A biomimetic non-noble metal oxygen reduction catalyst and a preparation method and application thereof

Abstract

The application provides a kind of bionic non-noble metal oxygen reduction catalyst and its preparation method and application, it is related to fuel cell material field.The ORR catalyst selects fluorinated carbon nanotube with high specific surface area, certain conductivity and chemical stability, then it is azido functionalized, the hydrophilicity / hydrophobicity of carbon material is controlled by controlling the degree of functionalization, then the stability of target catalyst is controlled, then it is grafted by "Click" reaction with nitrogen-containing ligand, and then it is coordinated with iron porphyrin to prepare a bionic single-atom catalyst with FeN5 site.The bionic catalyst of the application has a clear active center, good oxygen reduction reaction activity and excellent electrochemical stability.The bionic catalyst of the application has great application prospect in the oxygen reduction reaction of fuel cell, and provides a new method for the regulation of oxygen reduction reaction catalyst.

Description

Technical Field

[0001] This invention relates to the field of fuel cell materials, specifically to a biomimetic non-precious metal oxygen reduction catalyst, its preparation method, and its application. Background Technology

[0002] Electrochemical energy systems such as fuel cells and metal-air batteries have great potential as clean energy sources in the field of electric power transmission, reducing various energy and environmental problems. In these energy systems, the oxygen reduction reaction (ORR) at the cathode is the rate-determining factor for the overall system performance. To date, platinum (Pt) and its alloys-based catalysts, especially Pt, remain the highest-performing and most practical ORR electrocatalysts. However, the precious metal platinum (Pt) suffers from drawbacks such as resource scarcity, high price, and susceptibility to methanol poisoning, severely limiting the large-scale application of fuel cells. Therefore, developing efficient and stable non-precious metal cathode ORR electrocatalysts to replace traditional platinum catalysts is essential.

[0003] Most traditional non-precious metal catalysts are obtained through the pyrolysis of precursors. While pyrolysis improves the catalyst's activity, it also destroys its original structure. Therefore, pyrolysis-based catalysts are not conducive to the study of active sites, which often require the assistance of other indirect techniques and methods for identification. Summary of the Invention

[0004] The purpose of this invention is to provide a biomimetic non-precious metal oxygen reduction catalyst, its preparation method and application. This biomimetic catalyst material has a well-defined central structure, good catalytic activity for oxygen reduction reaction, excellent stability, and good methanol tolerance.

[0005] This invention first provides a biomimetic non-noble metal oxygen reduction catalyst, with the following structure:

[0006] This invention also provides a method for preparing a biomimetic non-noble metal oxygen reduction catalyst, the method comprising: Step 1: Weigh out fluorinated carbon nanotubes and sodium azide and disperse them in a mixed solvent. Reflux and stir under heating conditions to obtain azide-functionalized carbon nanotubes FCNT-N3. Step 2: Under argon atmosphere, imidazole, potassium phosphate, and cuprous iodide are added to DMF solution and reacted. Then, 4-bromoiodobenzene is added and the reaction is stirred under heating to obtain 4-bromo-phenylimidazolium 4-Br-PhIm. Step 3: Under argon atmosphere, 4-Br-PhIm from Step 2, along with palladium acetate, cuprous iodide, triphenylphosphine, and trimethylsilaneacetylene, are added to triethylamine and stirred under heating conditions to obtain 4-trimethylsilylacetylenebenzamide 4-TMSAce-PhIm. Step 4: Under argon atmosphere, disperse the 4-TMSAce-PhIm from Step 3 into DMF solution, add tetrabutylamine fluoride at 0 °C, then raise to room temperature and stir to deprotect, then add FCNTs-N3 obtained in Step 1, copper sulfate pentahydrate, and sodium ascorbate, and heat to react to obtain imidazole-functionalized carbon nanotubes FCNT-Im; Step 5: Under argon atmosphere, disperse the FCNT-Im from Step 4 and perfluoroiron porphyrin in methanol solvent and heat to react, thus obtaining a biomimetic non-noble metal oxygen reduction catalyst.

[0007] Preferably, the mass ratio of fluorinated carbon nanotubes to sodium azide in step one is 1:20.

[0008] Preferably, the mixed solvent in step one is a mixture of water and DMF, with a volume ratio of water to DMF of 1:4.

[0009] Preferably, the reflux stirring time in step one is 72 hours.

[0010] Preferably, the molar ratio of imidazole, potassium phosphate, and 4-bromoiodobenzene in step two is 1.2:1.2:1.

[0011] Preferably, the molar ratio of 4-Br-PhIm to trimethylsilaneacetylene in step three is 9:11.

[0012] Preferably, the mass ratio of 4-TMSAce-PhIm and FCNTs-N3 in step four is 4:1.

[0013] Preferably, the mass ratio of FCNT-Im to perfluoroiron porphyrin in step five is 3:1.

[0014] This invention also provides the application of the above-mentioned biomimetic oxygen reduction catalyst in the field of fuel cells.

[0015] Beneficial effects of the present invention This invention provides a biomimetic non-noble metal oxygen reduction catalyst, its preparation method, and its application. The biomimetic catalyst utilizes fluorinated carbon nanotubes (FCNTs) with high specific surface area, certain conductivity, and chemical stability. These FCNTs are then N3 functionalized. The hydrophilicity / hydrophobicity of the carbon material is controlled by varying the degree of functionalization (F / N3), thereby controlling the stability of the target catalyst. Subsequently, a "Click" reaction is performed with nitrogen-containing ligands for grafting, followed by coordination with iron porphyrin to prepare a biomimetic single-atom catalyst with FeN5 sites. The preparation method of this biomimetic catalyst is a non-pyrolytic covalent grafting process, resulting in a well-defined structure. Each grafting reaction and its outcome are characterized using corresponding techniques, thus ensuring a clear and well-defined structure. The F / N3 ratio is controlled by varying the degree of N3 functionalization of the FCNTs, thereby regulating the hydrophilicity / hydrophobicity and the catalyst's stability. Increasing the degree of N3 functionalization increases the grafting amount of imidazole (Im), which then coordinates with iron porphyrin to prepare a high-density FeN5-type single-atom catalyst, thus controlling the catalyst's activity.

[0016] This invention prepares a structurally controllable non-noble metal catalyst using a covalent grafting method. Fluorocarbon nanotubes are used as a substrate, subsequently functionalized with azide (N3), and then grafted with other groups via a "Click" reaction. Finally, the catalyst is coordinated with an iron-based macrocyclic compound to prepare a structurally controllable and highly efficient ORR catalyst. Experimental results show that the biomimetic catalyst of this invention has a well-defined active center, good oxygen reduction reaction activity, and excellent electrochemical stability. This biomimetic catalyst has great application potential in the oxygen reduction reaction of fuel cells and provides a new method for the regulation of oxygen reduction reaction catalysts. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the preparation process of the biomimetic catalyst FCNT-Im-FTPPFe described in this invention; Figure 2 This is the proton NMR spectrum of 4-trimethylsilylacetylenoid benzimidazole described in Example 1 of this invention; Figure 3 These are the infrared spectra of the biomimetic catalysts FCNT, FCNT-N3, FCNT-Im, and FCNT-Im-FTPPFe described in Example 1 of this invention; Figure 4 This is the energy dispersive spectroscopy (EDS) spectrum of FCNT-Im as described in Embodiment 1 of the present invention; Figure 5 This is the energy dispersive spectroscopy (EDS) spectrum of the biomimetic catalyst FCNT-Im-FTPPFe described in Example 1 of this invention; Figure 6The ORR polarization curve of the biomimetic catalyst FCNT-Im-FTPPFe described in Example 1 of this invention; Figure 7 This is the chronoamperometry spectrum of the biomimetic catalyst FCNT-Im-FTPPFe described in Example 1 of this invention; Figure 8 This is the methanol resistance test spectrum of the biomimetic catalyst FCNT-Im-FTPPFe described in Example 1 of this invention. Detailed Implementation

[0018] This invention first provides a biomimetic non-noble metal oxygen reduction catalyst, with the following structure:

[0019] This invention also provides a method for preparing a biomimetic non-noble metal oxygen reduction catalyst, such as... Figure 1 As shown, the method includes: Step 1: Weigh out fluorinated carbon nanotubes (FCNT) and sodium azide (NaN3) and disperse them in a mixed solvent, preferably a mixture of water and DMF, wherein the volume ratio of water to DMF is preferably 1:4. Reflux and stir under heating conditions, preferably for 24-96 hours, more preferably 72 hours. After the reaction is complete, wash the reaction liquid, filter, and dry to obtain azide-functionalized carbon nanotubes (FCNT-N3); the mass ratio of FCNT to NaN3 in Step 1 is preferably 1:20. Step 2: Under argon atmosphere, imidazole, potassium phosphate, and cuprous iodide are added to a DMF solution and reacted. The reaction time is preferably 30 minutes. Then, 4-bromoiodobenzene is added, and the mixture is stirred under heating. The heating temperature is preferably 90-130 °C, and the heating time is preferably 8-16 hours, more preferably 12 hours. After the reaction is complete, the mixture is purified, filtered, and dried to obtain 4-bromo-phenylimidazolium (4-Br-PhIm). The molar ratio of imidazole, potassium phosphate, and 4-bromoiodobenzene is preferably 1.2:1.2:1, and the molar ratio of cuprous iodide to imidazole is preferably 1:100.

[0020] Step 3: Under argon atmosphere, the 4-Br-PhIm from Step 2, along with palladium acetate, cuprous iodide, triphenylphosphine, and trimethylsilaneacetylene, are added to triethylamine. The mixture is stirred under heating at 70-90 °C for 18-30 hours, more preferably 24 hours. After the reaction, the liquid is concentrated, subjected to column chromatography, and rotary evaporation to obtain 4-trimethylsilylacetylbenzamide (4-TMSAce-PhIm). The preferred molar ratio of 4-Br-PhIm to trimethylsilaneacetylene is 9:11, and the preferred molar ratio of palladium acetate, cuprous iodide, and triphenylphosphine is 2:1:4. In the column chromatography step, the preferred eluents are ethyl acetate and petroleum ether, with a preferred volume ratio of 1:1. Step 4: Under argon atmosphere, disperse the 4-TMSAce-PhIm from Step 3 into a DMF solution, and add tetrabutylamine fluoride at 0 °C. Then, raise the temperature to room temperature and stir to remove the protection. The stirring time is preferably 2-4 hours, more preferably 3 hours. Then add FCNTs-N3, copper sulfate pentahydrate, and sodium ascorbate, and heat the reaction. The heating temperature is 40-60 °C, and the heating time is preferably 24-48 hours, more preferably 36 hours. Wash and dry to obtain imidazole-functionalized carbon nanotubes (FCNT-Im). The mass ratio of 4-TMSAce-PhIm to FCNTs-N3 is preferably 4:1, the volume ratio of tetrabutylamine fluoride is preferably 0.2 mL, and the molar ratio of copper sulfate pentahydrate to sodium ascorbate is preferably 2:1.

[0021] Step 5: Under argon atmosphere, disperse FCNT-Im from Step 4 and perfluoroiron porphyrin (FTPPFe) in methanol solvent and heat to react. The heating temperature is 40-60 °C, and the heating time is preferably 8-16 hours, more preferably 12 hours, to obtain the final sample biomimetic non-noble metal oxygen reduction catalyst (FCNT-Im-FTPPFe). The preferred mass ratio of FCNT-Im to FTPPFe is 3:1.

[0022] This invention also provides the application of the above-mentioned biomimetic oxygen reduction catalyst in the field of fuel cells.

[0023] The present invention will be further described in detail below with reference to specific embodiments. All raw materials involved in the embodiments are commercially available.

[0024] Example 1 Step 1: Weigh out fluorinated carbon nanotubes (FCNT) and sodium azide (NaN3) in a mass ratio of 1:20 and disperse them in a mixed solvent (H2O:DMF=1:4). Reflux and stir for 72 hours under heating conditions. After the reaction is complete, wash the reaction liquid, filter it, and collect the dried azide-functionalized carbon nanotubes (FCNT-N3) for later use. Step 2: Under argon atmosphere, 0.817 g imidazole, 1.659 g potassium phosphate, and 0.038 g cuprous iodide were added to 20 mL of DMF solution and reacted for half an hour. Then, 2.829 g of 4-bromoiodobenzene was added, and the mixture was stirred at 110 °C for 12 hours. After the reaction was completed, the mixture was purified, filtered, and dried to obtain 4-bromo-phenylimidazolium (4-Br-PhIm).

[0025] Step 3: Under argon atmosphere, 1.213 g of 4-Br-PhIm from Step 2, along with 0.045 g of palladium acetate, 0.019 g of cuprous iodide, 0.105 g of triphenylphosphine, and 1.6 mL of trimethylsilylacetylene, were added to 30 mL of triethylamine. The mixture was stirred at 80 °C for 24 hours. After the reaction was completed, the liquid was concentrated and subjected to column chromatography (eluent: ethyl acetate: petroleum ether = 1:1). The 4-trimethylsilylacetylenebenzamide (4-TMSAce-PhIm) was collected after rotary evaporation.

[0026] Step 4: Under argon atmosphere, disperse 120 mg of 4-TMSAce-PhIm from Step 3 into 40 mL of DMF solution, and add 0.2 mL of tetrabutylamine fluoride at 0 °C. Then, raise the temperature to room temperature and stir for 3 hours to remove the protection. Add 30 mg of FCNTs-N3, 6 mg of copper sulfate pentahydrate, and 25 mg of sodium ascorbate. React at 50 °C for 36 hours. Wash and dry to obtain imidazole-functionalized carbon nanotubes (FCNT-Im).

[0027] Step 5: Under argon atmosphere, disperse 30 mg FCNT-Im and 10 mg perfluoroiron porphyrin (FTPPFe) from Step 4 in 20 mL of methanol solvent, heat to 50 °C, and react for 12 hours to obtain the final sample (FCNT-Im-FTPPFe).

[0028] Figure 2 The image shows the 1H NMR spectrum of 4-trimethylsilylacetylenoid benzimidazole prepared in Example 1. 1 ¹H NMR (400MHz, deuterated chloroform) δ 7.83 (s, 1H), 7.54 – 7.48 (m, 2H), 7.30 – 7.21 (m, 3H), 7.16 (s, 1H). In addition, nine additional hydrogen atoms were observed at 0.20 ppm, corresponding to hydrogen atoms in the trimethyl group. This result verifies the successful preparation of 4-trimethylsilylacetylenide benzimidazole.

[0029] Figure 3 These are the infrared spectra of FCNT, FCNT-N3, FCNT-Im, and FCNT-Im-FTPPFe prepared in Example 1. The 2130 cm⁻¹ spectrum of FCNT-N3 is shown.-1 The N3 characteristic peak at 1426 cm⁻¹ indicates the azidation functionalization of the fluorinated carbon nanotubes in step one; the FCNT-Im peak at 1426 cm⁻¹... -1 A wider peak appears at 1091 cm. -1 The appearance of new peaks, all corresponding to the characteristic peaks of the triazole ring, indicates the successful execution of the Click reaction in step four, yielding imidazole-functionalized fluorinated carbon nanotubes. The appearance of multiple new peaks and broader peaks in FCNT-Im-FTPPFe indicates a difference from FCNT-Im, suggesting successful coordination between FCNT-Im and FTPPFe.

[0030] Figure 4 This is the energy dispersive spectroscopy (EDS) spectrum of FCNT-Im from Example 1. The detection of nitrogen in the spectrum also verifies the successful preparation of imidazole-functionalized FCNTs.

[0031] Figure 5 This is the energy dispersive spectroscopy (EDS) spectrum of FCNT-Im-FTPPFe in Example 1. (Compared to...) Figure 4 Compared to the previous year, the nitrogen content in the sample increased, which also verifies the successful coordination of FTPPFe and FCNT-Im.

[0032] Figure 6 This is the ORR polarization curve of the catalyst FCNT-Im-FTPPFe in Example 1. The test involved adding 4 mg of FCNT-Im-FTPPFe to 200 μL of a mixed solution of Nafion and isopropanol (volume ratio 1:9), followed by ultrasonic dispersion to prepare catalyst ink. This catalyst ink (10 μL) was drop-coated onto the working electrode and allowed to dry naturally, forming a uniform catalyst film. The testing instrument was a CHI 760D electrochemical workstation equipped with a three-electrode system: a graphite rod as the counter electrode and an Hg / HgO electrode as the reference electrode (under alkaline conditions). Under alkaline conditions, the electrolyte solution was a 0.1 M KOH solution. Before the test, oxygen was introduced for 25 min to ensure oxygen saturation in the electrolyte. Then, a linear scan test was started at 1600 rpm and a scan rate of 10 mV / s to test the performance of the FCNT-Im-FTPPFe sample. The results are shown in the figure. The biomimetic catalyst FCNT-Im-FTPPFe exhibits good ORR performance, with a half-wave potential E0. 1 / 2 = -0.12 V (vs. Hg / HgO).

[0033] Figure 7This is the chronoamperometry spectrum of the biomimetic catalyst FCNT-Im-FTPPFe in Example 1. The test was conducted at a constant voltage of 0.55V. After 22 hours of testing, the current density of the catalyst did not decrease and even increased to some extent, indicating that the catalyst has excellent stability. This is due to the presence of fluorine; as the constant voltage test continues, the fluorine is gradually replaced, allowing the current density to be maintained or even increased, thus protecting the active sites of the catalyst and enhancing its stability.

[0034] Figure 8 This is the methanol resistance test spectrum of the biomimetic catalyst FCNT-Im-FTPPFe in Example 1. Under a constant voltage test of 0.55 V, 2 M methanol was added to the electrolyte solution. The graph shows that the addition of methanol only slightly disturbed the current density of the catalyst, which subsequently returned to normal. This indicates that the biomimetic catalyst has good resistance to methanol cross-effects.

[0035] Example 2 Step 1: Weigh out fluorinated carbon nanotubes (FCNT) and sodium azide (NaN3) in a mass ratio of 1:20 and disperse them in a mixed solvent (H2O:DMF=1:4). Reflux and stir for 24 hours under heating conditions. After the reaction is complete, wash the reaction liquid, filter it, and collect the dried azide-functionalized carbon nanotubes (FCNT-N3) for later use. Step 2: Under argon atmosphere, 0.817 g imidazole, 1.659 g potassium phosphate, and 0.038 g cuprous iodide were added to 20 mL of DMF solution and reacted for half an hour. Then, 2.829 g of 4-bromoiodobenzene was added, and the mixture was stirred at 90 °C for 8 hours. After the reaction was completed, the mixture was purified, filtered, and dried to obtain 4-bromo-phenylimidazolium (4-Br-PhIm).

[0036] Step 3: Under argon atmosphere, 1.213 g of 4-Br-PhIm from Step 2, along with 0.045 g of palladium acetate, 0.019 g of cuprous iodide, 0.105 g of triphenylphosphine, and 1.6 mL of trimethylsilylacetylene, were added to 30 mL of triethylamine. The mixture was stirred at 70 °C for 18 hours. After the reaction was completed, the liquid was concentrated and subjected to column chromatography (eluent: ethyl acetate: petroleum ether = 1:1). The 4-trimethylsilylacetylenebenzamide (4-TMSAce-PhIm) was collected after rotary evaporation.

[0037] Step 4: Under argon atmosphere, disperse 120 mg of 4-TMSAce-PhIm from Step 3 into 40 mL of DMF solution, and add 0.2 mL of tetrabutylamine fluoride at 0 °C. Then, raise the temperature to room temperature and stir for 2 hours to deprotect the solution. Add 30 mg of FCNTs-N3, 6 mg of copper sulfate pentahydrate, and 25 mg of sodium ascorbate. React at 40 °C for 24 hours. Wash and dry to obtain imidazole-functionalized carbon nanotubes (FCNT-Im).

[0038] Step 5: Under argon atmosphere, disperse 30 mg FCNT-Im and 10 mg perfluoroiron porphyrin (FTPPFe) from Step 4 in 20 mL of methanol solvent, heat to 40 °C, and react for 8 hours to obtain the final sample (FCNT-Im-FTPPFe).

[0039] Example 3 Step 1: Weigh out fluorinated carbon nanotubes (FCNT) and sodium azide (NaN3) in a mass ratio of 1:20 and disperse them in a mixed solvent (H2O:DMF=1:4). Reflux and stir for 96 hours under heating conditions. After the reaction is complete, wash the reaction liquid, filter it, and collect the dried azide-functionalized carbon nanotubes (FCNT-N3) for later use. Step 2: Under argon atmosphere, 0.817 g imidazole, 1.659 g potassium phosphate, and 0.038 g cuprous iodide were added to 20 mL of DMF solution and reacted for half an hour. Then, 2.829 g of 4-bromoiodobenzene was added, and the mixture was stirred at 130 °C for 16 hours. After the reaction was completed, the mixture was purified, filtered, and dried to obtain 4-bromo-phenylimidazolium (4-Br-PhIm).

[0040] Step 3: Under argon atmosphere, 1.213 g of 4-Br-PhIm from Step 2, along with 0.045 g of palladium acetate, 0.019 g of cuprous iodide, 0.105 g of triphenylphosphine, and 1.6 mL of trimethylsilylacetylene, were added to 30 mL of triethylamine. The mixture was stirred at 90 °C for 30 hours. After the reaction was completed, the liquid was concentrated and subjected to column chromatography (eluent: ethyl acetate: petroleum ether = 1:1). The 4-trimethylsilylacetylenebenzamide (4-TMSAce-PhIm) was collected after rotary evaporation.

[0041] Step 4: Under argon atmosphere, disperse 120 mg of 4-TMSAce-PhIm from Step 3 into 40 mL of DMF solution, and add 0.2 mL of tetrabutylamine fluoride at 0 °C. Then, raise the temperature to room temperature and stir for 4 hours to remove the protection. Add 30 mg of FCNTs-N3, 6 mg of copper sulfate pentahydrate, and 25 mg of sodium ascorbate. React at 60 °C for 48 hours. Wash and dry to obtain imidazole-functionalized carbon nanotubes (FCNT-Im).

[0042] Step 5: Under argon atmosphere, disperse 30 mg FCNT-Im and 10 mg perfluoroiron porphyrin (FTPPFe) from Step 4 in 20 mL of methanol solvent, heat to 60 °C, and react for 16 hours to obtain the final sample (FCNT-Im-FTPPFe).

Claims

1. A biomimetic non-precious metal oxygen reduction catalyst, characterized in that, The structure is as follows: ， The method for preparing a biomimetic non-noble metal oxygen reduction catalyst includes: Step 1: Weigh out fluorinated carbon nanotubes and sodium azide and disperse them in a mixed solvent. Reflux and stir under heating conditions to obtain azide-functionalized carbon nanotubes FCNT-N3. Step 2: Under argon atmosphere, imidazole, potassium phosphate, and cuprous iodide are added to DMF solution and reacted. Then, 4-bromoiodobenzene is added and the reaction is stirred under heating to obtain 4-bromo-phenylimidazolium 4-Br-PhIm. Step 3: Under argon atmosphere, 4-Br-PhIm from Step 2, along with palladium acetate, cuprous iodide, triphenylphosphine, and trimethylsilaneacetylene, are added to triethylamine and stirred under heating conditions to obtain 4-trimethylsilylacetylenebenzamide 4-TMSAce-PhIm. Step 4: Under argon atmosphere, disperse the 4-TMSAce-PhIm from Step 3 into DMF solution, add tetrabutylamine fluoride at 0 °C, then raise to room temperature and stir to deprotect, then add FCNTs-N3 obtained in Step 1, copper sulfate pentahydrate, and sodium ascorbate, and heat to react to obtain imidazole-functionalized carbon nanotubes FCNT-Im; Step 5: Under argon atmosphere, disperse the FCNT-Im from Step 4 and perfluoroiron porphyrin in methanol solvent and heat to react, thus obtaining a biomimetic non-noble metal oxygen reduction catalyst.

2. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The mass ratio of fluorinated carbon nanotubes to sodium azide in step one is 1:

20.

3. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The mixed solvent in step one is a mixture of water and DMF, with a volume ratio of water to DMF of 1:

4.

4. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The reflux stirring time in step one is 72 hours.

5. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The molar ratio of imidazole, potassium phosphate, and 4-bromoiodobenzene in step two is 1.2:1.2:

1.

6. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The molar ratio of 4-Br-PhIm to trimethylsilaneacetylene in step three is 9:

11.

7. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The mass ratio of 4-TMSAce-PhIm and FCNTs-N3 in step four is 4:

1.

8. The biomimetic non-noble metal oxygen reduction catalyst according to claim 1, characterized in that, The mass ratio of FCNT-Im to perfluoroiron porphyrin in step five is 3:

1.

9. The application of the biomimetic non-precious metal oxygen reduction catalyst according to claim 1 in the field of fuel cells.

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