir at room temperature for 4 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 400°C at 3°C / min under nitrogen protection. It is held for 3 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0056] Figure 11 The graph shows the hydrogen evolution performance of the ruthenium-doped nickel catalyst obtained in Example 3 at 400 °C in 1 M KOH. Figure 11 It can be seen that the obtained ruthenium-doped nickel catalyst Ru&Ni tetramethylammonium hydroxide exhibited excellent catalytic performance at 400 ℃, demonstrating the effectiveness of different organic bases for this scheme.
[0057] Example 4
[0058] A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and p-hydroxyterephthalic acid (164 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add triethylamine (1 mL) to the solution and stir at room temperature for 4 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 800°C at 3°C / min under nitrogen protection. It is held for 3 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0059] Figure 12 The graph shows the hydrogen evolution performance of the ruthenium-doped nickel catalyst obtained in Example 4 at 800 °C in 1 M KOH. Figure 12 It can be seen that the obtained ruthenium-doped nickel catalyst Ru&Ni exhibits excellent catalytic performance of p-hydroxyterephthalic acid at 800 °C, demonstrating the effectiveness of different organic ligands for this scheme.
[0060] Comparative Example 1 A method for preparing a catalyst includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and terephthalic acid (150 mg, 0.9 mmol) in water (20 mL), add 50 mg of activated carbon, and stir for 0.5 hours to form solution A; (2) Weigh 10 mg of NaBH4 and dissolve it in 10 ml of water to form solution B; (3) Add solution B dropwise into solution A at a uniform rate and stir for 0.5 hours; (3) Filter, wash and dry, place in an atmosphere furnace, heat to 400°C at 5°C / min under nitrogen protection, keep warm for 4 hours, and cool naturally to obtain the catalyst.
[0061] Figure 13 The graph shows the hydrogen evolution performance of the ruthenium-nickel catalyst obtained by the reduction method of activated carbon supported on ruthenium-nickel metal at 400 °C in 1M KOH. Figure 13 It can be seen that the performance of the obtained Ru&Ni reduction catalyst at 400 ℃ and high current density is not as good as that of the commercial Pt / C catalyst, which proves the superior position of MOF pyrolysis in hydrogen evolution reaction.
[0062] Comparative Example 2 A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), platinum dichloride (8 mg) and terephthalic acid (150 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add triethylamine (1 mL) to the solution and stir at room temperature for 4 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 400°C at 5°C / min under nitrogen protection. The temperature is held for 2 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0063] Figure 14 The graph shows the hydrogen evolution performance of the platinum-doped nickel catalyst obtained in Comparative Example 2 at 400 °C in 1 M KOH. Figure 14It can be seen that the performance of the obtained platinum-doped nickel catalyst Pt&Ni at high current density at 400 ℃ is not as good as that of commercial platinum-carbon, which proves the superior position of ruthenium in hydrogen evolution catalysis.
[0064] Comparative Example 3 A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and terephthalic acid (150 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add triethylamine (1 mL) to the solution and stir at room temperature for 4 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 800°C at 5°C / min under nitrogen protection. It is held for 2 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0065] Figure 15 The graph shows the hydrogen evolution performance of the ruthenium-doped nickel catalyst obtained in Comparative Example 3 at 800 °C in 1 M KOH. Figure 15 It can be seen that the obtained ruthenium-doped nickel catalyst Ru&Ni exhibited poorer catalytic performance at 800 ℃ than at 400 ℃, proving that the increase in temperature leads to the aggregation of active sites, resulting in a decrease in performance.
[0066] Comparative Example 4 A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization includes the following steps: (1) First, dissolve nickel chloride (180 mg, 1.38 mmol), ruthenium trichloride (4 mg, 0.02 mmol) and terephthalic acid (150 mg, 0.9 mmol) in a mixed solvent (30 mL DMF and 2 mL deionized water) to form a homogeneous solution; (2) Then add triethylamine (1 mL) to the solution and stir at room temperature for 4 hours to obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heated to 350°C at 5°C / min under nitrogen protection. The temperature is held for 4 hours and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
[0067] Depend on Figure 8 It can be seen that the obtained ruthenium-doped nickel catalyst Ru&Ni exhibited poorer catalytic performance at 350 ℃ than at 400 ℃, proving that the appropriate temperature helps to form and expose active sites, thereby improving catalytic performance.
[0068] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.
Claims
1. A method for preparing ruthenium-doped transition metal carbide nanocatalysts based on Ru-catalyzed carbonization, characterized in that, Includes the following steps: (1) First, dissolve the transition metal salt, ruthenium salt and organic ligand in a mixed solvent to form a homogeneous solution; (2) Then add an organic base to the solution, stir to react, and obtain a precursor suspension; (3) The precursor suspension was then filtered, washed and dried to obtain a Ru-containing transition metal-organic framework precursor. (4) Finally, the precursor is placed in an atmosphere furnace and heat-treated under inert gas protection and then cooled naturally to obtain ruthenium-doped transition metal carbide nanocatalyst.
2. The method according to claim 1, characterized in that, In step (1), the transition metal salt is selected from any one or more salts of Ni, Co, and Fe; the ruthenium salt is ruthenium trichloride; and the organic ligand is selected from any one or more of terephthalic acid, phthalic acid, p-hydroxyterephthalic acid, or 4,4'-biphenyl.
3. The method according to claim 1, characterized in that, In steps (1) and (2), the ratio of transition metal salt, ruthenium salt, organic ligand, mixed solvent, and organic base is 0.5–1.5 mmol: 0.01–0.05 mmol: 0.3–1 mmol: 16–55 mL: 1–5 mL; the mixed solvent is obtained by mixing N,N'-dimethylformamide and deionized water in a volume ratio of 15–50: 1–5; the organic base is triethylamine or tetramethylammonium hydroxide.
4. The method according to claim 1, characterized in that, In step (2), the stirring reaction conditions are: stirring reaction at room temperature for 2 to 6 hours.
5. The method according to claim 1, characterized in that, In step (4), the inert gas is argon or nitrogen.
6. The method according to claim 1, characterized in that, In step (4), the heat treatment conditions are: heating to 400-800℃ at 2-5℃ / min and holding for 2-4 hours.
7. A ruthenium-doped transition metal carbide nanocatalyst, characterized in that, It is prepared by the method described in any one of claims 1 to 6.
8. The application of the ruthenium-doped transition metal carbide nanocatalyst of claim 7 in the hydrogen evolution reaction of water electrolysis.
9. The application according to claim 8, characterized in that, The hydrogen evolution reaction of water electrolysis is carried out at a current density ≥ 500 mA / cm². 2 Under the conditions.