CN110534755B - Zinc-based metal organic framework material and preparation method and application of iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst thereof - Google Patents

Zinc-based metal organic framework material and preparation method and application of iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst thereof Download PDF

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CN110534755B
CN110534755B CN201910827831.9A CN201910827831A CN110534755B CN 110534755 B CN110534755 B CN 110534755B CN 201910827831 A CN201910827831 A CN 201910827831A CN 110534755 B CN110534755 B CN 110534755B
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诸海滨
黄佳维
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Abstract

The invention discloses a zinc-based metal organic framework material and a preparation method and application of an iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst thereof. The material is simple and easy to obtain, the cost is low, the prepared iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst is high in oxygen reduction catalytic activity, good in stability and methanol tolerance, capable of replacing a noble metal Pt/C catalyst as a catalytic material to be applied to a fuel cell or a metal air cell, and wide in application prospect and practical value.

Description

Zinc-based metal organic framework material and preparation method and application of iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a zinc-based metal organic framework material, an iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material, and a preparation method and application thereof.
Background
Fuel cells and metal-air batteries are considered promising clean energy conversion devices. However, the slow kinetic nature of the Oxygen Reduction Reaction (ORR) at the cathode limits the energy conversion efficiency of these devices. Currently, precious platinum (e.g., Pt/C) and its alloys still represent the most advanced catalysts, but their high cost, scarce reserves and poor stability severely hamper their large-scale application. Therefore, there has been an increasing interest in recent years to develop cost-effective, earth-rich and efficient non-noble metal-based catalysts in this area. In this case, the transition metal (M) and nitrogen are codoped with a carbon electrocatalyst (M-N-C), in particular with Fe-NxThe active site Fe-N-C material, which has been identified as one of the most promising candidates, has excellent ORR performance, low cost, excellent methanol tolerance and environmental friendliness.
Metal Organic Frameworks (MOFs) are used as precursors, and the MOFs are used for regulating the ordered crystal structure, so that heteroatoms can be fully and uniformly mixed in the pretreatment process, and the heteroatom doped carbon material with uniform heteroatom distribution, rich active sites and large specific surface area is obtained. Porous structure and interpenetrating mode are two common structural phenomena in MOF materials. Recently, porous MOF materials have emerged as a new self-sacrificial template for a wide range of applications in electrochemical energy materials. Many porous nitrogen-doped carbon materials, such as ZIF-7, ZIF-8, ZIF-67, ZIF-9, MOF-5, MIL-100-Fe, etc., having a high specific surface area and good ORR electrocatalytic activity, are prepared by pyrolyzing conventional porous MOFs. However, there has been less interest to date in the use of interpenetrating non-porous MOF complexes as pyrolysis precursors than in topical studies using porous MOFs in the preparation of carbon catalysts.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a zinc-based metal organic framework material and an iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material. The zinc-based metal organic framework material provided by the invention is a 3D framework generated by connecting zinc ions, TTPA-4(4,4' -tris (1,2, 4-triazole-4-yl) triphenylamine) ligand and 1, 4-phthalic acid ligand, and the structure of the metal organic framework Zn-TTPA formed by the invention provides a high-density Zn-O coordination unit for an eight-fold interpenetrating network structure. The structural mode of the precursor facilitates the formation of a porous nitrogen-doped carbon catalyst after pyrolysis; the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst (Fe-N-C catalyst) based on the zinc-based metal organic framework material has the characteristics of a large number of micropores and mesopores, higher graphite nitrogen and pyridine nitrogen contents, lower cost and the like, and is expected to replace Pt/C to become a novel catalyst.
The invention also provides a zinc-based metal organic framework material and a preparation method and application of the zinc-based metal organic framework material-based iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst.
The technical scheme is as follows: in order to achieve the above object, the method for preparing a zinc-based metal organic framework material according to the present invention comprises the steps of:
(1) Adding 0.05-0.07mmol of zinc nitrate hexahydrate, 0.02-0.04mmol of 4,4' -tris (1,2, 4-triazole-4-yl) triphenylamine (TTPA-4), 0.05-0.07mmol of terephthalic acid, 2-10mL of water and 2-10mL of N, N-dimethylformamide into a reaction kettle, and uniformly stirring to obtain a mixture;
(2) heating the mixture to carry out hydrothermal reaction, and then cooling to obtain blocky crystals;
(3) and collecting the blocky crystals, washing, and drying at room temperature to obtain the zinc-based metal organic framework material.
Wherein, the mixture in the step (2) is heated to 80-110 ℃, subjected to hydrothermal reaction for 30-80 hours, and cooled to 10-30 ℃ to obtain bulk crystals.
Preferably, in the preparation method of the zinc-based metal organic framework material (Zn-TTPA) in the step (1), the volume ratio of the solvent water to the N, N-dimethylformamide is 1: 1-1: 3. Preferably in a volume ratio of 1: 1.
Preferably, the step (3) is washed with N, N-dimethylformamide, water and ethanol as solvents in sequence
The chemical formula of the zinc-based metal organic framework material (Zn-TTPA) prepared by the preparation method is C48H46Zn3N10O3。
Further, the crystal of the zinc-based metal organic framework material belongs to a trigonal system R3c (#161) space group, and the unit cell parameters are as follows:
Figure BDA0002189687570000021
α＝β＝90°，γ＝120°。
The invention discloses a preparation method of an iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on a zinc-based metal organic framework material, which comprises the following steps:
(1) adding 0.05-0.07mmol of zinc nitrate hexahydrate, 0.0025-0.0035mmol of ferric nitrate nonahydrate, 0.02-0.04mmol of 4,4' -tris (1,2, 4-triazole-4-yl) triphenylamine (TTPA-4), 0.05-0.07mmol of terephthalic acid, 2-10mL of water and 2-10mL of N, N-dimethylformamide into a container, and uniformly stirring to obtain a mixture;
(2) stirring the mixture, heating for reaction, cooling again to obtain a filtrate, and drying to obtain a powdery solid serving as a carbonization precursor (Fe-Zn-TTPA);
(3) carbonizing the powdery solid (Fe-Zn-TTPA) under inert gas to obtain the iron-nitrogen co-doped non-noble metal carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material.
And (3) stirring the mixture obtained in the step (2), heating to 80-110 ℃, stirring for reacting for 30-80 hours, cooling to 10-30 ℃, filtering, and drying to obtain powdery solid. The stirring in the present invention is usually magnetic stirring.
Preferably, the carbonization in the step (2) is carried out for 1 to 3 hours at the temperature of 900-1100 ℃ under the condition that the inert gas is nitrogen or argon; the carbonization temperature rise rate is 5-10 ℃/min.
Preferably, the volume ratio of the water to the N, N-dimethylformamide in the step (1) is 1: 1.
the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material prepared by the preparation method provided by the invention.
The invention discloses application of an iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on a zinc-based metal organic framework material as a catalytic material in a fuel cell or a metal air cell.
The invention relates to a zinc-based metal organic framework material (Zn-TTPA) which is prepared by adding zinc nitrate hexahydrate, 4' -tris (1,2, 4-triazole-4-yl) triphenylamine (TTPA-4), terephthalic acid, water and N, N-dimethylformamide into a reaction kettle and uniformly stirring. And heating the mixture, carrying out hydrothermal reaction, and cooling to obtain blocky crystals. And collecting the blocky crystals, washing with a solvent, and drying at room temperature to obtain the Zn-TTPA.
The catalyst is based on a zinc-based metal organic framework material, a precursor Fe-Zn-TTPA is prepared on the basis of the zinc-based metal organic framework material by a one-pot method, and the precursor Fe-Zn-TTPA is carbonized at high temperature to obtain the iron-nitrogen-carbon-oxygen reduction electrocatalyst. Specifically, a carbonization precursor (Fe-Zn-TTPA) is synthesized on the basis of a zinc-based metal organic framework material by a one-pot method, zinc nitrate hexahydrate, ferric nitrate nonahydrate, 4' -tris (1,2, 4-triazole-4-yl) triphenylamine (TTPA-4), terephthalic acid, water and N, N-dimethylformamide are added into a flask, and the precursor Fe-Zn-TTPA is obtained by uniformly stirring and heating for reaction. And carbonizing the precursor Fe-Zn-TTPA at high temperature in an inert gas to obtain the iron-nitrogen co-doped oxygen reduction catalyst.
Has the beneficial effects that: compared with the prior art, the invention has the following advantages:
the zinc-based metal organic framework material prepared by the invention has an eight-fold interpenetrating metal organic framework structure and provides high-density Zn-O coordination units. The zinc-based metal organic framework material has a large amount of Zn-O coordination bonds, and a large amount of micropores can be generated after carbonization, so that the structural mode of the precursor is favorable for forming the porous nitrogen-doped carbon catalyst after pyrolysis. The iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material has the characteristics of a large number of micropores and mesopores, higher graphite nitrogen and pyridine nitrogen contents, lower cost and the like, and is expected to replace Pt/C to become a novel catalyst.
The preparation method is simple and easy to implement, wide in raw material source, free of a large amount of capital compared with platinum carbon, and easy to industrialize. The iron-nitrogen co-doped carbon-based catalyst prepared by the method has excellent catalytic activity, long-term stability and methanol tolerance, and can replace noble metal Pt/C to be used as a catalytic material to be applied to fuel cells or metal air cells.
Drawings
FIG. 1 is a structural view of a zinc-based metal organic framework material Zn-TTPA obtained in example 1 of the present invention, viewed in a direction c;
FIG. 2 is an eight-fold insertion schematic diagram of a Zn-TTPA integral framework of a zinc-based metal organic framework material obtained in example 1 of the present invention;
FIG. 3 is an XRD spectrum of Zn-TTPA and a precursor Fe-Zn-TTPA before carbonization obtained in examples 1 and 2 of the present invention.
Fig. 4 is an XRD spectrogram of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of an iron-nitrogen co-doped carbon-based catalyst obtained in example 2 of the present invention;
fig. 6 is a nitrogen adsorption and desorption curve of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2 of the present invention;
FIG. 7 is a graph comparing the oxygen reduction catalytic activity of the iron and nitrogen co-doped carbon based catalyst obtained in example 2 with a commercial 20% platinum carbon catalyzed ORR reaction;
FIG. 8 is a schematic diagram of an accelerated aging test of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2;
FIG. 9 is a schematic diagram of a methanol poisoning test of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2;
Detailed Description
The invention will be further described with reference to specific embodiments and the accompanying drawings.
Example 1
Preparation of zinc-based metal organic framework material (Zn-TTPA):
ligand TTPA-4(13.4mg,0.03mmol), terephthalic acid (10.0mg,0.06mmol) and zinc nitrate hexahydrate (17.8mg,0.06mmol) are dissolved in 10mL of mixed solvent of DMF and deionized water (V: V is 1: 1), the mixture is placed in a tetrafluoroethylene hydrothermal kettle to be uniformly stirred, the mixture is heated to 100 ℃ to react for 50 hours, the temperature is slowly reduced to 15 ℃, generated crystals are collected, the crystals are sequentially washed by solvents (N, N-dimethylformamide, water and ethanol), and the zinc-based metal organic framework material is obtained after drying at room temperature. The yield was about 65%.
FIG. 1 is a structural view of a Zn-TTPA frame material obtained in example 1 of the present invention, viewed along the c-axis direction, in which a quasi-hexagonal channel is formed in the Zn-TTPA frame, viewed along the c-axis direction, and the window size is about
Figure BDA0002189687570000041
FIG. 2 is an eight-fold insertion schematic diagram of the overall framework of Zn-TTPA made of Zn-based metal organic framework material in example 1 of the present invention. Due to the eight-fold intercrossing structure, a compact Zn-O coordination bond can be formed.
In addition, the crystal of the zinc-based metal organic framework material prepared in the embodiment belongs to a trigonal system R3c (#161) space group, and the unit cell parameters are:
Figure BDA0002189687570000042
α＝β＝90°，γ＝120°。
example 2
Step one, preparing a precursor Fe-Zn-TTPA:
ligand TTPA-4(13.4mg,0.03mmol), terephthalic acid (10.0mg,0.06mmol), zinc nitrate hexahydrate (17.8mg,0.06mmol), iron nitrate nonahydrate (1.01mg,0.0025mmol) were added to a mixed solvent of 10mL of DMF and deionized water (V: V ═ 1: 1), heated to 100 ℃ with stirring, reacted with stirring for 72 hours, slowly cooled to 15 ℃, and filtered to give a solid in powder form with a yield of about 67%.
Step two, preparation of iron-nitrogen co-doped carbon material
Putting a powdery solid precursor Fe-Zn-TTPA material into a tube furnace, heating to 950 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, maintaining the temperature for 2h, and cooling to room temperature at the speed of 5 ℃ per minute to obtain the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst.
Fig. 3 is XRD spectrograms of the zinc-based metal organic framework material Zn-TTPA and the precursor Fe-Zn-TTPA before carbonization obtained in examples 1 and 2, and fig. 3 illustrates that the precursor Fe-Zn-TTPA obtained by one-pot stirring does not change the structure of the original zinc-based metal organic framework material Zn-TTPA after iron is doped.
Fig. 4 is an XRD spectrum of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2, which illustrates that the XRD spectrum of the iron-nitrogen co-doped carbon-based catalyst after carbonization shows a derivative peak at 25 °, which is designated as a characteristic (002) plane of graphite carbon, and the peak type is relatively sharp, which illustrates that the degree of graphitization is relatively high; in addition, Fe and Fe are observed3Peak of C.
FIG. 5 is a scanning electron micrograph of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2. It can be seen that a porous carbon material is formed after high temperature carbonization.
Fig. 6 is a nitrogen adsorption and desorption curve of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2 of the present invention; it can be seen from the figure that the hysteresis ring belongs to H4 type, which indicates that the carbon material has a large number of micropores and mesopores.
Electrochemical tests were performed in a three-electrode cell at room temperature using an electrochemical workstation (CHI 604E). An Ag/AgCl electrode and a graphite rod were used as a reference electrode and a counter electrode, respectively. The working electrode is a glassy carbon rotating disk electrode drop cast with Fe/N/C catalyst ink The sample loading amount is 0.6mg/cm2. To prepare the working electrode, 6mg of Fe-N-C catalyst (prepared in example 2) was ultrasonically dispersed in a mixture of 1.0mL of water and Nafion (5 wt%) solution to form an ink. By LSV at O2Saturated 0.1M KOH and 2% CH3In OH at 50mV s-1Scan rate of (2) to estimate CH of the catalyst3OH resistance. Accelerated aging test of ORR by continuous Cyclic voltammetry in KOH electrolyte at 50mV s-1The scan rate of (2) was 10,000 cycles in the potential range of 0.6-1.0V (versus RHE), the results of which are shown in fig. 7-9.
FIG. 7 is a graph comparing the oxygen reduction catalytic activity of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2 with that of commercial platinum-carbon with a mass fraction of 20% (under the same conditions) for catalyzing an ORR reaction, wherein the oxygen reduction catalytic activity of the iron-nitrogen co-doped carbon-based catalyst is close to that of the commercial platinum-carbon, half-waves of the iron-nitrogen co-doped carbon-based catalyst and commercial platinum-carbon reach 0.85V (vs RHE), and the limiting current of the iron-nitrogen co-doped carbon-based catalyst reaches 5.3 mA/cm-2(Pt/C 4.9mA cm-2) The cost of the catalyst prepared by the present invention is significantly less than commercial 20% platinum carbon.
Fig. 8 is an accelerated aging test of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2, and it can be seen that the material still can maintain higher catalytic activity after 10000 cycles of CV scan test, the half-wave potential is only reduced by 7mV, and the limiting diffusion current density is hardly attenuated, which indicates that the obtained material has better catalytic stability.
Fig. 9 is a methanol poisoning test of the iron-nitrogen co-doped carbon-based catalyst obtained in example 2, and it can be seen that the cyclic voltammetry curve does not change significantly after methanol is added, which indicates that the obtained material has better methanol tolerance.
Example 3
Step one, preparing a precursor Fe-Zn-TTPA:
ligand TTPA-4(17.9mg,0.04mmol), terephthalic acid (11.7mg,0.07mmol), zinc nitrate hexahydrate (20.8mg,0.07mmol), ferric nitrate nonahydrate (1.21mg,0.003mmol) were added to a mixed solvent of 20mL of DMF and deionized water (V: V ═ 1: 1), heated to 95 ℃ with stirring, reacted for 45 hours with stirring, slowly cooled to 30 ℃ and filtered to give a solid in powder form with a yield of about 64%.
Step two, preparation of iron-nitrogen co-doped carbon material
Putting a powdery solid precursor Fe-Zn-TTPA material into a tube furnace, heating to 1100 ℃ at a speed of 10 ℃/min in an argon atmosphere, keeping the temperature for 2h, and cooling to room temperature at a speed of 10 ℃ per minute to obtain the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst.
Example 4
Step one, preparing a precursor Fe-Zn-TTPA:
ligand TTPA-4(17.9mg,0.025mmol), terephthalic acid (11.7mg,0.05mmol), zinc nitrate hexahydrate (20.8mg,0.05mmol), iron nitrate nonahydrate (1.21mg,0.0025mmol) were added to a mixed solvent of 16mL DMF and deionized water (V: V ═ 1: 1), heated to 95 ℃ with stirring, reacted for 35 hours with stirring, slowly cooled to 20 ℃ and filtered to give a solid in powder form with a yield of about 65%.
Step two, preparation of iron-nitrogen co-doped carbon material
Putting a powdery solid precursor Fe-Zn-TTPA material into a tube furnace, heating to 1000 ℃ at 8 ℃/min in an argon atmosphere, keeping the temperature for 2h, and cooling to room temperature at 8 ℃ per minute to obtain the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst.
Example 5
Ligand TTPA-4(0.02mmol), terephthalic acid (0.05mmol) and zinc nitrate hexahydrate (0.05mmol) are dissolved in a mixed solvent of 4mL of DMF and deionized water (V: V ═ 1: 1), the mixture is placed in a hydrothermal kettle of tetrafluoroethylene to be uniformly stirred, the mixture is heated to 80 ℃ to react for 80 hours, the temperature is slowly reduced to 30 ℃, and generated crystals are collected. And washing the crystal with N, N-dimethylformamide, water and ethanol, and drying at room temperature to obtain the zinc-based metal organic framework material.
Example 6
Ligand TTPA-4(0.04mmol), terephthalic acid (0.07mmol) and zinc nitrate hexahydrate (0.07mmol) are dissolved in 20mL of mixed solvent of DMF and deionized water (V: V ═ 1: 1), the mixture is placed in a tetrafluoroethylene hydrothermal kettle and stirred uniformly, the mixture is heated to 110 ℃ to react for 30 hours, the temperature is slowly reduced to 10 ℃, and generated crystals are collected. And washing the crystal with N, N-dimethylformamide, water and ethanol, and drying at room temperature to obtain the zinc-based metal organic framework material.
Example 7
Step one, preparing a precursor Fe-Zn-TTPA:
ligand TTPA-4(0.02mmol), terephthalic acid (0.05mmol), zinc nitrate hexahydrate (0.05mmol) and ferric nitrate nonahydrate (0.0025mmol) were added to a mixed solvent of 4mL of DMF and deionized water (V: V ═ 1: 1), heated to 80 ℃ with stirring, reacted for 80 hours with stirring, slowly cooled to 10 ℃ and filtered to obtain a powdery solid.
Step two, preparation of iron-nitrogen co-doped carbon material
Putting a powdery solid precursor Fe-Zn-TTPA material into a tube furnace, heating to 900 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, maintaining the temperature for 3h, and cooling to room temperature at the speed of 5 ℃ per minute to obtain the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst.
Example 8
Step one, preparing a precursor Fe-Zn-TTPA:
ligand TTPA-4(0.04mmol), terephthalic acid (0.07mmol), zinc nitrate hexahydrate (0.07mmol) and ferric nitrate nonahydrate (0.0035mmol) were added to a mixed solvent of 20mL of DMF and deionized water (V: V ═ 3: 1), heated to 110 ℃ with stirring, reacted with stirring for 30 hours, slowly cooled to 30 ℃, and filtered to obtain a powdery solid.
Step two, preparation of iron-nitrogen co-doped carbon material
Putting a powdery solid precursor Fe-Zn-TTPA material into a tube furnace, heating to 1100 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, maintaining the temperature for 1h, and cooling to room temperature at a speed of 10 ℃ per minute to obtain the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst.
The method has the advantages of simple and easy operation, wide raw material source, low production cost, mature technology, no need of a large amount of capital and easy industrialization. The iron-nitrogen co-doped carbon-based catalyst prepared by the method has excellent catalytic activity and long-term stability, and can replace Pt to be applied to fuel cells and metal air cells as a catalytic material. The battery manufactured by the invention can be applied to various products, such as new energy automobiles, mobile phones, notebook computers and the like, and has a wider application prospect.

Claims (4)

1. A preparation method of an iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on a zinc-based metal organic framework material with an eight-fold interpenetrating network structure is characterized by comprising the following steps:
(1) adding 0.05-0.07mmol of zinc nitrate hexahydrate, 0.0025-0.0035mmol of ferric nitrate nonahydrate, 0.02-0.04mmol of 4,4',4' ' -tris (1,2, 4-triazole-4-yl) triphenylamine, 0.05-0.07mmol of terephthalic acid, 2-10mL of water and 2-10mL of N, N-dimethylformamide into a container, and uniformly stirring to obtain a mixture;
(2) stirring the mixture, heating to react, cooling, filtering and drying to obtain powdery solid;
(3) carbonizing the powdery solid under inert gas to obtain the eight-fold interpenetrating network structure-based iron-nitrogen co-doped non-noble metal carbon-based oxygen reduction electrocatalyst made of the zinc-based metal organic framework material;
Stirring the mixture obtained in the step (2), heating to 80-110 ℃, stirring for reacting for 30-80 hours, cooling to 10-30 ℃, filtering, and drying to obtain powdery solid;
carbonizing at the temperature of 900-1100 ℃ for 1-3 hours under the condition that the inert gas is nitrogen or argon;
the chemical formula of the zinc-based metal organic framework material with the eight-fold interpenetration network structure is C48H46Zn3N10O3(ii) a The crystal of the zinc-based metal organic framework material with the eight-fold interpenetrating network structure belongs to a trigonal system R3c (# 161) space group, and the unit cell parameters are as follows: a = b =18.8874 a, c =23.696 a, α = β =90 °, γ =120 °.
2. The preparation method according to claim 1, wherein the volume ratio of the water to the N, N-dimethylformamide in the step (1) is 1:1 to 1: 3.
3. An iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material with the eight-fold interpenetrating network structure prepared by the preparation method of claim 1.
4. The application of the iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst based on the zinc-based metal organic framework material with the eight-fold interpenetrating network structure, disclosed by claim 3, as a catalytic material in a fuel cell.
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