Preparation method and application of high-curvature carbon nano onion-loaded diatomic catalyst

Abstract

The invention relates to the field of catalytic materials and nanotechnology, in particular to a preparation method and application of a high-curvature carbon nano onion loaded diatomic catalyst, and the preparation method comprises the step of uniformly dispersing and anchoring chromium and iron atoms on a carbon nano onion skeleton through a chemical impregnation method and annealing heat treatment to form an efficient and stable diatomic catalyst. According to the method, the dispersity and stability of metal atoms are remarkably improved by utilizing a high-curvature structure and topological defects of the carbon nano onions, and the coordination environment is optimized through the ammonia atmosphere. The obtained catalyst shows the advantages of excellent oxygen reduction reaction performance, long-term stability and low cost in alkaline electrolyte, and can be widely applied to the technical field of clean energy such as metal-air batteries.

Description

Technical Field

[0001] This invention relates to the field of electrocatalytic material preparation technology, specifically to a method for preparing and applying a high-curvature carbon nanotube onion-supported diatomic catalyst. Background Technology

[0002] With the increasing global demand for clean energy, the application of electrocatalytic materials in energy conversion and storage has attracted much attention. Especially in the oxygen reduction reaction (ORR), efficient and stable electrocatalysts are crucial for improving the performance of hydrogen fuel cells and metal-air batteries. However, existing electrocatalytic materials still have significant shortcomings in terms of active site utilization efficiency, long-term stability, and preparation cost, limiting their large-scale commercial application.

[0003] A search revealed a patent, CN113174608B, which discloses a dual-doped porous cobalt phosphide nanosheet electrocatalytic material and its preparation method, published on October 25, 2022. This patent improves the specific surface area and conductivity of cobalt phosphide nanosheets by doping them with Cr and Fe bimetals, exhibiting good electrocatalytic hydrogen evolution and oxygen evolution performance. However, in this technical solution, the distribution of metal atoms mainly depends on the doping process, making atomic-level precise control difficult and potentially leading to uneven distribution of active sites, affecting catalytic efficiency. Furthermore, the structural stability of the cobalt phosphide substrate may be challenged at high current densities, especially during long-term operation, where metal atom migration or aggregation can easily occur, leading to catalyst deactivation.

[0004] A search revealed a non-metallic electrocatalytic material, its preparation method, and its applications, published on August 18, 2023, with publication number CN115011972B. This patent describes the preparation of a non-metallic electrocatalytic material with good conductivity and bifunctional catalytic activity by combining graphene oxide with black phosphorus nanosheets. However, in this technical solution, the surface defect types of graphene oxide as a support are relatively homogeneous, making it difficult to achieve strong anchoring of active sites. This may lead to the migration or leaching of metal atoms in the electrochemical environment, reducing the long-term stability of the catalyst. Furthermore, black phosphorus nanosheets exhibit poor chemical stability in humid environments, which may further limit their durability in practical applications.

[0005] The aforementioned problems indicate that existing electrocatalytic materials still have shortcomings in terms of precise anchoring of active sites, long-term stability, and optimized design of support materials. In particular, regarding the preparation and application of diatomic catalysts supported on high-curvature carbon substrates, current technologies have not fully exploited the unique structural advantages of high-curvature carbon materials, nor have they effectively solved the stability problem of diatomic sites under harsh electrochemical environments. Therefore, this invention aims to provide a method for preparing and applying diatomic catalysts supported on high-curvature carbon nanotubes. By fully utilizing the abundant topological defects and electronic properties of high-curvature carbon materials, precise and stable anchoring of diatomic sites can be achieved, thereby significantly improving the ORR activity, selectivity, and long-term stability of the catalyst, meeting the needs of next-generation high-performance electrocatalysts. Summary of the Invention

[0006] This application provides a high-curvature carbon nanotube onion-supported diatomic catalyst (Onion-CrFe). DSA The preparation method and application of the catalyst aim to uniformly disperse and anchor chromium and iron atoms on a carbon nanotube onion framework through a combination of chemical impregnation and annealing heat treatment, forming a highly active and stable diatomic catalyst.

[0007] One objective of this invention is to provide a method for preparing high-curvature carbon nanotube onion-supported diatomic catalysts, comprising the following steps:

[0008] Carbon nanoparticles and chromium trichloride were added to an ethanol solvent, and chromium atoms from the chromium trichloride were uniformly dispersed on the surface of the carbon nanoparticles through chemical impregnation. Subsequent annealing heat treatment yielded Onion-Cr. SA Precursor;

[0009] The above Onion-Cr SA The precursor is mixed with phthalocyanine iron, and the iron atoms in phthalocyanine iron are uniformly dispersed on the surface of the precursor through a two-stage chemical impregnation method, finally obtaining the target catalyst Onion-CrFe. DSA .

[0010] This invention uses ethanol as a solvent, which improves the environmental friendliness of the process and reduces solvent costs.

[0011] Preferably, the mass ratio of the carbon nano-onion to chromium trichloride is 100:(1-5).

[0012] Preferably, the reaction temperature of the chemical impregnation method is 80–200°C.

[0013] Preferably, the annealing heat treatment temperature is 200-500℃ and the time is 1-5 hours.

[0014] Preferably, the annealing heat treatment is carried out in an ammonia atmosphere.

[0015] Preferably, the Onion-Cr SA The mass ratio of the precursor to ferrophthalocyanine is 100:(10-25).

[0016] Preferably, the secondary chemical impregnation method is carried out at room temperature for 12 to 36 hours.

[0017] A second objective of this invention is to provide a high-curvature carbon nanotube onion-supported diatomic catalyst obtained by the above-described preparation method. The main morphology of the high-curvature carbon nanotube onion-supported diatomic catalyst is onion-shaped, wherein chromium and iron atoms are uniformly supported on the onion framework.

[0018] A third objective of this invention is to provide the application of the aforementioned high-curvature carbon nanoparticle onion-supported diatomic catalyst in electrochemical catalytic reactions.

[0019] Preferably, the electrochemical catalysis includes an oxygen reduction reaction, particularly an alkaline oxygen reduction reaction.

[0020] The beneficial effects of this invention are:

[0021] (1) The high curvature carbon nanotube onion-supported diatomic catalyst prepared by the present invention precisely controls the formation density and coordination environment of diatomic sites, thereby achieving efficient and uniform loading of diatomic sites.

[0022] (2) The high curvature carbon nanotube onion-supported diatomic catalyst prepared in this invention exhibits superior ORR catalytic activity in alkaline electrolytes compared to commercial platinum-carbon (Pt / C) catalysts, with higher half-wave potential (E1 / 2) and onset potential.

[0023] (3) The high curvature carbon nanotube onion-supported diatomic catalyst prepared in this invention uses two non-precious metals, chromium and iron, as active centers, which greatly reduces material costs.

[0024] (4) The present invention uses a simple chemical impregnation method and annealing heat treatment to obtain a high curvature carbon nanotube onion-supported diatomic catalyst. Its preparation process is simple, the conditions are controllable, and it is easy to scale up production.

[0025] (5) The high curvature carbon nanotube onion-supported diatomic catalyst prepared in this invention can be widely used as a cathode catalyst in energy conversion and storage devices such as metal-air batteries (e.g., zinc-air batteries) based on its excellent ORR performance. It is expected to significantly improve the output power, energy efficiency and cycle life of the battery and promote the practical application of clean energy technology. Attached Figure Description

[0026] Figure 1 Onion-CrFe prepared in Example 1 of this inventionDSA X-ray diffraction pattern of the catalyst;

[0027] Figure 2 Onion-CrFe prepared in Example 1 of this invention DSA Transmission electron microscopy image of the catalyst;

[0028] Figure 3 Onion-CrFe prepared in Example 1 of this invention DSA Polarization curves of the catalyst and a commercial Pt / C catalyst in 0.1 M KOH electrolyte for electrocatalytic oxygen reduction reaction;

[0029] Figure 4 Onion-CrFe prepared in Example 1 of this invention DSA A schematic diagram of a zinc-air battery assembled with the catalyst as the cathode material. Detailed Implementation

[0030] To make the technical means, creative features, and achieved objectives and effects of this invention readily understandable, the invention is further described below with reference to specific embodiments and illustrations. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used without specified manufacturers are all conventional products that can be obtained commercially.

[0031] Example 1

[0032] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0033] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 3.13 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 80 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 350°C for 2 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0034] (2) 100 mg of the above Onion-Cr SAThe precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 18 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 24 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0035] Onion-CrFe prepared in Example 1 DSA The catalyst was characterized and the results are shown in the figure. Figure 1-3 .

[0036] First, the Onion-CrFe prepared in this embodiment... DSA The catalyst was subjected to X-ray diffraction (XRD) testing, and the obtained XRD pattern is as follows: Figure 1 As shown in the figure, analysis reveals that the Onion-CrFe prepared in Example 1... DSA The XRD pattern of the catalyst showed two broad peaks near 26° and 44°, which are typical diffraction planes of the carbon framework. No related elemental metal peaks or metal oxide peaks were found in the pattern, indicating that the influence of the incorporation of Cr and Fe atoms on the crystal phase is negligible.

[0037] Next, the Onion-CrFe prepared in this embodiment was analyzed. DSA The catalyst was tested using transmission electron microscopy (TEM), and the results are as follows: Figure 2 As shown, from Figure 2 (a) High-resolution TEM (HRTEM) images show Onion-CrFe DSA The catalyst exhibits a high curvature characteristic of an onion-like morphology, with a diameter of approximately 5 nanometers; from Figure 2 (b) Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) revealed that isolated metal single atoms were highly dispersed on carbon nanoparticles, indicating Onion-CrFe DSA Successful synthesis of the catalyst.

[0038] Example 2

[0039] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0040] (1) First, 100 mg of carbon nanoparticles were dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nanoparticles in the ethanol. Then, 2.5 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 150 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 300℃ for 3 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0041] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 15 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 12 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0042] Example 3

[0043] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0044] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 2 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 100 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 200℃ for 3 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0045] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 10 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 15 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0046] Example 4

[0047] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0048] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 1.5 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 150 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 400℃ for 4 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0049] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 20 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 24 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0050] Example 5

[0051] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0052] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 3 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 200 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 500℃ for 5 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0053] (2) 100 mg of the above Onion-Cr SAThe precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 25 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 36 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0054] Example 6

[0055] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0056] (1) First, 100 mg of carbon nanoparticles were dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nanoparticles in the ethanol. Then, 3 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 150 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 350℃ for 3.5 hours, successfully yielding black Onion-Cr. SA Precursor.

[0057] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 20 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 24 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0058] Example 7

[0059] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0060] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 2.5 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 120 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1The heating rate was annealed at 300℃ for 2 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0061] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 15 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 36 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0062] Example 8

[0063] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0064] (1) First, 100 mg of carbon nanoparticles were dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nanoparticles in the ethanol. Then, 1 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 100 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 400℃ for 3 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0065] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 25 mg of iron phthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 18 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0066] Example 9

[0067] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0068] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 1.5 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 80 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 300℃ for 4 hours, and black Onion-Cr was successfully obtained. SA Precursor.

[0069] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 20 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 30 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0070] Example 10

[0071] This embodiment of Onion-CrFe DSA The catalyst is prepared as follows:

[0072] (1) First, 100 mg of carbon nano-onion was dissolved in 25 mL of ethanol and sonicated for 30 minutes to ensure uniform dispersion of the carbon nano-onion in the ethanol. Then, 2.5 mL of 0.01 M CrCl3 ethanol solution was slowly added to the solution, and the mixture was sonicated again for 30 minutes. The resulting solution was then magnetically stirred at 160 °C to evaporate the remaining ethanol. The solid product obtained after evaporation was ground into a fine powder and then subjected to an ammonia atmosphere at 5 °C for 1 minute. -1 The heating rate was annealed at 450℃ for 1 hour, and black Onion-Cr was successfully obtained. SA Precursor.

[0073] (2) 100 mg of the above Onion-Cr SA The precursor was uniformly dispersed in 25 mL of ethanol to form solution A, and then 25 mg of ferrophthalocyanine was dispersed in 10 mL of ethanol to form solution B. Solution B was added to solution A, and the mixture was sonicated and magnetically stirred at room temperature for 24 hours to ensure thorough mixing. The resulting mixture was then centrifuged several times, and the final solid product was ground into a fine powder to obtain black Onion-CrFe. DSA Catalyst powder.

[0074] The following are examples of applications of high-curvature carbon nanotube onion-supported diatomic catalysts in electrochemical catalytic reactions.

[0075] Application Example 1

[0076] The Onion-CrFe prepared in Example 1 DSA The catalyst is used in the electrocatalytic alkaline oxygen reduction reaction, and the specific process is as follows:

[0077] Take 5 mg of the Onion-CrFe prepared in Example 1 above. DSA The catalyst was dissolved in a mixed solution of 300 μL deionized water and 700 μL isopropanol, and 50 μL of 5 wt% Nafion reagent was added. The solution was ultrasonically dispersed for 40–60 minutes to obtain a uniformly dispersed catalyst ink. Subsequently, 10 μL of the catalyst ink was dropped onto GCE (with a loading of 0.256 mg / cm³). -2 The electrode was dried at room temperature to obtain the working electrode; using a standard three-electrode system with 0.1M KOH as the electrolyte and a platinum mesh (1cm) as the electrode, the electrode was prepared. 2 The electrode used was the counter electrode, and the silver / silver chloride electrode was the reference electrode. Oxygen reduction tests were performed on an electrochemical workstation. Before the test, the electrolyte was bubbled with N2 / O2 for 30 minutes, and bubbling continued throughout the test to ensure N2 / O2 saturation. Linear sweep voltammetry (LSV) was performed in the range of 0.2–1.1 V (vs RHE) at a scan rate of 5 mV / s and a rotation speed of 1600 rpm. The polarization curves are shown below. Figure 3 As shown.

[0078] from Figure 3 It can be seen that the Onion-CrFe prepared in Example 1 DSA The polarization curve of the catalyst in 0.1M KOH electrolyte for the electrocatalytic oxygen reduction reaction has an onset potential of approximately 0.986V (vs RHE) and a half-wave potential (E) 1 / 2 The voltage reached 0.916V (vs RHE), which is superior to commercial Pt / C catalysts (E). 1 / 2 ≈0.884V (vs RHE) can be used as an alternative. Figure 3 The commercially available Pt / C catalyst used is a 20% Pt / C catalyst, model SPT-20.

[0079] Application Example 2

[0080] The Onion-CrFe prepared in Example 1 DSA The catalyst is used in zinc-air batteries, and the specific process is as follows:

[0081] The anode material is a 0.3 mm thick polished zinc plate, and the cathode material is a composite structure consisting of carbon paper / hydrophobic layer / nickel foam (catalyst loading is 1 mg cm⁻¹). -2 The electrolyte is 6M KOH containing 0.2M zinc acetate; assembling it yields a zinc-air battery that can power an LED display, such as... Figure 4 As shown.

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A method for preparing high-curvature carbon nanooilive supported diatomic catalysts, characterized by: It comprises the following steps: Carbon nanometer onion and chromium trichloride are added into an ethanol solvent, chromium atoms in the chromium trichloride are uniformly dispersed on the surface of the carbon nanometer onion by a chemical immersion method, and then annealing heat treatment is performed, so that the Onion-Cr is obtained SA precursor The Onion-Cr Fe was prepared by the following steps: SA The precursor was mixed with iron phthalocyanine, and the iron atoms in the iron phthalocyanine were uniformly dispersed on the surface of the precursor by a secondary chemical immersion method, and finally the target catalyst Onion-Cr Fe was obtained. DSA .

2. The production method according to claim 1, characterized by: The mass ratio of the carbon nano-onions to the chromium trichloride is 100:(1-5).

3. The production method according to claim 1, wherein: The reaction temperature of the chemical immersion method is 80-200 ℃.

4. The production method according to claim 1, wherein: The Onion-Cr SA The mass ratio of the precursor to the iron phthalocyanine is 100:(10-25).

5. The production method according to claim 1, wherein: The annealing heat treatment temperature is 200-500 ℃, and the time is 1-5 hours.

6. The production method according to claim 1, wherein: The reaction temperature of the secondary chemical immersion method is room temperature, and the reaction time is 12-36 hours.

7. A high-curvature carbon nanonion supported diatomic catalyst prepared according to the method of any one of claims 1 to 6, characterized by: The catalyst body morphology is onion-shaped, and the diameter is about 5 nanometers, wherein the chromium and iron atoms are uniformly loaded on the onion skeleton.

8. Application of the high-curvature carbon nano-onion loaded diatomic catalyst of claim 7 in an electrochemical catalytic reaction.

9. Use according to claim 8, characterized in that: The electrochemical catalytic reaction comprises an electrocatalytic oxygen reduction reaction.

10. Use according to claim 8, characterized in that: The electrocatalytic reaction is an alkaline oxygen reduction reaction.

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