Composite nano material mutually doped with ruthenium dioxide and cobaltosic oxide for oxygen evolution reaction as well as preparation method and application of composite nano material
By forming a heterojunction structure in a ruthenium-cobalt composite nanomaterial, the adsorption capacity for oxygen-containing intermediates was optimized, solving the problems of durability and catalytic activity of ruthenium-based oxides in the acidic oxygen evolution reaction, and achieving a highly efficient oxygen evolution reaction catalytic effect.
Patent Information
- Application Number
- CN202511666834.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-14
- Publication Date
- 2026-01-23
AI Technical Summary
In the existing technology, ruthenium-based oxides have insufficient durability in acidic oxygen evolution reaction, and the doping of foreign metal atoms leads to lattice strain and changes in electronic state, affecting catalytic activity and stability. There is a lack of effective synergistic doping and heterojunction structure strategies.
By employing interdoped ruthenium dioxide and cobalt tetroxide composite nanomaterials, the adsorption capacity for oxygen-containing intermediates is optimized by forming a heterojunction structure through ruthenium-doped cobalt tetroxide and cobalt-doped ruthenium dioxide. The oxygen evolution reaction is accelerated and the overpotential is reduced by utilizing the Ru-doped Co3O4 and Co-doped RuO2 composite.
It significantly enhances catalytic activity, reduces the overpotential of the oxygen evolution reaction, and has a simple and cost-controllable preparation method, showing good prospects for large-scale production.
Smart Images
Figure CN121381069A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of nanomaterials, and particularly relates to a mutual-doped ruthenium dioxide and tricobalt tetroxide composite nanomaterial for oxygen evolution reaction and a preparation method and application thereof. BACKGROUND
[0002] Developing non-iridium-based electrocatalysts for acid oxygen evolution reaction (Oxygen Evolution Reaction) is of great significance to promote the development of high-efficiency proton exchange membrane water electrolysis (PEMWE) to support the hydrogen energy industry. Ruthenium-based oxides have long been considered as potential candidate materials, but their durability in practical applications is still insufficient (Applied Catalysis B: Environmental, 324 (2023): 122294). In recent years, researchers have proposed various strategies to improve the oxygen evolution reaction (OER) performance of RuO2 in acidic media, mainly including the introduction of foreign metal atom doping (such as Li, Zn, Sn, Nb, and Ta), which can form Ru-O-M (M = metal ion) local structures inside the lattice or at the interface, thereby producing a tensile stress effect on the Ru-O bond (Energy & Environmental Science, 14 (2021): 4647-4671). For example, through a rapid heat-driven cation exchange method, a high enough density of microcrystalline grain boundaries (GB) is introduced into the V-doped RuO2 matrix without using any template agent, which can form stable Ru-O-V structures and further stretch the Ru-O bond (Nature Communications, 16 (2025): 4482); constructing heterostructures (such as RuO2 / CeO2, RuO2 / ZrO2, and RuCo@RuCoO x core-shell nanospheres) (Journal of Materials Chemistry A, 9 (2021): 14352-14362); for example, in the RuO2 / (Co, Mn)3O4 heterostructure, Mn doping induces electron enrichment at Ru sites, weakens O adsorption, and reduces the *OOH formation energy barrier. Studies have shown that lattice strain plays an important role in improving OER catalytic performance (Applied Catalysis B: Environmental, 297 (2021): 120442). However, in these systems, the foreign ions not only induce lattice strain, but also change the charge state of ruthenium ions as electron donors, which makes it complex to understand the influence mechanism of lattice strain on the catalytic activity and stability of ruthenium oxides.
[0003] Therefore, how to coordinate the doping and heterojunction structure strategy, construct a new structure of oxygen evolution catalyst, and improve the catalytic activity of the oxygen evolution catalyst still need to be solved. SUMMARY
[0004] The purpose of the present application is to provide a mutual doping of ruthenium dioxide and cobalt trioxide composite nanomaterial for oxygen evolution reaction and its preparation method and application, which can be used as an oxygen evolution catalyst and has excellent catalytic activity.
[0005] The purpose of the present application can be achieved by the following technical solutions: One of the purposes of the present application is to provide a mutual doping of ruthenium dioxide and cobalt trioxide composite nanomaterial for oxygen evolution reaction, which includes ruthenium-doped cobalt trioxide and cobalt-doped ruthenium dioxide, the ruthenium-doped cobalt trioxide and the cobalt-doped ruthenium dioxide form a heterojunction structure, the ruthenium doping is in the crystal lattice of the cobalt trioxide, and the cobalt doping is in the crystal lattice of the ruthenium dioxide.
[0006] Preferably, the atomic ratio of ruthenium and cobalt in the mutual doping of ruthenium dioxide and cobalt trioxide composite nanomaterial is 0.2-5:1.
[0007] The second purpose of the present application is to provide a preparation method of the mutual doping of ruthenium dioxide and cobalt trioxide composite nanomaterial for oxygen evolution reaction, which includes the following steps: uniformly mixing a carbon precursor, a cobalt salt precursor, and a ruthenium salt precursor, then sequentially performing first-stage calcination in a specific atmosphere and second-stage calcination in an oxygen-containing atmosphere to obtain the mutual doping of ruthenium dioxide and cobalt trioxide composite nanomaterial.
[0008] Preferably, the carbon precursor includes any one of natural carbon materials, artificial carbon materials, or derived carbon materials.
[0009] Preferably, the cobalt salt precursor includes any one or more of cobalt nitrate, cobalt chloride, cobalt acetate, or cobalt sulfate.
[0010] Preferably, the ruthenium salt precursor includes any one or more of ruthenium nitrate, ruthenium chloride, or ruthenium acetate.
[0011] Preferably, the specific method of mixing includes any one or more of grinding mixing method, impregnation method, ultrasonic mixing method, and rotary evaporation method.
[0012] Further preferably, the solvent used in the impregnation method, ultrasonic mixing method, and rotary evaporation method includes any one or more of water, ethanol, methanol, acetone, ethylene glycol, or isopropyl alcohol.
[0013] Preferably, the total mass of cobalt element in the cobalt salt precursor and ruthenium element in the ruthenium salt precursor accounts for 0.5%-50% of the mass of the carbon precursor when the carbon precursor, the cobalt salt precursor and the ruthenium salt precursor are mixed.
[0014] Further preferably, the total mass of cobalt element in the cobalt salt precursor and ruthenium element in the ruthenium salt precursor accounts for 10%-30% of the mass of the carbon precursor.
[0015] Preferably, the molar ratio of the ruthenium element in the ruthenium salt precursor and the cobalt element in the cobalt salt precursor is 0.2-5:1.
[0016] Preferably, the temperature of the first-stage calcination is 600-1200℃, and the calcination time is 0.5-12 h.
[0017] Further preferably, the temperature of the first-stage calcination is 700-900℃, and the calcination time is 2-5 h.
[0018] Preferably, the specific atmosphere includes any one of argon, nitrogen, helium, hydrogen-nitrogen mixed gas, hydrogen-argon mixed gas, hydrogen-helium mixed gas, carbon monoxide-nitrogen mixed gas, carbon monoxide-argon mixed gas, carbon monoxide-helium mixed gas, hydrogen gas or carbon monoxide.
[0019] Further preferably, in the nitrogen mixed gas, the hydrogen-argon mixed gas and the hydrogen-helium mixed gas, the volume concentration of the hydrogen gas is 0.1-30%.
[0020] Further preferably, in the carbon monoxide-nitrogen mixed gas, the carbon monoxide-argon mixed gas and the carbon monoxide-helium mixed gas, the volume concentration of the carbon monoxide is 0.1-30%.
[0021] Preferably, the temperature of the second-stage calcination is 300-800℃, and the calcination time is 0.5-5 h.
[0022] Further preferably, the temperature of the second-stage calcination is 400-600℃, and the calcination time is 1-3 h.
[0023] Preferably, the oxygen-containing atmosphere includes any one of air or oxygen.
[0024] The third object of the present application is to provide the application of the mutual-doped ruthenium dioxide and tricobalt tetraoxide composite nanomaterial for oxygen evolution reaction in an OER catalyst.
[0025] Compared with single doped materials (Co-doped RuO2 or Ru-doped Co3O4), the heterostructure of Ru-doped Co3O4 and Co-doped RuO2 optimizes the adsorption capacity of oxygen-containing intermediates (such as OH*, O*, OOH*), accelerates the rate of oxygen evolution reaction, and reduces the overpotential of oxygen evolution reaction.
[0026] Compared with the prior art, the present application has the following beneficial effects: (1) The present application provides a mutual doping ruthenium dioxide and tricobalt tetroxide composite nanomaterial, which forms a new interface structure by mutual doping of metal atoms into the oxide structure of the other, which can greatly improve the catalytic activity as an oxygen evolution reaction catalyst.
[0027] (2) The present application synthesizes a composite of Ru-doped Co3O4 and Co-doped RuO2 based on mutual doping and heterojunction structure strategy, Ru atoms are doped into Co3O4 lattice, Co atoms are doped into RuO2 lattice, and a stable heterojunction is formed, which optimizes the adsorption capacity of oxygen-containing intermediates (such as OH*, O*, OOH*), accelerates the rate of oxygen evolution reaction, and reduces the overpotential of oxygen evolution reaction.
[0028] (3) When the atomic ratio of Ru and Co is 1:1, the overpotential of the mutual doping ruthenium dioxide and tricobalt tetroxide composite nanomaterial prepared by the present application for catalytic oxygen evolution reaction is as low as 237 mV, which is significantly lower than the overpotential of pure Co3O4, pure RuO2, Co-doped RuO2, or Ru-doped Co3O4 catalyst, showing better catalytic efficiency and application potential.
[0029] (4) The preparation method of the present application is simple, which can be completed by only core steps such as precursor mixing, calcination and cooling, and the process parameters can be flexibly adjusted to adapt to the optimal preparation effect, which has low operation difficulty, controllable cost, good large-scale production prospect and practical application value. BRIEF DESCRIPTION OF DRAWINGS
[0030] Figure 1 Figure 1 is an XRD pattern of the mutual doping RuO2-Co3O4 (atomic ratio of Ru and Co is 1:1) composite nanomaterial prepared in Example 1.
[0031] Figure 2 Figure 2 is an XRD pattern of the mutual doping RuO2-Co3O4 (atomic ratio of Ru and Co is 2:1) composite nanomaterial prepared in Example 2.
[0032] Figure 3 Figure 3 is an XRD pattern of the mutual doping RuO2-Co3O4 (atomic ratio of Ru and Co is 1:2) composite nanomaterial prepared in Example 3.
[0033] Figure 4 Figure 3 is an XRD pattern of the Ru-doped Co3O4 composite nanomaterial prepared in Comparative Example 3.
[0034] Figure 5 Figure 4 is an XRD pattern of the Co-doped RuO2 composite nanomaterial prepared in Comparative Example 4.
[0035] Figure 6 Figure 5 is an OER performance of the inter-doped RuO2-Co3O4 (atomic ratio of Ru and Co is 1:1) composite nanomaterial prepared in Example 1 and the materials of Comparative Examples 1-4. DETAILED DESCRIPTION
[0036] This embodiment is implemented on the basis of the technical solution of the present application, and gives a detailed implementation and specific operation process, but the protection scope of the present application is not limited to the following examples.
[0037] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present application are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
[0038] An inter-doped ruthenium dioxide and tricobalt tetraoxide composite nanomaterial for oxygen evolution reaction, comprising ruthenium-doped tricobalt tetraoxide and cobalt-doped ruthenium dioxide, the ruthenium-doped tricobalt tetraoxide and the cobalt-doped ruthenium dioxide form a heterojunction structure, the ruthenium doping is in the crystal lattice of the tricobalt tetraoxide, the cobalt doping is in the crystal lattice of the ruthenium dioxide, and the atomic ratio of ruthenium and cobalt in the inter-doped ruthenium dioxide and tricobalt tetraoxide composite nanomaterial is 0.2-5:1.
[0039] The specific preparation method comprises the following steps: uniformly mixing a carbon precursor, a cobalt salt precursor and a ruthenium salt precursor, and then sequentially performing first-stage calcination in a specific atmosphere and second-stage calcination in an oxygen-containing atmosphere to obtain the inter-doped ruthenium dioxide and tricobalt tetraoxide composite nanomaterial.
[0040] The present application will be described in detail below in combination with the drawings and specific examples.
[0041] Example 1: This embodiment provides an inter-doped RuO2-Co3O4 composite nanomaterial, wherein the carbon precursor is conductive carbon black (specific model is Ketjenblack EC-600 JD), and the atomic ratio of ruthenium element and cobalt element is 1:1. The specific preparation method of this embodiment is as follows: Take 0.05 g Ketjenblack EC-600 JD in a 20 ml sample bottle, add a solution of 0.0187 g ruthenium trichloride (RuCl3) and 0.0117 g cobalt chloride (CoCl2) dissolved in anhydrous ethanol, ultrasonic for 2 h, and the obtained viscous sample is placed in a vacuum oven at 70 ℃ for 12 h. The obtained solid powder is placed in an agate mortar and ground into powder, and then moved to a tube furnace and calcined at 800 ℃ for 2 h under a hydrogen-argon mixed gas (5% H2 / 95% Ar) atmosphere, with a heating rate of 10 ℃ / min. The obtained solid powder is calcined at 400 ℃ for 1 h in air to obtain the inter-doped RuO2-Co3O4 composite nanomaterial.
[0042] Figure 1 The XRD spectrum of the inter-doped RuO2-Co3O4 composite nanomaterial prepared in this example is shown in the figure. It can be seen from the figure that diffraction peaks corresponding to Co3O4 appear at 18.80°, 31.07°, 36.7° and 44.45°, and diffraction peaks corresponding to RuO2 appear at 28.08°, 35.26°, 40.22°, 54.67° and 67.42°. The above peaks are all shifted by a certain angle from the standard diffraction peaks of the two. The above results show that the inter-doped RuO2-Co3O4 composite nanomaterial is successfully prepared in this example.
[0043] Example 2: This example provides an inter-doped RuO2-Co3O4 composite nanomaterial, in which carbon is conductive carbon black (specific model Ketjenblack EC-600 JD), and the atomic ratio of ruthenium element and cobalt element is 2:1. The specific preparation method of this example is as follows: Take 0.05 g Ketjenblack EC-600 JD in a 20 ml sample bottle, then add a solution of 0.0249 g ruthenium trichloride (RuCl3) and 0.0078 g cobalt chloride (CoCl2) in anhydrous ethanol, ultrasonic for 2 h, and the obtained viscous sample is placed in a vacuum oven at 70 ℃ for 12 h. The obtained solid powder is placed in an agate mortar and ground into powder, and then moved to a tube furnace and calcined at 800 ℃ for 2 h under a hydrogen-argon mixed gas (5% H2 / 95% Ar) atmosphere, with a heating rate of 10 ℃ / min. The obtained solid powder is calcined at 400 ℃ for 1 h in air to obtain the inter-doped RuO2-Co3O4 composite nanomaterial.
[0044] Figure 2The XRD spectrum of the inter-doped RuO2-Co3O4 composite nanomaterial prepared in the embodiment is shown in the figure, from which it can be seen that diffraction peaks corresponding to Co3O4 appear at 31.05°, 36.84° and 45.27°, and diffraction peaks corresponding to RuO2 appear at 28.14°, 35.32°, 40.43°, 54.59° and 58.34°, and the above peaks are all shifted by a certain angle from the standard diffraction peaks of the two. The above results show that the inter-doped RuO2-Co3O4 composite nanomaterial is successfully prepared in the embodiment.
[0045] Embodiment 3 The embodiment provides an inter-doped RuO2-Co3O4 composite nanomaterial, wherein carbon is conductive carbon black (specific model Ketjenblack EC-600 JD), and the atomic ratio of ruthenium elements and cobalt elements is 1:2. The specific preparation method of the embodiment is as follows: 0.05 g of Ketjenblack EC-600 JD is placed in a 20 ml sample bottle, and then 0.0124 g of ruthenium trichloride (RuCl3) and 0.0156 g of cobalt chloride (CoCl2) in anhydrous ethanol solution are ultrasonically treated for 2 h, and the obtained viscous sample is placed in a vacuum oven and dried at 70 ℃ for 12 h. The obtained solid powder is ground into powder in an agate mortar, and then moved to a tube furnace and calcined at 800 ℃ for 2 h in a hydrogen-argon mixed gas (5% H2 / 95% Ar) atmosphere, and the temperature rising rate is 10 ℃ / min, and the obtained solid powder is calcined at 400 ℃ for 1 h in air to obtain the inter-doped RuO2-Co3O4 composite nanomaterial.
[0046] Figure 3 The XRD spectrum of the inter-doped RuO2-Co3O4 composite nanomaterial prepared in the embodiment is shown in the figure, from which it can be seen that diffraction peaks corresponding to Co3O4 appear at 31.05°, 36.84° and 45.27°, and diffraction peaks corresponding to RuO2 appear at 28.14°, 35.32°, 40.43°, 54.59° and 58.34°, and the above peaks are all shifted by a certain angle from the standard diffraction peaks of the two. The above results show that the inter-doped RuO2-Co3O4 composite nanomaterial is successfully prepared in the embodiment.
[0047] Embodiment 4 The embodiment provides an inter-doped RuO2-Co3O4 composite nanomaterial, wherein carbon is conductive carbon black (specific model Ketjenblack EC-300 JD), and the atomic ratio of ruthenium elements and cobalt elements is 1:1. The specific preparation method of the embodiment is as follows: Take 0.05 g Ketjenblack EC-300 JD in a mortar, then add 0.0278 g ruthenium acetate (C4H6O4Ru) and 0.0291 g cobalt nitrate (Co(NO3)2·6H2O) and grind them well, then move to a tube furnace, calcine at 900 ℃ for 2 h under argon atmosphere, the heating rate is 10 ℃ / min, the obtained solid powder is calcined at 500 ℃ for 3 h in air to obtain the inter-doped RuO2-Co3O4 composite nanomaterial.
[0048] Example 5: The present example provides an inter-doped RuO2-Co3O4 composite nanomaterial, wherein the atomic ratio of ruthenium element and cobalt element is 1:1, and the carbon precursor is conductive carbon black (specific model BP 2000). The specific preparation method of the present example is as follows: Take 0.05 g BP 2000 in a beaker, then add 0.040 g ruthenium acetylacetonate (C 15 H 21 O6Ru) and 0.0291 g cobalt nitrate (Co(NO3)2·6H2O) in acetone solution, after stirring, rotary evaporation to obtain a solid powder, then place it in an agate mortar and grind it into a powder, then move it to a tube furnace, calcine at 700 ℃ for 2 h under hydrogen-argon mixed gas (10% H2 / 90% Ar) atmosphere, the heating rate is 10 ℃ / min, the obtained solid powder is calcined at 500 ℃ for 2 h in air to obtain the inter-doped RuO2-Co3O4 composite nanomaterial.
[0049] Comparative Example 1: The present comparative example provides a pure Co3O4 nanomaterial, wherein the carbon is conductive carbon black (specific model Ketjenblack EC-600 JD). The specific preparation method of the present comparative example is as follows: Take 0.05 g Ketjenblack EC-600 JD in a 20 ml sample bottle, add a solution of 0.0234 g cobalt chloride (CoCl2) in anhydrous ethanol, ultrasonic for 2 h, the obtained viscous sample is placed in a vacuum oven and dried at 70 ℃ for 12 h. The obtained solid powder is placed in an agate mortar and ground into a powder, then moved to a tube furnace, calcined at 800 ℃ for 2 h under hydrogen-argon mixed gas (5% H2 / 95% Ar) atmosphere, the heating rate is 10 ℃ / min, the obtained solid powder is calcined at 450 ℃ for 1 h in air to obtain the Co3O4 nanomaterial.
[0050] Comparative Example 2: The present comparative example provides a pure RuO2 nanomaterial, wherein the carbon is conductive carbon black (specific model Ketjenblack EC-600 JD). The specific preparation method of the present comparative example is as follows: Take 0.05 g Ketjenblack EC-600 JD in a 20 ml sample bottle, add a solution of 0.0373 g ruthenium trichloride (RuCl3) dissolved in anhydrous ethanol, ultrasonic for 2 h, the obtained viscous sample is placed in a vacuum oven at 70 ℃ for 12 h. The obtained solid powder is placed in an agate mortar and ground into powder, then moved to a tube furnace, calcined at 800 ℃ for 2 h under a hydrogen-argon mixed gas (5% H2 / 95% Ar) atmosphere, the heating rate is 10 ℃ / min, the obtained solid powder is calcined at 400 ℃ for 1 h in air to obtain RuO2 nanomaterial.
[0051] Comparative Example 3: This comparative example provides a Ru-doped Co3O4 nanomaterial, in which the carbon is conductive carbon black (specific model Ketjenblack EC-600 JD). The specific preparation method of this comparative example is as follows: Take 0.05 g Ketjenblack EC-600 JD in a 20 ml sample bottle, add a solution of 0.0021 g ruthenium trichloride (RuCl3) and 0.0221 g cobalt chloride (CoCl2) dissolved in anhydrous ethanol, ultrasonic for 2 h, the obtained viscous sample is placed in a vacuum oven at 70 ℃ for 12 h. The obtained solid powder is placed in an agate mortar and ground into powder, then moved to a tube furnace, calcined at 800 ℃ for 2 h under a hydrogen-argon mixed gas (5% H2 / 95% Ar) atmosphere, the heating rate is 10 ℃ / min, the obtained solid powder is calcined at 550 ℃ for 1.5 h in air to obtain Ru-doped Co3O4 nanomaterial.
[0052] Figure 4 The XRD spectrum of the Ru-Co3O4 composite nanomaterial prepared in this example is shown in the figure, it can be seen from the figure that diffraction peaks corresponding to Co3O4 appear at 18.9°, 31.18°, 36.81°, 44.68°, 55.53°, 65.18° and 77.24°, and no diffraction peak corresponding to RuO2 appears. The above peaks are all shifted by a certain angle from the standard diffraction peaks of Co3O4. The above results show that the Ru-doped Co3O4 nanomaterial is successfully prepared in this comparative example.
[0053] Comparative Example 4: This comparative example provides a Co-RuO2 nanomaterial, in which the carbon is conductive carbon black (specific model Ketjenblack EC-600 JD). The specific preparation method of this comparative example is as follows: 0.05 g of Ketjenblack EC-600 JD was placed in a 20 ml sample vial, and an anhydrous ethanol solution containing 0.0353 g of ruthenium trichloride (RuCl3) and 0.0013 g of cobalt chloride (CoCl2) was added. After sonication for 2 h, the resulting viscous sample was dried in a vacuum oven at 70 ℃ for 12 h. The resulting solid powder was ground into powder in an agate mortar, and then transferred to a tube furnace and calcined at 800 ℃ for 2 h in a hydrogen-argon mixed atmosphere (5% H2 / 95% Ar) at a heating rate of 10 ℃ / min. The resulting solid powder was then calcined in air at 400 ℃ for 4 h to obtain Co-doped RuO2 nanomaterials.
[0054] Figure 5 The XRD pattern of the Co-doped RuO2 composite nanomaterial prepared in this embodiment shows that diffraction peaks corresponding to RuO2 appear at 27.97°, 35.15°, 40.18°, 40.66°, 54.33°, 57.95°, 59.55°, 65.7°, 67.08°, and 74.25°, while no diffraction peaks corresponding to Co3O4 appear. These peaks are all shifted by a certain angle from the standard diffraction peaks of RuO2. These results indicate that Co-doped RuO2 nanomaterials were successfully prepared in this comparative example.
[0055] The present invention conducted the following tests on the interdoped RuO2-Co3O4 composite nanomaterials prepared in Example 1 and Comparative Examples 1-4: A three-electrode testing system was used with 0.1 M HClO4 as the electrolyte at room temperature using a CHI-760E electrochemical station. Platinum foil was used as the counter electrode, and Ag / AgCl as the reference electrode. A catalyst slurry was prepared using ultrapure water, isopropanol (v / v = 3:1), and a certain amount of 5 wt% Nafion solution. 10 μL of the catalyst slurry was placed on carbon paper (d = 5 mm, geometric electrode area 0.196 cm²). 2 The catalyst was loaded onto a substrate and dried in air to prepare the working electrode. All samples had a catalyst loading of 0.8 mg / cm³. -2 Linearity scans were tested in an O2-saturated 0.1 M HClO4 solution at a scan rate of 5 mV / s. -1 .
[0056] In evaluating the catalytic activity of catalysts for the oxygen evolution reaction, a current density of 10 mA cm⁻¹ is typically selected. -2 The overpotential is calculated using the voltage at a given point. A lower overpotential indicates higher catalytic activity for the oxygen evolution reaction.
[0057] from Figure 6As can be seen, the inter-doped RuO2-Co3O4 (atomic ratio of Ru and Co is 1:1) catalyst of Example 1 has an overpotential of 237 mV at a current density of 10 mA cm -2 which is significantly lower than the pure Co3O4 provided by Comparative Example 1, the pure RuO2 catalyst provided by Comparative Example 2, the Ru-doped Co3O4 catalyst provided by Comparative Example 3, and the Co-doped RuO2 catalyst provided by Comparative Example 4 (respectively: 506 mV, 310 mV, 520 mV, and 247 mV). This indicates that the inter-doped ruthenium dioxide and tricobalt tetroxide composite nanomaterial effectively improves the performance of OER, and the ruthenium doping and cobalt doping regulates the electronic structure of the oxide; and the material with an atomic ratio of Ru and Co of 1:1 reduces the use of noble metal Ru to a certain extent.
[0058] The above description of the embodiments is to facilitate the understanding and use of the invention by those of ordinary skill in the art. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to go through creative labor. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.
Claims
1. A mutual doped ruthenium dioxide and tricobalt tetraoxide composite nanomaterial for oxygen evolution reaction, characterized in that, The ruthenium-doped cobalt trioxide and cobalt-doped ruthenium dioxide form a heterojunction structure, the ruthenium doping is in the crystal lattice of cobalt trioxide, and the cobalt doping is in the crystal lattice of ruthenium dioxide. 2.The inter-doped RuO 2 and Co 3 O 4 composite nanomaterial for oxygen evolution reaction according to claim 1, wherein, The atomic ratio of ruthenium and cobalt in the ruthenium-doped cobalt trioxide and cobalt-doped ruthenium dioxide composite nanomaterial is 0.2-5:
1.
3. A method for preparing the inter-doped Ru02 and Co3O4 composite nanomaterial for oxygen evolution reaction according to any one of claims 1-2, characterized in that, The method comprises the following steps: uniformly mixing a carbon precursor, a cobalt salt precursor and a ruthenium salt precursor, and then sequentially performing first-stage calcination in a specific atmosphere and second-stage calcination in an oxygen-containing atmosphere to obtain the ruthenium-doped cobalt trioxide and cobalt-doped ruthenium dioxide composite nanomaterial.
4. The method for preparing the inter-doped Ru02 and Co3O4 composite nanomaterial for oxygen evolution reaction according to claim 3, characterized in that, The carbon precursor comprises any one of natural carbon materials, artificial carbon materials or derived carbon materials; the cobalt salt precursor comprises any one or more of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt acetylacetonate or cobalt sulfate; and the ruthenium salt precursor comprises any one or more of ruthenium nitrate, ruthenium chloride, ruthenium acetylacetonate or ruthenium acetate.
5. The method for preparing the inter-doped Ru02 and Co3O4 composite nanomaterial for oxygen evolution reaction according to claim 3, characterized in that, The specific mixing method comprises any one or more of grinding mixing, dipping, ultrasonic mixing and rotary evaporation, wherein the solvent used in the dipping, ultrasonic mixing and rotary evaporation comprises any one or more of water, ethanol, methanol, acetone, ethylene glycol or isopropyl alcohol. 6.The method for preparing the inter-doped RuO 2 and Co 3 O 4 composite nanomaterial for oxygen evolution reaction according to claim 3, characterized in that, When the carbon precursor, the cobalt salt precursor and the ruthenium salt precursor are mixed, the total mass of cobalt in the cobalt salt precursor and ruthenium in the ruthenium salt precursor accounts for 0.5%-50% of the mass of the carbon precursor, and the molar ratio of ruthenium in the ruthenium salt precursor to cobalt in the cobalt salt precursor is 0.2-5:
1. 7.The method for preparing the inter-doped RuO 2 and Co 3 O 4 composite nanomaterial for oxygen evolution reaction according to claim 3, characterized in that, The first-stage calcination is performed at a temperature of 600-1200 ℃ for 0.5-12 h. 8.The method for preparing the inter-doped RuO 2 and Co 3 O 4 composite nanomaterial for oxygen evolution reaction according to claim 3, characterized in that, The specific atmosphere comprises any one of argon, nitrogen, helium, hydrogen-nitrogen mixed gas, hydrogen-argon mixed gas, hydrogen-helium mixed gas, carbon monoxide-nitrogen mixed gas, carbon monoxide-argon mixed gas, carbon monoxide-helium mixed gas, hydrogen or carbon monoxide, the volume concentration of hydrogen in the hydrogen-nitrogen mixed gas, the hydrogen-argon mixed gas and the hydrogen-helium mixed gas is 0.1-30%, and the volume concentration of carbon monoxide in the carbon monoxide-nitrogen mixed gas, the carbon monoxide-argon mixed gas and the carbon monoxide-helium mixed gas is 0.1-30%. 9.The method for preparing the inter-doped RuO 2 and Co 3 O 4 composite nanomaterial for oxygen evolution reaction according to claim 3, characterized in that, The second-stage calcination is performed at a temperature of 300-800 ℃ for 0.5-5 h, and the oxygen-containing atmosphere comprises any one of air or oxygen. 10.A use of the ruthenium-doped cobalt trioxide and cobalt-doped ruthenium dioxide composite nanomaterial for an oxygen evolution reaction in an OER catalyst according to any one of claims 1-2.