CN111261877B - Supported hollow sphere carbon material, preparation method thereof and application thereof in electrocatalysis - Google Patents

Supported hollow sphere carbon material, preparation method thereof and application thereof in electrocatalysis Download PDF

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CN111261877B
CN111261877B CN201811459789.1A CN201811459789A CN111261877B CN 111261877 B CN111261877 B CN 111261877B CN 201811459789 A CN201811459789 A CN 201811459789A CN 111261877 B CN111261877 B CN 111261877B
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carbon material
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CN111261877A (en
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金新新
谢妍
黄家辉
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method of a supported hollow sphere carbon material and application of the supported hollow sphere carbon material in electrocatalysis performance. The metal macrocyclic complex is loaded by taking a hollow sphere carbon material as a carrier. The preparation method of the catalyst comprises the following steps: (1) adding a certain amount of template agent into ethanol and aqueous alkali, adding dopamine hydrochloride and derivatives thereof, stirring, centrifuging, drying, performing high-temperature treatment, removing the template by alkali washing, washing with water to be neutral, and drying to obtain a hollow sphere carbon carrier; (2) dissolving or dispersing the transition metal macrocyclic complex in an organic solvent, mixing with the hollow sphere carbon carrier prepared in the step (1), removing impurities by ultrasonic treatment, rotary evaporation, high-temperature roasting and acid washing, and washing with water to be neutral to obtain the supported non-noble metal electrocatalyst. The preparation method has the advantages that the preparation method is simple and easy to control, and is easy for large-scale application, and the prepared non-noble metal catalyst has high oxygen reduction catalytic activity, selectivity and methanol poisoning resistance while reducing the cost, so that the preparation method has a wide application prospect.

Description

Supported hollow sphere carbon material, preparation method thereof and application thereof in electrocatalysis
Technical Field
The invention belongs to the field of composite material preparation and fuel cell catalysts, and relates to preparation of a supported hollow sphere carbon material and application of electrocatalysis performance of the supported hollow sphere carbon material.
Background
Since the 21 st century, energy shortage and environmental pollution become two major problems facing this century, and efforts are being made worldwide to develop safe and clean new energy technologies. Under the environment, the fuel cell is taken as a power generation device for directly converting chemical energy into electric energy, and the advantages of cleanness, safety, no dependence on fossil energy, high power generation efficiency, low pollution, low noise and the like are taken out of consideration in various fields, so that the fuel cell becomes one of the most effective new energy technologies and is known as the first high-tech of the 21 st century by the national periodicals. As a high-efficiency power generation device for directly converting chemical energy stored in fuel into electric energy, a fuel cell is mainly classified into 5 types according to the type of electrolyte: alkaline Fuel Cell (AFC), Phosphoric Acid Fuel Cell (PAFC), Molten Carbonate Fuel Cell (MCFC), solid oxide electrolyte fuel cellCells (SOFC) and Proton Exchange Membrane Fuel Cells (PEMFC). In the research direction of fuel cells, proton exchange membrane fuel cells are most expected to break through the barrier to realize marketization. One of the important factors that currently hinder the commercialization process of pem fuel cells is the cost of its cathode catalyst. The best fuel cell cathode oxygen reduction catalyst still mainly adopts commercial Pt/C catalyst, but the defects of resource scarcity, high cost, easy corrosion and the like become main obstacles for large-scale commercialization. Therefore, the development of non-noble metal catalysts, which are less expensive than Pt noble metals and have more excellent catalytic performance and stability, has been increasingly considered. Thus, over the past few decades, researchers have been working on non-noble metal ORR catalysts, including: non-noble metal oxides, non-noble metal nitrides and oxynitrides, non-noble metal carbonitrides, non-noble metal chalcogenides, N-doped carbon materials, M-N/C catalysts and the like. Aims to reform the fuel cell catalyst industry and develop a high-efficiency high-stability non-noble metal catalyst which can replace a Pt-based catalyst. As for the development of the prior non-noble metal catalyst, the M-N/C catalyst presents considerable catalytic performance and becomes the most possible alternative to the Pt-based catalyst for the electrolytic reduction of O2A catalyst of the group (1).
Jasinski published a new era of using cobalt phthalocyanine as a cathode oxygen reduction catalyst of an alkaline fuel cell in 1964, and a carbon-supported non-noble metal (Co, Fe and the like) catalyst and a metal-free catalyst are created to replace a platinum-based catalyst; subsequently, more research on non-noble metal catalysts has emerged, mainly by pyrolysis of metal-tetradentate N-containing macrocyclic compounds supported on high surface area carbon; in 1989, the Yeager's topic group adopts different N-rich compounds (small molecules to polymers) as ligands to coordinate with Fe or Co, and selects different carbons as catalyst carriers to prepare non-noble metal catalysts, so that the specific gravity of active sites can be increased, and the properties of the non-noble metal catalysts can be changed by selecting different precursors. Article (Zhongjie Qian, ZHaowen Hu, Zhengping Zhang, Zhilin Li, Meiling Dou and Feng WangII-N4moiety modified Fe-N codoped porous carbons as high-perforce electrolytes for the oxidative reaction, Catal. Sci. Technol.,2017,7, 4017-. Although the method has the advantages of few steps, low energy consumption, greenness, no pollution, simplicity and feasibility, the electrochemical activity of the catalyst in alkaline electrolyte and acidic electrolyte is different from that of commercial 20 wt.% Pt/C. Therefore, how to prepare a supported non-noble metal catalyst M-N/C which can further improve the activity of the electrocatalyst is a problem which needs to be solved at present.
In the 60's of the 20 th century, people discovered that pitch compounds undergo mesophase transformation during heat treatment to form mesophase spheres during the research of coke formation. The mesocarbon microbeads have good physical and chemical properties, such as chemical stability, thermal stability, excellent electrical and thermal conductivity, and the like, and attract wide attention. With the development of scientific technology, inorganic oxides having specific structures and properties have attracted extensive attention from researchers. Among them, inorganic oxides having a hollow structure are a class of materials having a special structure, and the hollow structure provides the materials with many excellent characteristics, such as: low density, high specific surface area and short transmission path through the shell layer, thereby having important application prospect in the fields of light filler, catalyst, controllable transmission and the like and greatly enriching the research field of carbon materials. The hollow nanospheres are used as a novel nano structure, one of the obvious characteristics is that the hollow nanospheres have a large internal space and a shell layer with the thickness within a nanoscale range, and the special structure enables the hollow nanospheres to be used as carriers of guest substances, so that the application range of the hollow nanospheres is continuously expanded, and the hollow nanospheres are expanded to the fields of material science, pharmacology, biology, dye industry and the like.
Disclosure of Invention
The invention aims to prepare the electrocatalyst with high specific surface area by taking the hollow sphere carbon carrier as a carrier to carry non-noble metal compounds, so as to improve the density and the dispersity of active sites and further improve the activity of the electrocatalyst. Experimental results show that the catalyst exhibits superior oxygen reduction activity in alkaline electrolyte compared to commercial 20 wt.% Pt/C.
The invention aims to provide preparation of a supported hollow sphere carbon material and application of electrocatalysis performance of the supported hollow sphere carbon material. The catalyst in the method has the characteristics of simple preparation process, easy control, environmental protection, no pollution and the like; a hollow sphere carbon material with high specific surface area and uniform size is used as a carrier to carry a nitrogen-containing non-noble metal macrocyclic compound, so as to prepare a supported electrocatalyst with oxygen reduction activity and methanol resistance exceeding commercial 20 wt.% Pt/C.
The invention provides a preparation method of a supported hollow sphere carbon material, which comprises the following steps:
(1) preparation of hollow ball carbon carrier
Adding a certain amount of template agent into a mixed solution of ethanol and an alkali solution a, adding dopamine hydrochloride or dopamine hydrochloride derivatives, stirring, centrifuging, washing with water to be neutral, drying, performing temperature programming in an inert atmosphere to 600-1000 ℃ for treatment for 0.5-4h, washing with an alkali solution b to remove the template agent, washing with water to be neutral, and drying to obtain a hollow sphere carbon carrier; the template agent is one or a mixture of two of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate and the like;
(2) preparation of Supported catalysts
Dissolving or dispersing the transition metal macrocyclic complex and the carrier prepared in the step (1) in an organic solvent, performing ultrasonic treatment for 10-60 min, performing rotary evaporation, roasting at 500-1000 ℃ for 0.5-8 h in an inert atmosphere, washing with an acid solution at 25-80 ℃ to remove impurities, washing with water to be neutral, and drying to obtain the supported hollow sphere carbon material.
Based on the technical scheme, preferably, in the step (1), the volume ratio of the template to the ethanol is 1/1000-1/5; in the mixed solution of the ethanol and the alkali solution a, the volume ratio of the ethanol to the alkali solution a is 0.1-5; the alkali solution a in the step (1) is a mixed solution of one or more than two of NaOH solution, KOH solution and ammonia water; the molar concentration range of the alkali solution a is 1-3M.
Based on the technical scheme, preferably, in the step (1), the dopamine hydrochloride and the derivative thereof are one or a mixture of more than two of levodopa, dihydroxyphenyl propyl methacrylamide, hydroquinone and catechol; in the step (1), the stirring speed is 200-1000 rpm; the stirring time is 0.5-24 h; the centrifugation speed is 3000-15000 rpm; the centrifugation time is 3-20 min.
Based on the technical scheme, preferably, the inert atmosphere in the step (1) and the inert atmosphere in the step (2) are independently selected from at least one of argon, nitrogen, ammonia, carbon dioxide or helium; the gas flow is 50-100 mLmin-1。
Based on the technical scheme, preferably, the temperature rise rate of the programmed temperature rise is 2-10 ℃ min-1。
Based on the above technical scheme, preferably, in the step (1), the alkali solution b is NaOH, KOH, NaHCO3、KHCO3、Na2CO3、K2CO3One or a mixture of two or more of them; the molar concentration is 1-3M; the alkali washing temperature is 25-60 ℃; the alkali washing time is 6-24 h.
Based on the above technical scheme, preferably, in the step (2), the transition metal macrocyclic complex is one or a mixture of two or more of hemin, iron phthalocyanine, cobalt phthalocyanine, vitamin B12, tetramethoxyphenyl porphyrin cobalt, tetramethoxyphenyl porphyrin iron, tetramethoxyphenyl porphyrin cobalt, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin iron (iii), 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin cobalt (II), 5,10,15, 20-tetrakis (4-sulfophenyl) porphyrin iron, 5,10,15, 20-tetrakis (4-sulfophenyl) porphyrin cobalt, tetraphenylporphyrin iron, tetracarboxylphenylporphyrin cobalt, tetracarboxylphenylporphyrin iron, tetrahydroxyphenylporphyrin cobalt, and tetrahydroxyphenylporphyrin iron; the mass ratio of the transition metal to the hollow sphere carbon carrier is 0.1-5%.
Based on the above technical scheme, preferably, in the step (2), the organic solvent is one or a mixed solvent of more than two of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide and dichloromethane;
based on the above technical scheme, preferably, in the step (2), the acid for removing impurities by acid washing is one or a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and perchloric acid; the concentration of the acid is 0.1-2M; the pickling temperature is 25-80 ℃; the pickling time is 3-24 h.
The invention also provides a supported hollow sphere carbon material prepared by the preparation method.
The invention further provides an application of the supported hollow sphere carbon material in electrocatalysis.
Advantageous effects
Compared with the reported preparation method of the supported non-noble metal catalyst, the preparation method has the advantages that:
(1) the preparation of the catalyst is simple and controllable, energy is saved, pollution is avoided, and the prepared hollow sphere carbon carrier has a higher specific surface area and is beneficial to supporting other precursors, so that the dispersion degree of active sites is improved.
(2) The catalyst prepared by the method has the advantages of high oxygen reduction catalytic activity and stability, strong anti-poisoning performance and excellent mass transfer performance in alkaline electrolyte, can be applied to the field of alkaline fuel cells, is expected to replace commercial platinum-based electrocatalysts, and promotes the commercialization process of fuel cells.
(3) The prepared non-noble metal catalyst has high oxygen reduction catalytic activity, selectivity and methanol poisoning resistance while reducing the cost of the fuel cell catalyst, and therefore, has wide application prospects.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of a hollow sphere carbon support prepared in example 1.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the supported hollow sphere carbon material catalyst prepared in example 1.
FIG. 3 is a schematic diagram of the structure of hemin used in the catalyst prepared in example 1.
Fig. 4 is a schematic structural view of vitamin B12 used in the catalyst prepared in example 2.
Fig. 5 is a schematic view of the structure of iron phthalocyanine used in the catalyst prepared in example 3.
Figure 6 is a graph comparing the electrocatalytic performance of the catalyst prepared in example 1 with commercial 20 wt.% Pt/C.
Detailed Description
The invention is described in more detail below with reference to examples:
example 1
(1) Preparation of hollow ball carbon carrier
Adding 0.5mL of ethyl orthosilicate into a mixed solution containing 10mL of ethanol and 30mL of KOH and 1M of KOH, adding 100mg of levodopa, stirring for 6h at a stirring speed of 500rpm, centrifuging for 5min at a centrifuging speed of 10000rpm, washing with water for three times, drying at 80 ℃ for 12h, and performing gas flow of 60mLmin-1And the heating rate is 2 ℃ for min-1Keeping the temperature of 800 ℃ for 2 hours in the argon atmosphere; then carrying out alkali washing for 12h at 60 ℃ by 200mL of 1.5M NaOH to remove the template, and washing to be neutral to obtain the hollow sphere carbon carrier;
as shown in fig. 1, a transmission electron microscope picture of the hollow sphere carbon carrier prepared in example 1 shows that the carbon carrier has uniform particle size and size distribution range of 200-300 nm;
(2) preparation of Supported catalysts
Dissolving 15mg of hemin in 150mL of dichloromethane solvent, adding 150mg of the hollow sphere carbon carrier prepared in the step (1), performing ultrasonic treatment for 10min, performing rotary evaporation at room temperature, and performing rotary evaporation at the gas flow of 80mLmin-1And the heating rate is 5 ℃ for min-1Keeping the temperature of 800 ℃ for 8H under argon atmosphere, and then adding 200mL of 0.5M H2SO4Pickling for 10h at 60 ℃ to remove impurities, and washing with water to be neutral to obtain a supported non-noble metal electrocatalyst;
referring to fig. 2, a Transmission Electron Microscope (TEM) image of the supported hollow sphere carbon material catalyst prepared in example 1 shows that the supported catalyst has distinct metal particles while maintaining the morphology of the carbon support.
As shown in FIG. 6, the oxygen reduction activity of the supported catalyst (M-HCS) prepared in this example was superior to that of commercial 20 wt.% Pt/C
Example 2
(1) Preparation of hollow ball carbon carrier
Adding 0.5mL of methyl orthosilicate into a mixed solution containing 20mL of ethanol and 40mL of KOH and 2M of KOH, adding 250mg of dihydroxyphenyl propyl methacrylamide, stirring for 6h at a stirring speed of 600rpm, centrifuging for 5min at a centrifuging speed of 10000rpm, washing with water for three times, drying at 80 ℃ for 12h, and controlling the gas flow rate to be 60mLmin-1And the heating rate is 2 ℃ for min-1Keeping the temperature of 800 ℃ for 2 hours in the ammonia atmosphere; then carrying out alkali washing for 12h at 40 ℃ by 200mL of 2M NaOH to remove the template, and carrying out water washing to neutrality to obtain the hollow sphere carbon carrier;
(2) preparation of Supported catalysts
Dissolving 20mg of vitamin B12 in 150mL of ethanol, adding 150mg of the hollow sphere carbon carrier prepared in the step (1), performing ultrasonic treatment for 30min, performing rotary evaporation at room temperature, and performing rotary evaporation at a gas flow of 60mLmin-1And the heating rate is 10 ℃ for min-1Keeping the temperature of 900 ℃ for 1H under the helium atmosphere, and then carrying out 200mL of 0.5M H2SO4Pickling for 6h at 60 ℃ to remove impurities, and washing with water to be neutral to obtain a supported non-noble metal electrocatalyst;
example 3
(1) Preparation of hollow ball carbon carrier
Adding 1.5mL of tetraethoxysilane into a mixed solution containing 12mL of ethanol, 12mL of ammonia water and 2M of ammonia water, then adding 200mg of levodopa, stirring for 12h at a stirring speed of 600rpm, centrifuging for 3min at a centrifugation speed of 13000rpm, washing for three times, drying for 12h at 80 ℃, and performing drying at the gas flow of 80mLmin-1And the heating rate is 5 ℃ for min-1Keeping the temperature of the mixture constant for 0.5h at 1000 ℃ in nitrogen atmosphere; then carrying out alkali washing with 200mL of 1.5M KOH at 30 ℃ for 24h to remove the template, and carrying out water washing to neutrality to obtain the hollow sphere carbon carrier;
(2) preparation of Supported catalysts
Dissolving 70mg of iron phthalocyanine in 150mL of dichloromethane solvent, adding 200mg of the hollow sphere carbon carrier prepared in the step (1), performing ultrasonic treatment for 50min, performing rotary evaporation at room temperature, and performing rotary evaporation at a gas flow rate of 100mLmin-1And the heating rate is 5 ℃ for min-1Keeping the temperature of 900 ℃ for 2h under the ammonia gas atmosphere, then carrying out acid washing for 3h at 80 ℃ by 200mL and 1M HCl to remove impurities, and carrying out water washing to neutrality to obtain the supported non-noble metal electrocatalyst;
example 4
(1) Preparation of hollow ball carbon carrier
Adding 3.5mL of n-butyl silicate into a mixed solution containing 30mL of ethanol and 6mL of 1M NaOH, adding 100mg of dihydroxyphenyl propyl methacrylamide, stirring at 200rpm for 10h, centrifuging at 15000rpm for 5min, washing with water three times, drying at 80 ℃ for 12h, and controlling gas flow at 60mLmin-1And the heating rate is 2 ℃ for min-1Keeping the temperature of 800 ℃ for 4 hours in the argon atmosphere; then carrying out alkali washing for 12h at 60 ℃ by 200mL of 1.5M NaOH to remove the template, and washing to be neutral to obtain the hollow sphere carbon carrier;
(2) preparation of Supported catalysts
Dissolving 80mg of iron tetraphenylporphyrin in 150mL of dichloromethane solvent, adding 150mg of the hollow sphere carbon carrier prepared in the step (1), performing ultrasonic treatment for 10min, performing rotary evaporation at room temperature, and performing rotary evaporation at a gas flow rate of 50mLmin-1And the heating rate is 5 ℃ for min-1Keeping the temperature of 800 ℃ for 2H under argon atmosphere, and then adding 200mL of 0.5M H2SO4Pickling for 6h at 60 ℃ to remove impurities, and washing with water to be neutral to obtain a supported non-noble metal electrocatalyst;
example 5
(1) Preparation of hollow ball carbon carrier
Adding 0.5mL of methyl orthosilicate into a mixture containing 60mL of ethanol and 30mL of KOH and 1M of KOH, adding 120mg of hydroquinone, stirring at 500rpm for 6h, centrifuging at 13000rpm for 5min, washing with water three times, drying at 80 ℃ for 12h, and controlling the gas flow rate to be 60mLmin-1And the heating rate is 2 ℃ for min-1Keeping the temperature of 900 ℃ for 2 hours in the argon atmosphere; then carrying out alkali washing for 24h at 25 ℃ by 200mL of 1.5M NaOH to remove the template, and washing to be neutral to obtain the hollow sphere carbon carrier;
(2) preparation of Supported catalysts
Dissolving 15mg of iron phthalocyanine in 150mL of dichloromethane solvent, adding 150mg of the hollow sphere carbon carrier prepared in the step (1), performing ultrasonic treatment for 60min, performing rotary evaporation at room temperature, and performing rotary evaporation at a gas flow rate of 60mLmin-1And the heating rate is 2 ℃ for min-1Keeping the temperature of 900 ℃ for 2h under the argon atmosphere, and then adding 200mL of 0.5M HNO3Acid at 60 ℃Washing for 10h to remove impurities, and washing with water to be neutral to obtain a supported non-noble metal electrocatalyst;
the size and particle distribution of the hollow sphere carbon carriers and supported hollow sphere carbon material catalysts prepared in examples 2-5 were similar to those of example 1.

Claims (10)

1. A preparation method of a supported hollow sphere carbon material is characterized by comprising the following steps:
(1) preparation of hollow ball carbon carrier
Adding a certain amount of template agent into a mixed solution of ethanol and an alkali solution a, adding dopamine hydrochloride or dopamine hydrochloride derivative, stirring, centrifuging, washing with water to be neutral, drying, and then sequentially heating to 800-1000 ℃ in an inert atmosphereoC, treating for 0.5-4h, washing away the template agent by using an alkali solution b, then washing to be neutral, and drying to obtain a hollow sphere carbon carrier; the template agent is one or a mixture of more than two of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate;
(2) preparation of Supported catalysts
Dissolving or dispersing the transition metal macrocyclic complex and the carrier prepared in the step (1) in an organic solvent, performing ultrasonic treatment for 10-60 min, performing rotary evaporation, and performing 500-1000 ℃ in an inert atmosphereoAnd C, roasting for 0.5-8 h, washing with an acid solution at 25-80 ℃ to remove impurities, washing with water to be neutral, and drying to obtain the supported hollow sphere carbon material.
2. The preparation method according to claim 1, wherein the volume ratio of the template to the ethanol is 1/1000-1/5; in the mixed solution of the ethanol and the alkali solution a, the volume ratio of the ethanol to the alkali solution a is 0.1-5; the alkali solution a in the step (1) is a mixed solution of one or more than two of NaOH solution, KOH solution and ammonia water; the molar concentration range of the alkali solution a is 1-3M.
3. The preparation method according to claim 1, wherein in step (1), the dopamine hydrochloride and its derivatives are one or a mixture of two or more of levodopamine, dihydroxyphenyl propyl methacrylamide, hydroquinone and catechol; in the step (1), the stirring speed is 200-1000 rpm; the stirring time is 0.5-24 h; the centrifugation speed is 3000-15000 rpm; the centrifugation time is 3-20 min.
4. The method according to claim 1, wherein the inert atmosphere in step (1) and step (2) is independently selected from at least one of argon, nitrogen, ammonia, carbon dioxide or helium; the gas flow is 50-100 mLmin-1。
5. The method according to claim 1, wherein in step (1), the alkali solution b is NaOH, KOH or NaHCO3、KHCO3、Na2CO3、K2CO3One or a mixture of two or more of them; the molar concentration is 1-3M; the alkali washing temperature is 25-60 ℃; the alkali washing time is 6-24 h.
6. The method according to claim 1, wherein in the step (2), the transition metal macrocyclic complex is one or a mixture of two or more of hemin, iron phthalocyanine, cobalt phthalocyanine, vitamin B12, cobalt tetramethoxyphenylporphyrin, iron 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (III), cobalt 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (II), iron 5,10,15, 20-tetrakis (4-sulfophenyl) porphyrin, cobalt tetraphenylporphyrin, iron tetraphenylporphyrin, cobalt tetracarboxylphenylporphyrin, iron tetracarboxylphenylporphyrin, cobalt tetrahydroxyphenyl porphyrin, and iron tetrahydroxyphenyl porphyrin; the mass ratio of the transition metal to the hollow sphere carbon carrier is 0.1-5%.
7. The method according to claim 1, wherein in the step (2), the organic solvent is one or a mixture of two or more of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, and dichloromethane.
8. The method according to claim 1, wherein in the step (2), the acid for removing impurities by acid washing is a mixed solution of one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and perchloric acid; the concentration of the acid is 0.1-2M; pickling temperature is 25-80 ℃; the pickling time is 3-24 h.
9. A supported hollow sphere carbon material prepared by the preparation method of any one of claims 1-8.
10. Use of the supported hollow sphere carbon material of claim 9 in electrocatalysis.
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CN108232212A (en) * 2018-03-26 2018-06-29 济南大学 A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application

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