Carbon-doped ru / ruo2 nanosheets, preparation method and application thereof

Abstract

The present application relates to the technical field of nanomaterials, and particularly relates to carbon-doped Ru / RuO2 nanosheets, a preparation method and application thereof. In the present application, COF (2C-COF) with abundant carbon-carbon bonds is first prepared, C atoms are introduced into the 2C-COF as a carrier to play a carbon-doping role. Carbon doping can improve electronic conductivity, structural stability, dispersion of active sites, and coordination of catalytic effects, and is suitable for neutral and a wide pH value range. Then, 2C-Ru is prepared from the 2C-COF and a ruthenium trichloride solution. Finally, carbon-doped Ru / RuO2 nanosheets are obtained by calcining the 2C-Ru. The carbon-doped Ru / RuO2 nanosheets contain Ru / RuO2 heterojunctions, so that they have excellent HER and OER catalytic performance.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials technology, specifically to carbon-doped Ru / RuO2 nanosheets, their preparation methods, and applications. Background Technology

[0002] Hydrogen production technologies via water electrolysis mainly include alkaline water electrolysis (ALK), proton exchange membrane (PEM), anion exchange membrane (AEM), and solid oxide electrolysis (SOEC). Among these, alkaline water electrolysis is the most mature, commercially widespread, and relatively low-cost, but it suffers from slow response, poor flexibility, gas cross-contamination and purity issues, and difficulty in achieving high-pressure differential operation. Proton exchange membrane (PEM) water electrolysis is highly efficient, has a fast response, is compact, and produces high-purity hydrogen, but it is expensive and has poor membrane lifespan and stability. Anion exchange membrane (AEM) water electrolysis combines low cost and high performance, but it is currently in the transition phase from laboratory to pilot-scale demonstration, lacking long-term, large-scale practical operational data for verification.

[0003] Ruthenium-based catalysts exhibit higher intrinsic activity, lower cost, and higher abundance in PEM electrolysis, but suffer from poor stability and conductivity. In AEM electrolysis, ruthenium-based catalysts show high activity, with a dissolution rate far lower than in acidic environments. Using high-performance ruthenium-based anodes can reduce the operating voltage of AEM electrolyzers, improving energy efficiency and reducing power consumption costs. However, ruthenium remains a precious metal, and the initial goal of AEM technology is to reduce dependence on precious metals. Therefore, ruthenium-based catalysts are considered a "transitional bridge" in the early stages of AEM's high-performance commercialization, rather than the ultimate goal. Improving the activity and durability of ruthenium-based catalysts and reducing costs through rational structural design has become an important research direction. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide carbon-doped Ru / RuO2 nanosheets, their preparation methods, and applications.

[0005] In a first aspect, the present invention provides a method for preparing carbon-doped Ru / RuO2 nanosheets, comprising the following steps: A solution of 2,4,6-tricarboxymethyl phloroglucinol (Tp) and a solution of 4,4-diaminobiphenyl (2C-NH2) were mixed, sonicated, and then acetic acid (AcOH) solution was added. The mixture was reacted at 90℃-110℃ to obtain 2C-COF. 2C-COF and ruthenium trichloride solution were placed in a reaction vessel and reacted at 110℃-130℃ to obtain 2C-Ru; 2C-Ru was calcined at 200℃-450℃ to obtain carbon-doped Ru / RuO2 nanosheets (2C-Ru / RuO2).

[0006] In this invention, a COF (2C-COF) with abundant carbon-carbon bonds is first prepared. Using 2C-COF as a support, carbon atoms are introduced to act as carbon dopant. Carbon doping can improve electronic conductivity, structural stability, dispersion of active sites, and synergistic catalytic effects, and is suitable for neutral and a wide pH range. Then, 2C-Ru is prepared from 2C-COF and ruthenium trichloride solution. Finally, 2C-Ru is calcined to obtain carbon-doped Ru / RuO2 nanosheets. The carbon-doped Ru / RuO2 nanosheets contain Ru / RuO2 heterojunctions, giving them excellent HER and OER catalytic performance. Ru is a known excellent HER catalyst with a suitable hydrogen adsorption free energy (ΔG_H* ≈ 0), which is beneficial for the adsorption / desorption of hydrogen intermediates and promotes H2 generation. RuO2 is a highly efficient OER catalyst that maintains its structure and activity in acidic media and is one of the key materials for proton exchange membrane electrolyzers (PEMWE). In Ru / RuO2 heterojunctions, the HER performance mainly comes from metallic Ru, while the OER performance mainly comes from RuO2. The interfacial synergistic effect is the key to improving the bifunctional performance. Metallic Ru improves conductivity and mechanical stability, while RuO2 provides OER active sites and inhibits excessive Ru oxidation.

[0007] In some optional embodiments, a solution of 2,4,6-triformylphloroglucinol and a solution of 4,4-diaminobiphenyl are mixed, sonicated, and then acetic acid solution is added. The mixture is reacted at 100°C to obtain 2C-COF. 2C-COF and a solution of ruthenium trichloride are placed in a reaction vessel and reacted at 120°C to obtain 2C-Ru. 2C-Ru is calcined at 350°C to obtain carbon-doped Ru / RuO2 nanosheets.

[0008] The 2,4,6-triformylresorcinol solution refers to a solution obtained by dissolving 2,4,6-triformylresorcinol in a solvent. In some optional embodiments, the solvent for the 2,4,6-triformylresorcinol solution is a mixed solvent of o-dichlorobenzene and n-butanol, wherein the volume ratio of o-dichlorobenzene to n-butanol is 1:1; the concentration of the 2,4,6-triformylresorcinol solution is 0.05-0.15 mol / L.

[0009] The 4,4-diaminobiphenyl solution refers to a solution obtained by dissolving 4,4-diaminobiphenyl in a solvent. In some optional embodiments, the solvent for the 4,4-diaminobiphenyl solution is a mixed solvent of o-dichlorobenzene and n-butanol, wherein the volume ratio of o-dichlorobenzene to n-butanol is 1:1; and the concentration of the 4,4-diaminobiphenyl solution is 0.05-0.15 mol / L.

[0010] The acetic acid solution refers to a solution obtained by dissolving acetic acid in a solvent. In some optional embodiments, the solvent for the acetic acid solution is water; the concentration of the acetic acid solution is 4-6 mol / L.

[0011] In some optional embodiments, the volume ratio of the 2,4,6-tricarboxymethyl phloroglucinol solution to the 4,4-diaminobiphenyl solution is 1:1.

[0012] The ruthenium trichloride solution refers to a solution obtained by dissolving ruthenium trichloride in a solvent. In some optional embodiments, the solvent for the ruthenium trichloride solution is a mixed solvent of methanol and DMF, wherein the volume ratio of methanol to DMF is 1:1; and the concentration of the ruthenium trichloride solution is 0.007-0.025 mol / L.

[0013] Secondly, the present invention provides a carbon-doped Ru / RuO2 nanosheet, which is obtained by the preparation method of the carbon-doped Ru / RuO2 nanosheet. The morphology of the carbon-doped Ru / RuO2 nanosheet is a nanosheet with a thickness of about 0.9 nm.

[0014] In some optional embodiments, the Ru loading in the carbon-doped Ru / RuO2 nanosheets is 60 wt%-70 wt%.

[0015] Thirdly, the present invention provides the application of the carbon-doped Ru / RuO2 nanosheets in water splitting reaction, oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR) or organic catalytic reaction.

[0016] In some alternative embodiments, the present invention provides the application of the carbon-doped Ru / RuO2 nanosheets in hydrogen production through acidic or alkaline water electrolysis.

[0017] Due to the adoption of the above technical solutions, the embodiments of the present invention have at least the following beneficial effects: using COF as a template for carbon doping, ultrathin carbon-doped Ru / RuO2 nanosheets are prepared, and the preparation method is simple and low in cost; the carbon-doped Ru / RuO2 nanosheets contain Ru / RuO2 heterojunctions and can be used as bifunctional catalysts for acidic and alkaline water electrolysis; the carbon-doped Ru / RuO2 nanosheets have excellent electrochemical stability and have high potential application value in the field of energy catalysis. Attached Figure Description

[0018] Figure 1 This is an X-ray powder diffraction pattern of 2C-Ru / RuO2 in an embodiment of the present invention.

[0019] Figure 2 This is a scanning electron microscope image of 2C-Ru / RuO2 in an embodiment of the present invention.

[0020] Figure 3 This is a transmission electron microscope image of 2C-Ru / RuO2 in an embodiment of the present invention.

[0021] Figure 4 This is a linear sweep voltammetry curve of acidic OER on a glassy carbon electrode for 2C-Ru / RuO2 in an embodiment of the present invention.

[0022] Figure 5 This is a linear sweep voltammetry curve of acidic HER on a glassy carbon electrode for 2C-Ru / RuO2 in an embodiment of the present invention.

[0023] Figure 6 This is a Tafel curve of the acidic OER reaction of 2C-Ru / RuO2 in an embodiment of the present invention.

[0024] Figure 7 This is a Tafel curve of the acidic HER reaction of 2C-Ru / RuO2 in an embodiment of the present invention.

[0025] Figure 8 In this embodiment of the invention, the 2C-Ru / RuO2 acidic OER reaction was carried out at 50 mA·cm⁻¹. -2 Diagram of constant current electrolysis at current density.

[0026] Figure 9 This is the electrochemical impedance spectroscopy of the acidic OER reaction of 2C-Ru / RuO2 in an embodiment of the present invention.

[0027] Figure 10 This is the electrochemical impedance spectroscopy of the 2C-Ru / RuO2 acidic HER reaction in an embodiment of the present invention.

[0028] Figure 11 This is a conversion diagram of the electrochemical specific surface area of ​​the acidic OER reaction of 2C-Ru / RuO2 in the embodiments of the present invention.

[0029] Figure 12 This is a conversion diagram of the electrochemical specific surface area of ​​the acidic HER reaction of 2C-Ru / RuO2 in an embodiment of the present invention.

[0030] Figure 13 This is a linear sweep voltammetry curve of alkaline OER on a glassy carbon electrode for 2C-Ru / RuO2 in an embodiment of the present invention.

[0031] Figure 14 This is a linear sweep voltammetry curve of alkaline HER on a glassy carbon electrode for 2C-Ru / RuO2 in an embodiment of the present invention.

[0032] Figure 15 This is a Tafel curve of the alkaline OER reaction of 2C-Ru / RuO2 in an embodiment of the present invention.

[0033] Figure 16 This is a Tafel curve of the basic HER reaction of 2C-Ru / RuO2 in an embodiment of the present invention.

[0034] Figure 17 In this embodiment of the invention, the 2C-Ru / RuO2 alkaline OER reaction was carried out at 500 mA·cm⁻¹. -2 Diagram of constant current electrolysis at current density.

[0035] Figure 18 This is the electrochemical impedance spectroscopy of the 2C-Ru / RuO2 alkaline OER reaction in the embodiments of the present invention.

[0036] Figure 19 This is the electrochemical impedance spectroscopy of the 2C-Ru / RuO2 alkaline HER reaction in an embodiment of the present invention.

[0037] Figure 20 This is a conversion diagram of the electrochemical specific surface area of ​​the 2C-Ru / RuO2 alkaline OER reaction in the embodiments of the present invention.

[0038] Figure 21 This is a conversion diagram of the electrochemical specific surface area of ​​the 2C-Ru / RuO2 alkaline HER reaction in the embodiments of the present invention.

[0039] Figure 22 The X-ray powder diffraction pattern of Ru / RuO2 prepared in Comparative Example 1 is shown.

[0040] Figure 23 Scanning electron microscope image of Ru / RuO2 prepared for Comparative Example 1.

[0041] Figure 24 The linear sweep voltammetry curve of acidic OER for Ru / RuO2 prepared in Comparative Example 1 on a glassy carbon electrode is shown.

[0042] Figure 25 The linear sweep voltammetry curve of acidic HER on a glassy carbon electrode for Ru / RuO2 prepared in Comparative Example 1 is shown.

[0043] Figure 26 The linear sweep voltammetry curve of alkaline OER on a glassy carbon electrode for Comparative Example 1 is shown.

[0044] Figure 27 The linear sweep voltammetry curve of alkaline HER on a glassy carbon electrode for Comparative Example 1 is shown.

[0045] Figure 28 The image shows the X-ray powder diffraction pattern of Com.RuO2 in Comparative Example 2.

[0046] Figure 29 The image shows the linear sweep voltammetry curve of the acidic OER of Comparative Example 2, Com.RuO2, on a glassy carbon electrode.

[0047] Figure 30The image shows the linear sweep voltammetry curve of acidic HER on a glassy carbon electrode for Comparative Example 2, specifically Com.RuO2.

[0048] Figure 31 The image shows the linear sweep voltammetry curve of the alkaline OER of Comparative Example 2, Com.RuO2, on a glassy carbon electrode.

[0049] Figure 32 The graph shows the linear sweep voltammetry curve of alkaline HER on a glassy carbon electrode for Comparative Example 2, specifically for Com.RuO2. Detailed Implementation

[0050] The following will clearly and completely describe the concept of the present invention and the resulting technical effects, so as to fully explain the purpose, solution and effects of the present invention.

[0051] Example 1 Carbon-doped Ru / RuO2 nanosheets (2C-Ru / RuO2) were prepared according to the following steps: (1) Dissolve 2,4,6-triformylphloroglucinol (210 mg, 1 mmol) in o-dichlorobenzene / n-butanol (1:1 v / v, 10 mL) to obtain a 2,4,6-triformylphloroglucinol solution, and place it in a 100 mL reaction tube; dissolve 4,4-diaminobiphenyl (297.2 mg, 1.4 mmol) in o-dichlorobenzene / n-butanol (1:1 v / v, 14 mL) to obtain a 4,4-diaminobiphenyl solution; add the 4,4-diaminobiphenyl solution to the 2,4,6-triformylphloroglucinol solution, sonicate the resulting mixed solution to form yellow flocs, and then add AcOH solution (6 M, 2 mL) to the reaction tube; evacuate the reaction system, heat at 100 °C for 72 h, filter and collect the product, wash with a large amount of dichloromethane and methanol, and dry under vacuum at 60 °C for 12 h. h, yielded a yellow powder 2C-COF (yield 86%). (2) Place 100 mg of 2C-COF in a 20 mL polytetrafluoroethylene reactor liner, add 10 mL of ruthenium trichloride in methanol and DMF solution (ruthenium trichloride 35 mg, methanol and DMF volume ratio 1:1), stir for 30 min, place in a forced-air drying oven, heat at 120℃ for 24 h; after cooling, centrifuge three times each with deionized water and methanol, and finally place in a 60℃ vacuum drying oven to dry for 24 h to obtain 2C-Ru; (3) Place 200 mg of 2C-Ru powder in a muffle furnace and heat at 350°C for 90 min (heating rate 5°C·min). -1 The black powder 2C-Ru / RuO2 was obtained (yield 13%).

[0052] The X-ray diffraction pattern of the 2C-Ru / RuO2 prepared in this embodiment is shown below. Figure 1 As can be seen, the catalyst prepared in Example 1 contains ruthenium and ruthenium dioxide phases, proving that the product 2C-Ru / RuO2 was successfully synthesized.

[0053] The scanning electron microscope image of the 2C-Ru / RuO2 prepared in this embodiment is shown below. Figure 2 As can be seen, 2C-Ru / RuO2 has a nanosheet structure with a thickness of approximately 0.89 nm.

[0054] The transmission electron microscope image of the 2C-Ru / RuO2 prepared in this embodiment is shown below. Figure 3 As can be seen, the surface of 2C-Ru / RuO2 contains nanoparticles and is a Ru / RuO2 heterostructure.

[0055] The performance of the product 2C-Ru / RuO2 prepared in Example 1 was tested. The test methods and results are as follows: (a) Electrocatalytic acidic OER and HER performance tests of 2C-Ru / RuO2 Electrochemical tests were performed at room temperature using a classic three-electrode system on a CHI760E electrochemical workstation. The electrolyte was 0.5 M H₂SO₄ solution under acidic conditions. Ag / AgCl and Pt plates were used as the reference and counter electrodes, respectively. 2 mg of 2C-Ru / RuO₂ was mixed with 1 mg of acetylene black, 200 μL of isopropanol, and 20 μL of Nafion. After sonication for 20 minutes, the mixture was dropped onto a glassy carbon electrode as the working electrode.

[0056] Figure 4 , Figure 5 The linear sweep voltammetry curve shown was obtained at a scan rate of 10 mV / s, indicating that 2C-Ru / RuO2 drives a 10 mA·cm² voltammetry curve in the anolyte acidic OER reaction. -2 The required overpotential for the current density is 150 mV, driving 10 mA·cm in the cathodic acidic HER reaction. -2 The required overpotential for the current density is 47 mV.

[0057] Figure 6 , Figure 7 The Tafel curve shown is based on Figure 4 , 5 Calculations show that the Tafel slope of the acidic OER of 2C-Ru / RuO2 on a glassy carbon electrode is 49.71 mV·dec. -1 The Tafel slope of acidic HER is 52.43 mV·dec. -1 .

[0058] like Figure 8As shown, at 50 mA·cm -2 The fact that 2C-Ru / RuO2 can be electrolyzed for 1000 hours at the specified current density indicates that 2C-Ru / RuO2 has good stability.

[0059] (b) Acidic electrochemical impedance spectroscopy of 2C-Ru / RuO2 Electrochemical impedance spectroscopy (EIS) measurements were performed in the frequency range of 0.01 Hz to 100 kHz.

[0060] Electrochemical impedance spectroscopy (EIS) is shown below Figure 9 , Figure 10 ,Depend on Figure 9 It can be seen that the charge transfer resistance of 2C-Ru / RuO2 in the acidic OER reaction is approximately 30 Ω; from Figure 10 It can be seen that the charge transfer resistance in the acidic HER reaction is about 15 Ω, and the charge transfer resistance of the catalyst is relatively small, indicating that 2C-Ru / RuO2 has a fast reaction rate.

[0061] (c) Acidic electrochemical specific surface area test of 2C-Ru / RuO2 To determine the electrochemical surface area (ECSA), the electrochemical double-layer capacitance (C0) of the prepared electrode was measured by cyclic voltammetry (CV). dl CV was performed within the non-Radial range (0.9–1.0 V vs RHE) at a scan rate of 20 mV / s. -1 40mV s -1 60 mV s -1 80 mV s -1 100 mV s -1 and 120 mV s -1 A linear graph was obtained by plotting the current density versus scan rate at 0.95 V vs RHE. dl It is half the slope of the linear graph and is used to represent ECSA.

[0062] Electrochemical specific surface area diagram is shown below Figure 11 and Figure 12 As can be seen, 2C-Ru / RuO2 has a large electrochemical surface area, indicating that the catalyst has many active sites and good performance.

[0063] (d) Electrocatalytic alkaline OER and HER performance tests of 2C-Ru / RuO2 Electrochemical tests were performed at room temperature using a classic three-electrode system on a CHI760E electrochemical workstation. Under alkaline conditions, the electrolyte was 1 M KOH solution, and Hg / HgO and Pt plates were used as the reference and counter electrodes. 2 mg of 2C-Ru / RuO2 was mixed with 1 mg of acetylene black, 200 μL of isopropanol, and 20 μL of Nafion. After sonication for 20 minutes, the mixture was dropped onto a glassy carbon electrode as the working electrode.

[0064] Figure 13 , Figure 14 The linear sweep voltammetry curve shown was obtained at a scan rate of 10 mV / s, indicating that 2C-Ru / RuO2 drives a 10 mA·cm² reaction in the anolytical alkaline OER reaction. -2 The required overpotential for the current density is 166 mV, driving 10 mA·cm in the cathodic alkaline HER reaction. -2 The required overpotential for the current density is 11 mV.

[0065] Figure 15 , Figure 16 The Tafel curve shown is based on Figure 13 , 14 Calculations show that the Tafel slope of the basic OER of 2C-Ru / RuO2 on a glassy carbon electrode is 57.32 mV·dec. -1 The Tafel slope of the basic HER is 30.86 mV·dec. -1 . Figure 17 As shown at 500 mA·cm -2 The fact that 2C-Ru / RuO2 can be electrolyzed for 200 hours at the current density indicates that 2C-Ru / RuO2 has good stability.

[0066] (e) Basic electrochemical impedance spectroscopy of 2C-Ru / RuO2 Electrochemical impedance spectroscopy (EIS) measurements were performed in the frequency range of 0.01 Hz to 100 kHz.

[0067] Electrochemical impedance spectroscopy (EIS) is shown below Figure 18 , Figure 19 ,Depend on Figure 18 It can be seen that the charge transfer resistance of 2C-Ru / RuO2 in the alkaline OER reaction is approximately 20 Ω; from Figure 19 It can be seen that the charge transfer resistance in the alkaline HER reaction is about 5 Ω, and the charge transfer resistance of the catalyst is relatively small, indicating that 2C-Ru / RuO2 has a fast reaction rate.

[0068] (f) Alkaline electrochemical specific surface area test of 2C-Ru / RuO2 To determine the electrochemical surface area (ECSA), the electrochemical double-layer capacitance (C0) of the prepared electrode was measured by cyclic voltammetry (CV). dl CV was performed within the non-Radial range (0.1–0.2 V vs RHE) at a scan rate of 20 mV / s. -1 40mV s -1 60 mV s -1 80 mV s -1 100 mV s -1 and 120 mV s -1 A linear graph was obtained by plotting the current density versus scan rate at 0.95 V vs RHE. dl It is half the slope of the linear graph and is used to represent ECSA.

[0069] Electrochemical specific surface area diagram is shown below Figure 20 and Figure 21 As can be seen, 2C-Ru / RuO2 has a large electrochemical surface area, indicating that the catalyst has many active sites and good performance.

[0070] Comparative Example 1 Carbon-free Ru / RuO2 spherical nanomaterials (Ru / RuO2) were prepared according to the following steps: (1) Place 100 mg RuCl3 in a 20 mL polytetrafluoroethylene reactor liner, add 10 mL of methanol and DMF solution with a volume ratio of 1:1, stir for 30 min, and then place in a forced-air drying oven and heat at 120 °C for 24 h. After cooling, centrifuge three times each with deionized water and methanol, and finally place in a vacuum drying oven at 60 °C for 24 h to obtain Ru powder; (2) Place 50 mg of Ru powder in a muffle furnace and heat at 350°C for 90 min (heating rate 5°C / min). -1 The black powder Ru / RuO2 was obtained (yield 80%).

[0071] The X-ray diffraction pattern of Ru / RuO2 prepared in this comparative example is shown below. Figure 22 As can be seen, Ru / RuO2 contains ruthenium and ruthenium dioxide phases, proving that the product Ru / RuO2 was successfully synthesized.

[0072] The scanning electron microscope image of Ru / RuO2 prepared in this comparative example is shown below. Figure 23 As can be seen, Ru / RuO2 has a spherical structure.

[0073] The performance of the Ru / RuO2 product prepared in Comparative Example 1 was tested. The test methods and results are as follows: (a) Electrocatalytic OER and HER performance tests of Ru / RuO2 Electrochemical tests were performed at room temperature using a classic three-electrode system on a CHI760E electrochemical workstation. Under acidic conditions, the electrolyte was 0.5 M H₂SO₄ solution, with Ag / AgCl and Pt plates used as the reference and counter electrodes. Under alkaline conditions, the electrolyte was 1 M KOH solution, with Hg / HgO and Pt plates used as the reference and counter electrodes. 2 mg of Ru / RuO₂ was mixed with 1 mg of acetylene black, 200 μL of isopropanol, and 20 μL of Nafion, and after sonication for 20 minutes, the sample was dropped onto a glassy carbon electrode as the working electrode.

[0074] Figures 24-27 The linear scanning voltammetry curve shown was obtained at a scan rate of 10 mV / s, from... Figure 24 and Figure 25 It can be seen that Ru / RuO2 drives 10 mA·cm in the anolyte acidic OER reaction. -2 The required overpotential for the current density is 196 mV, driving 10 mA·cm in the cathodic acidic HER reaction. -2 The required overpotential for the current density is 60 mV. (From...) Figure 26 and Figure 27 It can be seen that Ru / RuO2 drives the anodic alkaline OER reaction by 10 mA·cm -2 The required overpotential for the current density is 231 mV, driving a current density of 10 mA·cm⁻¹ in the cathodic alkaline HER reaction. -2 The required overpotential for the current density is 25 mV.

[0075] The test results show that the catalytic performance of the carbon-free Ru / RuO2 spherical nanomaterials is not as good as that of 2C-Ru / RuO2.

[0076] Comparative Example 2 Purchase a commercial RuO2 sample (labeled Com.RuO2) for performance testing and comparison with 2C-Ru / RuO2.

[0077] The X-ray diffraction pattern of the comparative sample Com.RuO2 is shown below. Figure 28 As can be seen, Com.RuO2 contains a ruthenium dioxide phase.

[0078] Performance tests were conducted on Comparative Example 2 product Com.RuO2. The test methods and results are as follows: (a) Electrocatalytic OER and HER performance tests of Com.RuO2 Electrochemical tests were performed at room temperature using a classic three-electrode system on a CHI760E electrochemical workstation. Under acidic conditions, the electrolyte was 0.5 M H₂SO₄ solution, with Ag / AgCl and Pt plates used as the reference and counter electrodes. Under alkaline conditions, the electrolyte was 1 M KOH solution, with Hg / HgO and Pt plates used as the reference and counter electrodes. 2 mg of Com.RuO₂ was mixed with 1 mg of acetylene black, 200 μL of isopropanol, and 20 μL of Nafion, and after sonication for 20 minutes, the mixture was dropped onto a glassy carbon electrode as the working electrode.

[0079] Figures 29-32 The linear scanning voltammetry curve shown was obtained at a scan rate of 10 mV / s, from... Figure 29 and Figure 30 It can be seen that Com.RuO2 drives 10 mA·cm in the anolyte acidic OER reaction. -2 The required overpotential for the current density is 293 mV, driving a current density of 10 mA·cm⁻¹ in the cathodic acidic HER reaction. -2 The required overpotential for the current density is 79 mV. (From...) Figure 31 and Figure 32 It can be seen that Com.RuO2 drives 10 mA·cm in the anodic alkaline OER reaction. -2 The required overpotential for the current density is 278 mV, driving a 10 mA·cm² current density in the cathodic alkaline HER reaction. -2 The required overpotential for the current density is 58 mV.

[0080] The test results show that Com.RuO2 does not perform as well as 2C-Ru / RuO2 in oxygen evolution and hydrogen evolution reactions under acidic conditions. This indicates that the catalyst prepared by this invention can not only achieve the synthesis of multifunctional catalysts and reduce costs, but also improve the performance of the catalyst in water electrolysis under both acidic and alkaline conditions.

[0081] The above description is merely a preferred embodiment of the present invention. The present invention is not limited to the above-described embodiments. Any embodiment that achieves the technical effects of the present invention by the same or equivalent means should fall within the protection scope of the present invention. Within the protection scope of the present invention, various modifications and variations can be made to the technical solutions and / or implementation methods.

Claims

1. A method for preparing carbon-doped Ru / RuO2 nanosheets, characterized in that, Includes the following steps: A solution of 2,4,6-triformylphloroglucinol and a solution of 4,4-diaminobiphenyl were mixed, sonicated, and then acetic acid solution was added. The mixture was reacted at 90℃-110℃ to obtain 2C-COF. 2C-COF and ruthenium trichloride solution were placed in a reaction vessel and reacted at 110℃-130℃ to obtain 2C-Ru. 2C-Ru was calcined at 200℃-450℃ to obtain carbon-doped Ru / RuO2 nanosheets.

2. The method according to claim 1, characterized in that, A solution of 2,4,6-triformylphloroglucinol and a solution of 4,4-diaminobiphenyl were mixed, sonicated, and then acetic acid solution was added. The mixture was reacted at 100 °C to obtain 2C-COF. 2C-COF and ruthenium trichloride solution were placed in a reaction vessel and reacted at 120 °C to obtain 2C-Ru. 2C-Ru was calcined at 350 °C to obtain carbon-doped Ru / RuO2 nanosheets.

3. The method according to claim 1, characterized in that, The solvent for the 2,4,6-tricarboxymethyl phloroglucinol solution is a mixed solvent of o-dichlorobenzene and n-butanol, wherein the volume ratio of o-dichlorobenzene to n-butanol is 1:1; the concentration of the 2,4,6-tricarboxymethyl phloroglucinol solution is 0.05-0.15 mol / L.

4. The method according to claim 1, characterized in that, The solvent for the 4,4-diaminobiphenyl solution is a mixed solvent of o-dichlorobenzene and n-butanol, wherein the volume ratio of o-dichlorobenzene to n-butanol is 1:1; the concentration of the 4,4-diaminobiphenyl solution is 0.05-0.15 mol / L.

5. The method according to claim 1, characterized in that, The solvent for the acetic acid solution is water; the concentration of the acetic acid solution is 4-6 mol / L.

6. The method according to claim 1, characterized in that, The volume ratio of the 2,4,6-tricarboxymethyl phloroglucinol solution to the 4,4-diaminobiphenyl solution is 1:

1.

7. The method according to claim 1, characterized in that, The solvent for the ruthenium trichloride solution is a mixture of methanol and DMF, wherein the volume ratio of methanol to DMF is 1:1; the concentration of the ruthenium trichloride solution is 0.007-0.025 mol / L.

8. A carbon-doped Ru / RuO2 nanosheet, characterized in that, It is obtained by the preparation method of carbon-doped Ru / RuO2 nanosheets according to any one of claims 1-7.

9. The carbon-doped Ru / RuO2 nanosheets according to claim 8, characterized in that, The Ru loading in the carbon-doped Ru / RuO2 nanosheets is 60 wt%-70 wt%.

10. The application of the carbon-doped Ru / RuO2 nanosheets according to claim 8 in water splitting, oxygen reduction, carbon dioxide reduction or organic catalytic reactions.

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