CN108565474B - Synthetic method of iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance - Google Patents
Synthetic method of iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance Download PDFInfo
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Abstract
The invention discloses a synthesis method of an iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance. Mixing DMF, pentacyano amino ferrate, SBA-15 and [ VMlm ] DCA, performing ultrasonic homogenization, performing hydrothermal treatment, adding DMF, transferring to a flask, adding 2, 2' -azo bis, performing continuous ultrasonic treatment, continuously stirring in an oil bath, stopping reaction, dropping into an acetone solution, standing, performing suction filtration to obtain a precipitate, drying, and grinding to obtain a powder product: calcining in a tubular furnace to obtain a black powder product; treating with dilute hydrofluoric acid to obtain an iron-loaded nitrogen-doped porous carbon material; the invention has the advantages that the metal iron is used as a metal source, the earth reserves are rich, the price is low, the material is easy to prepare, and the environmental pollution is very small; the obtained material has good electrocatalytic oxygen reduction performance, excellent cycle stability, stable methanol antitoxicity, great economic and social benefits and wide application prospect.
Description
Technical Field
The invention relates to a synthesis method of an iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance, belonging to the field of inorganic nano materials and electrochemistry.
Background
A fuel cell is a power generation device that converts chemical energy stored in a fuel and an oxidant directly into electrical energy isothermally, efficiently, and environmentally friendly. It has been considered to be the most environmentally friendly and reliable power generation device due to its advantages of high energy conversion efficiency, low pollution, low noise, high continuity and reliability, etc. But the cost is high and the technology is immature, so that the industrialization is difficult at present. The cathode oxygen reduction reaction is an important part of the fuel cell, and Pt alloys are mainly used for the cathode oxygen reduction catalyst in commerce. However, because of their relatively high cost, susceptibility to poisoning and deactivation, it is imperative to develop low cost and reliable alternatives.
Transition metal loaded doped porous carbon materials have excellent performances of low cost, high strength, good stability, environmental protection, strong adsorption capacity, easy processing and the like, and have the potential possibility of replacing commercial platinum carbon, and the transition metal (iron and cobalt … …) loaded heteroatom doped porous carbon materials have attracted extensive attention due to abundant earth reserves and excellent performance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for synthesizing an iron-supported nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance, which is simple in operation, low in cost, high in product yield, and high in economic and practical values.
The technical scheme of the invention is as follows:
a synthetic method of an iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that sodium pentacyano ammine ferrate and [ VMlm ] DCA are used as raw materials, a molecular sieve SBA-15 is used as a template, and the materials are synthesized according to the mass fraction ratio. The method comprises the following steps:
1) 150 parts of sodium pentacyano amino ferrite, 600 parts of molecular sieve SBA-15, 2000 parts of [ VMlm ] DCA and 5 parts of anhydrous N, N-dimethylformamide solution (DMF) were mixed (feed ratio 30: 120: 400: 1) uniformly adding the mixture into a hydrothermal kettle by ultrasonic wave, and performing hydrothermal treatment at 80-100 ℃ for 6 hours. Taking out the hydrothermal kettle, adding 20 parts of anhydrous N, N-dimethylformamide solution into the hydrothermal kettle, and transferring the hydrothermal kettle into a flask; dissolving 20 parts of 2, 2' -azobis (isobutyronitrile) in 5 parts of anhydrous N, N-dimethylformamide solution, performing ultrasonic homogenization, and pouring into a flask; introducing nitrogen into the flask for 30-40 minutes, sealing, transferring into an oil bath kettle at 60-80 ℃, stirring for 6-10 hours, and stopping reaction;
introducing nitrogen into the mixed solution for 30-40 minutes, sealing, transferring into an oil bath kettle at 60-80 ℃, stirring for 6-10 hours, and stopping reaction;
2) dripping the solution obtained in the step 1) into 200 parts of acetone solution, standing, performing suction filtration to obtain a precipitate, placing the precipitate in a vacuum drying oven for drying, and grinding the precipitate into powder for storage after the drying is finished.
3) Putting the powder in the step 2) into a quartz boat, heating to 400-900 ℃ at a heating rate of 5-10 ℃/min in a tube furnace under a nitrogen atmosphere, and maintaining the temperature for 1-4 hours to obtain a black powder product;
4) treating the black powder product obtained in the step 3) with dilute hydrofluoric acid, washing with deionized water, and drying in a vacuum drying oven to obtain the iron-loaded nitrogen-doped porous carbon material.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that nitrogen is introduced for 30-40 minutes in the step 1), the oil bath temperature is 60-80 ℃, and the stirring time is 6-10 hours.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that the vacuum drying temperature in the step 2) is 80-100 ℃, and the drying time is 10-15 hours.
The method for synthesizing the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that the temperature rise rate of the tubular furnace in the step 3) is 6 ℃/min, the temperature is 400-.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that in the step 3), the temperature rise rate of the tubular furnace is 6 ℃/min, the temperature is 500 ℃, and the temperature is maintained for 2 hours.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that in the step 3), the temperature rise rate of the tubular furnace is 6 ℃/min, the temperature is 600 ℃, and the temperature is maintained for 2 hours.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that in the step 3), the temperature rise rate of the tubular furnace is 6 ℃/min, the temperature is 700 ℃, and the temperature is maintained for 2 hours.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that in the step 3), the temperature rise rate of the tubular furnace is 6 ℃/min, the temperature is 800 ℃, and the temperature is maintained for 2 hours.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that in the step 3), the temperature rise rate of the tubular furnace is 6 ℃/min, the temperature is 900 ℃, and the temperature is maintained for 2 hours.
The synthesis method of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that in the step 4), the concentration of dilute hydrofluoric acid is 10 wt%, the acid treatment time is 6 hours, the vacuum drying temperature is 80 ℃, and the time is 12 hours.
The application of the iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance as the fuel cell oxygen reduction catalyst is provided.
The invention has the advantages that the metallic iron is used as a metal source, the earth reserves are rich, and the price is far lower than that of commercial platinum carbon; the material is easy to prepare and has little pollution to the environment; the obtained material has better electrocatalytic oxygen reduction performance than commercial platinum carbon, the half-wave potential of 0.836V (vs RHE) of the material is better than that of platinum carbon of 0.81V (vs RHE), the performance is not obviously reduced after 50000 seconds of circulation stability test, the methanol has stable toxicity resistance, huge economic and social benefits and wide application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of Fe @ NCNTs-800 at a 20 micron scale according to the present invention;
FIG. 2 is a transmission electron microscope image of Fe @ NCNTs-800 at 10 nm scale according to the present invention;
FIG. 3 is a transmission electron microscope image of Fe @ NCNT-800 at 5 nm scale according to the present invention;
FIG. 4 is a graph of the scanning of a rotating disk electrode at 1600 rpm for Fe @ NCNTs-800 and Pt/C in accordance with the present invention;
FIG. 5 shows the Fe @ NCNTs-800 of the present invention filled with O20.1M KOH (400rpm to 2025 rpm).
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the specific embodiments, but the scope of the present invention is not limited thereto:
a synthetic method of an iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance comprises the following steps:
1) mixing 150 parts of sodium pentacyano amino ferrate, 600 parts of molecular sieve SBA-15, 2000 parts of [ VMlm ] DCA and 5 parts of anhydrous N, N-dimethylformamide solution (DMF), and then carrying out ultrasonic homogenization; adding the mixture into a hydrothermal kettle, carrying out hydrothermal treatment at the temperature of 80-100 ℃ for 6 hours, adding 20 parts of anhydrous N, N-dimethylformamide solution, and transferring the anhydrous N, N-dimethylformamide solution into a flask; dissolving 20 parts of 2, 2' -azobis (isobutyronitrile) in 5 parts of anhydrous N, N-dimethylformamide solution, performing ultrasonic homogenization, and pouring into a flask; introducing nitrogen into the flask for 30-40 minutes, sealing, transferring into an oil bath kettle at 60-80 ℃, stirring for 6-10 hours, and stopping reaction;
2) dripping the solution obtained in the step 1) into 200 parts of acetone solution, standing, performing suction filtration to obtain a precipitate, placing the precipitate in a vacuum drying oven for drying, and grinding the precipitate into powder for storage after the drying is finished.
3) Putting the powder in the step 2) into a quartz boat, heating to 400-900 ℃ at a heating rate of 5-10 ℃/min in a tube furnace under a nitrogen atmosphere, and maintaining the temperature for 2-4 hours to obtain a black powder product;
4) treating the black powder product obtained in the step 3) with dilute hydrofluoric acid, washing with deionized water, and drying in a vacuum drying oven to obtain the iron-loaded nitrogen-doped porous carbon material.
The performance test method of the iron-loaded nitrogen-doped porous carbon material as the oxygen reduction catalyst of the fuel cell comprises the following steps:
the prepared iron-loaded nitrogen-doped porous carbon material, absolute ethyl alcohol and Nafion solution are dispersed uniformly by ultrasound, the mixture is dripped on an electrode, then the electrode is prepared by drying in the air, a testing device of an oxygen reduction catalyst is assembled by taking the electrode as a working electrode, a platinum sheet electrode as a counter electrode, Ag/AgCl as a reference electrode and KOH as electrolyte, CV and RDE are tested, and the dosage ratio of the porous carbon material to the ethanol Nafion solution is 4 mg: 0.9 mL: 0.1 mL. The electrolyte is a KOH solution with the molar concentration of 0.1 mol/L.
Example 1
Preparation of metallic iron loaded nitrogen doped porous carbon material Fe @ NCNTs-800:
5mL of N, N-Dimethylformamide (DMF) solution was weighed into a 50 mL beaker, 150mg of sodium pentacyanoferrate and 2000 mg of [ VMlm ] DCA were added, the mixture was homogenized by sonication, the mixture was transferred to the inner container of a hydrothermal kettle, and after 6 hours of hydrothermal treatment at 80 ℃, 20 mL of N, N-Dimethylformamide (DMF) solution was added and transferred to a 100 mL flask. Another 5mL of N, N-Dimethylformamide (DMF) was taken in a 50 mL beaker, and 20mg of 2, 2' -azobis (isobutyronitrile) was added thereto, homogenized by sonication, and then added to the flask. And introducing nitrogen into the flask for 40 minutes, sealing the flask, transferring the flask into an oil bath kettle at 70 ℃, stirring and heating for 8 hours, stopping the reaction, cooling to room temperature, dripping the cooled flask into 200 mL of acetone solution, standing for 2 hours, and performing suction filtration to obtain the product. The product was dried in a vacuum oven at 80 ℃ for 10 hours and then ground to give a powder. The powder is evenly poured into a quartz boat, heated to 800 ℃ at the heating rate of 6 ℃/min, maintained for 2 hours, and naturally cooled to room temperature. And (3) treating the calcined product with 10% wt hydrofluoric acid solution for 6 hours, performing suction filtration, and cleaning with deionized water. And (3) drying the obtained product in a vacuum drying oven at 80 ℃ for 12 hours to obtain the final product, namely the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-800.
As shown in fig. 1-3, which are scanning electron microscope pictures of Fe @ NCNTs-800 at scales of 20 microns, 10 microns and 5 microns, respectively, fig. 4 is a scanning curve of a rotating disk electrode of Fe @ NCNTs-800 and Pt/C at 1600 rpm according to the present invention; FIG. 5 shows the Fe @ NCNTs-800 of the present invention filled with O20.1M KOH (400rpm to 2025 rpm); the amounts of the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-800, anhydrous ethanol and Nafion obtained in this example were calculated in the following ratio of 4 mg: 0.9 mL: 0.1 mL, dropping the mixture on a working electrode after ultrasonic uniform, assembling a testing device of the oxygen reduction catalyst by taking Ag/AgCl as a reference electrode and KOH as electrolyte, testing CV and RDE, wherein the scanning speed is 50 mV/s, and the electrolyte is 0 mV/s1M KOH. The half-wave potential of 0.836V (vs RHE) is superior to that of platinum carbon of 0.81V (vs RHE), the performance is not obviously reduced after 50000 seconds of circulation stability test, and the methanol has excellent toxicity resistance.
Example 2
Preparation of metallic iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-400:
a5 mL of N, N-Dimethylformamide (DMF) solution was weighed into a 50 mL beaker, 150mg of sodium pentacyanoferrate and 2000 mg of [ VMlm ] DCA were added, the mixture was homogenized by sonication, the mixture was transferred to the inner tank of a hydrothermal kettle, and after 6 hours of hydrothermal reaction at 80 ℃ 20 mL of N, N-Dimethylformamide (DMF) solution was added and transferred to a 100 mL flask. Another amount of 5mL of N, N-Dimethylformamide (DMF) was added to a 50 mL beaker, and 20mg of 2, 2' -azobis (isobutyronitrile) was added thereto and homogenized by sonication, and then the resulting mixture was added to the flask. And introducing nitrogen into the flask for 40 minutes, sealing the flask, transferring the flask into an oil bath kettle at 70 ℃, stirring and heating for 8 hours, stopping the reaction, cooling to room temperature, dripping the cooled solution into 200 mL of acetone solution, standing, and performing suction filtration to obtain the product. The product was dried in a vacuum oven at 80 ℃ for 10 hours and then ground to give a powder. The powder is evenly poured into a quartz boat, the temperature is raised to 400 ℃ at the heating rate of 6 ℃/min, and after the temperature is maintained for 2 hours, the quartz boat is naturally cooled to the room temperature. And (3) treating the calcined product with 10% wt hydrofluoric acid solution for 6 hours, performing suction filtration, and cleaning with deionized water. And (3) drying the obtained product in a vacuum drying oven at 80 ℃ for 12 hours to obtain the final product, namely the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-400.
The test conditions of the electrocatalytic oxygen reduction reaction performance are the same as those of the embodiment 1, the half-wave potential is 0.60V (vsRHE), the performance is not obviously reduced after 50000 seconds of circular stability test, and the methanol antitoxic property is excellent.
Example 2
Preparation of metallic iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-500:
a5 mL of N, N-Dimethylformamide (DMF) solution was weighed into a 50 mL beaker, 150mg of sodium pentacyanoferrate and 2000 mg of [ VMlm ] DCA were added, the mixture was homogenized by sonication, the mixture was transferred to the inner tank of a hydrothermal kettle, and after 6 hours of hydrothermal reaction at 80 ℃ 20 mL of N, N-Dimethylformamide (DMF) solution was added and transferred to a 100 mL flask. Another amount of 5mL of N, N-Dimethylformamide (DMF) was added to a 50 mL beaker, and 20mg of 2, 2' -azobis (isobutyronitrile) was added thereto and homogenized by sonication, and then the resulting mixture was added to the flask. And introducing nitrogen into the flask for 40 minutes, sealing the flask, transferring the flask into an oil bath kettle at 70 ℃, stirring and heating for 8 hours, stopping the reaction, cooling to room temperature, dripping the cooled solution into 200 mL of acetone solution, standing, and performing suction filtration to obtain the product. The product was dried in a vacuum oven at 80 ℃ for 10 hours and then ground to give a powder. The powder is evenly poured into a quartz boat, heated to 500 ℃ at the heating rate of 6 ℃/min, maintained for 2 hours, and naturally cooled to room temperature. And (3) treating the calcined product with 10% wt hydrofluoric acid solution for 6 hours, performing suction filtration, and cleaning with deionized water. And (3) drying the obtained product in a vacuum drying oven at 80 ℃ for 12 hours to obtain the final product, namely the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-500.
The test conditions of the electrocatalytic oxygen reduction reaction performance are the same as those of the embodiment 1, the embodiment 2 has the half-wave potential of 0.75V (vs RHE), and the performance is not obviously reduced after 50000 seconds of cycle stability test.
Preparation of metallic iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-600:
a5 mL of N, N-Dimethylformamide (DMF) solution was weighed into a 50 mL beaker, 150mg of sodium pentacyanoferrate and 2000 mg of [ VMlm ] DCA were added, the mixture was homogenized by sonication, the mixture was transferred to the inner tank of a hydrothermal kettle, and after 6 hours of hydrothermal reaction at 80 ℃ 20 mL of N, N-Dimethylformamide (DMF) solution was added and transferred to a 100 mL flask. Another amount of 5mL of N, N-Dimethylformamide (DMF) was added to a 50 mL beaker, and 20mg of 2, 2' -azobis (isobutyronitrile) was added thereto and homogenized by sonication, and then the resulting mixture was added to the flask. And introducing nitrogen into the flask for 40 minutes, sealing the flask, transferring the flask into an oil bath kettle at 70 ℃, stirring and heating for 8 hours, stopping the reaction, cooling to room temperature, dripping the cooled solution into 200 mL of acetone solution, standing, and performing suction filtration to obtain the product. The product was dried in a vacuum oven at 80 ℃ for 10 hours and then ground to give a powder. The powder is evenly poured into a quartz boat, heated to 600 ℃ at the heating rate of 6 ℃/min, maintained for 2 hours, and naturally cooled to room temperature. And (3) treating the calcined product with 10% wt hydrofluoric acid solution for 6 hours, performing suction filtration, and cleaning with deionized water. And (3) drying the obtained product in a vacuum drying oven at 80 ℃ for 12 hours to obtain the final product, namely the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-600.
The test conditions of electrocatalytic oxygen reduction reaction performance are the same as those of the example 1, the half-wave potential is 0.76V (vs RHE), the performance is not obviously reduced after 50000 seconds of cyclic stability test, and the methanol toxicity resistance is excellent.
Example 3
Preparation of metallic iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-700:
5mL of N, N-Dimethylformamide (DMF) solution was weighed into a 50 mL beaker, 150mg of sodium pentacyanoferrate and 2000 mg of [ VMlm ] DCA were added, the mixture was homogenized by sonication, the mixture was transferred to the inner container of a hydrothermal kettle, and after 6 hours of hydrothermal treatment at 80 ℃, 20 mL of N, N-Dimethylformamide (DMF) solution was added and transferred to a 100 mL flask. Another 5mL of N, N-Dimethylformamide (DMF) was taken in a 50 mL beaker, and 20mg of 2, 2' -azobis (isobutyronitrile) was added thereto, homogenized by sonication, and then added to the flask. And introducing nitrogen into the flask for 40 minutes, sealing the flask, transferring the flask into an oil bath kettle at 70 ℃, stirring and heating for 8 hours, stopping the reaction, cooling to room temperature, dripping the cooled solution into 200 mL of acetone solution, standing, and performing suction filtration to obtain the product. The product was dried in a vacuum oven at 80 ℃ for 10 hours and then ground to give a powder. The powder is evenly poured into a quartz boat, the temperature is raised to 700 ℃ at the heating rate of 6 ℃/min, the temperature is maintained for 2 hours, and then the quartz boat is naturally cooled to the room temperature. And (3) treating the calcined product with 10% wt hydrofluoric acid solution for 6 hours, performing suction filtration, and cleaning with deionized water. And (3) drying the obtained product in a vacuum drying oven at 80 ℃ for 12 hours to obtain the final product, namely the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-700.
The test conditions of the electrocatalytic oxygen reduction reaction are the same as those of the example 1, the half-wave potential is 0.82V (vs RHE), the performance is not obviously reduced after 50000 seconds of the cycling stability test, and the methanol has excellent toxicity resistance.
Example 4
Preparation of metallic iron loaded nitrogen doped porous carbon material Fe @ NCNTs-900:
5mL of N, N-Dimethylformamide (DMF) solution was weighed into a 50 mL beaker, 150mg of sodium pentacyanoferrate and 2000 mg of [ VMlm ] DCA were added, the mixture was homogenized by sonication, the mixture was transferred to the inner container of a hydrothermal kettle, and after 6 hours of hydrothermal treatment at 80 ℃, 20 mL of N, N-Dimethylformamide (DMF) solution was added and transferred to a 100 mL flask. Another 5mL of N, N-Dimethylformamide (DMF) was taken in a 50 mL beaker, and 20mg of 2, 2' -azobis (isobutyronitrile) was added thereto, homogenized by sonication, and then added to the flask. And introducing nitrogen into the flask for 40 minutes, sealing the flask, transferring the flask into an oil bath kettle at 70 ℃, stirring and heating for 8 hours, stopping the reaction, cooling to room temperature, dripping the cooled solution into 200 mL of acetone solution, standing, and performing suction filtration to obtain the product. The product was dried in a vacuum oven at 80 ℃ for 10 hours and then ground to give a powder. The powder is evenly poured into a quartz boat, heated to 900 ℃ at the heating rate of 6 ℃/min, maintained for 2 hours, and naturally cooled to the room temperature. And (3) treating the calcined product with 10% wt hydrofluoric acid solution for 6 hours, performing suction filtration, and cleaning with deionized water. And (3) drying the obtained product in a vacuum drying oven at 80 ℃ for 12 hours to obtain the final product, namely the iron-loaded nitrogen-doped porous carbon material Fe @ NCNTs-900.
The test conditions of the electrocatalytic oxygen reduction reaction are the same as those of the example 1, the half-wave potential is 0.81V (vs RHE), the performance is not obviously reduced after 50000 seconds of the cycling stability test, and the methanol has excellent toxicity resistance.
The above description is only a few examples of the present invention, and is not intended to limit the present invention; but all equivalent variations and modifications made in accordance with the teachings of the present invention are within the scope of the present invention.
Claims (9)
1. A synthetic method of an iron-loaded nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance is characterized in that sodium pentacyano-ammine ferrate and 1-vinyl-3-methylimidazolium dinitrile amine salt [ VMlm ] DCA are used as raw materials, and a molecular sieve SBA-15 is used as a template, and the method is characterized by comprising the following steps:
1) mixing sodium pentacyano-amino ferrate, a molecular sieve SBA-15, [ VMlm ] DCA and an anhydrous N, N-dimethylformamide solution uniformly by ultrasound, adding the mixture into a hydrothermal kettle, maintaining the mixture at 80-100 ℃ for a period of time, taking out the hydrothermal kettle after the completion of the ultrasonic mixing, adding the anhydrous N, N-dimethylformamide solution into the hydrothermal kettle, transferring the solution into a flask, dissolving 2, 2' -azobis (isobutyronitrile) in the anhydrous N, N-dimethylformamide solution uniformly by ultrasound, and pouring the solution into the flask; introducing nitrogen into the flask for 30-40 minutes, sealing, transferring into an oil bath kettle at 60-80 ℃, and stirring for reacting for 6-10 hours to obtain a solution;
2) dripping the solution obtained in the step 1) into an acetone solution, standing, performing suction filtration to obtain a precipitate, drying the precipitate in a vacuum drying oven, grinding the dried precipitate into powder, and storing the powder, wherein the vacuum drying temperature is 80-100 ℃, and the drying time is 10-15 hours;
3) putting the powder in the step 2) into a quartz boat, heating to 400-900 ℃ at a heating rate of 5-10 ℃/min in a tube furnace under a nitrogen atmosphere, and preserving heat for 1-4 hours to obtain a black powder product;
4) treating the black powder product obtained in the step 3) with hydrofluoric acid, washing with deionized water, and drying in a vacuum drying oven to obtain the iron-loaded nitrogen-doped porous carbon material, wherein the concentration of the dilute hydrofluoric acid is 10 wt%, the acid treatment time is 6 hours, the vacuum drying temperature is 80 ℃, and the vacuum drying time is 12 hours.
2. The method for synthesizing an iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties as claimed in claim 1, wherein the nitrogen gas is introduced for 30 to 40 minutes in step 1), the oil bath temperature is 60 to 80 ℃, and the stirring time is 6 to 10 hours.
3. The method for synthesizing an iron-supported nitrogen-doped porous carbon material with excellent electrocatalytic oxygen reduction performance as claimed in claim 1, wherein the temperature rise rate of the tubular furnace in the step 3) is 6 ℃/min, the temperature is 400-.
4. The method for synthesizing an iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties as claimed in claim 1, wherein the temperature rise rate of the tube furnace in the step 3) is 6 ℃/min, the temperature is 500 ℃, and the temperature is maintained for 2 hours.
5. The method for synthesizing an iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties as claimed in claim 1, wherein the temperature rise rate of the tube furnace in the step 3) is 6 ℃/min, the temperature is 600 ℃, and the temperature is maintained for 2 hours.
6. The method for synthesizing an iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties as claimed in claim 1, wherein the temperature rise rate of the tube furnace in the step 3) is 6 ℃/min, the temperature is 700 ℃, and the temperature is maintained for 2 hours.
7. The method for synthesizing an iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties as claimed in claim 1, wherein the temperature rise rate of the tube furnace in the step 3) is 6 ℃/min, the temperature is 800 ℃, and the temperature is maintained for 2 hours.
8. The method for synthesizing an iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties as claimed in claim 1, wherein the temperature rise rate of the tube furnace in the step 3) is 6 ℃/min, the temperature is 900 ℃, and the temperature is maintained for 2 hours.
9. Use of the iron-supported nitrogen-doped porous carbon material having excellent electrocatalytic oxygen reduction properties prepared according to the method of claim 1 as a fuel cell oxygen reduction catalyst.
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