CN111477887A - Co3O4Composite oxygen reduction catalyst loaded with hollow carbon microspheres and preparation method thereof - Google Patents

Co3O4Composite oxygen reduction catalyst loaded with hollow carbon microspheres and preparation method thereof Download PDF

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CN111477887A
CN111477887A CN202010395745.8A CN202010395745A CN111477887A CN 111477887 A CN111477887 A CN 111477887A CN 202010395745 A CN202010395745 A CN 202010395745A CN 111477887 A CN111477887 A CN 111477887A
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hollow carbon
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oxygen reduction
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施克勤
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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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the technical field of oxygen reduction reaction catalysts, and discloses Co3O4The composite oxygen reduction catalyst loading the hollow carbon microspheres comprises the following formula raw materials and components: hollow carbon nano-microspheres, cobalt nitrate, urea, ammonium fluoride and hydrogen peroxide. Such a Co3O4The hollow carbon nano-microsphere has good small-size effect and huge specific surface area, and can accelerate Co3O4In the oxygen adsorption process of the oxygen reduction reaction, the carbon nano-microspheres generate a large amount of oxygen vacancies in the high-temperature heat treatment process, the oxygen vacancies can optimize the electronic structure distribution of the carbon nano-microspheres, enhance the catalytic performance of the oxygen reduction, and petal-shaped Co3O4Nanorod structure scaleLarger area, uniform distribution on the surface of the hollow carbon nano-microsphere, and inhibition of Co3O4The aggregation of the nano-rod exposes a large amount of electrochemical active centers, and the carbon nano-microsphere and Co with excellent conductivity3O4A multilevel conductive network is formed between the catalyst and the catalyst, so that the conductivity of the catalyst is enhanced.

Description

Co3O4Composite oxygen reduction catalyst loaded with hollow carbon microspheres and preparation method thereof
Technical Field
The invention relates to the technical field of oxygen reduction reaction catalysts, in particular to Co3O4A composite oxygen reduction catalyst loaded with hollow carbon microspheres and a preparation method thereof.
Background
With the increasing severity of energy crisis and environmental pollution problems, the development of novel efficient energy conversion and storage devices has become a research hotspot, wherein methanol fuel cells and metal-air cells have the advantages of wide temperature range, light volume, cleanness, environmental protection, high theoretical energy ratio, and the like, and are proton exchange membrane fuel cells with great development potential, wherein the cathode reaction in fuel cells and metal-air cells is Oxygen Reduction Reaction (ORR), but the oxygen reduction reaction is slow in kinetics, and a platinum-based noble metal catalyst needs to be added to promote the progress of the cathode oxygen reduction reaction at present, but the platinum-based noble metal has a rare content and a high price, so that the wide commercial application of fuel cells and metal-air cells is hindered, and therefore, the development of an oxygen reduction catalyst with high catalytic activity and low cost is needed.
Transition metal oxides, e.g. NiCo2O4、Co3O4、MnO2、Mn3O4Etc. may be used as a material in place of the noble metal catalyst, wherein Co3O4Has the advantages of low price, easy obtaining, high catalytic activity of oxygen reduction, and the like, is a non-noble metal oxygen reduction catalyst with great development potential, but Co3O4Has poor conductivity, low specific surface area, insufficient electrochemical active center and the like, and limits Co3O4Development of catalysts for oxygen reduction reaction.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Co3O4The composite oxygen reduction catalyst of load hollow carbon microsphere and the preparation method thereof solve the problem of Co3O4Poor conductivity of the oxygen reduction reaction catalyst, low specific surface area and insufficient electrochemical active center.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: co3O4The composite oxygen reduction catalyst loading the hollow carbon microspheres comprises the following raw materials and components: the hollow carbon nano-microsphere, the cobalt nitrate, the urea, the ammonium fluoride and the hydrogen peroxide in a mass ratio of 15-35:100:150-200:40-50: 120-180.
Preferably, said Co3O4The preparation method of the composite oxygen reduction catalyst loaded with the hollow carbon microspheres comprises the following steps:
(1) adding B into a reaction bottleAdding ammonia water to adjust the pH value of the solution to 8-10, adding resorcinol and stirring for dissolving, slowly dropwise adding ethyl orthosilicate, stirring uniformly, adding aqueous solution of formaldehyde and cetyl trimethyl ammonium bromide serving as a surfactant, placing the mixture in a constant-temperature water bath kettle, heating to 30-40 ℃, stirring at a constant speed for reacting for 20-30 hours, pouring the solution into a high-pressure reaction kettle, placing the solution in a reaction heating box, heating to 130-160 ℃, reacting for 20-30 hours, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying and grinding the solid product into fine powder to prepare the phenolic resin nano-coated nano SiO microspheres2。
(2) Coating phenolic resin nano-microspheres with nano-SiO2Placing the mixture in an atmosphere furnace, heating to 750-20% hydrofluoric acid solution at a heating rate of 5-10 ℃/min and 850 ℃ in a nitrogen atmosphere, keeping the temperature and calcining for 4-6h, and etching to remove SiO2And washing the solid product by using distilled water and ethanol and fully drying to prepare the hollow carbon nano-microsphere.
(3) Adding distilled water solvent, hollow carbon nano-microspheres, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, adding aqueous solution of hydrogen peroxide after uniform ultrasonic dispersion, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box, heating to 140 ℃ for reaction for 4-8h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating to 300 ℃ at the heating rate of 2-5 ℃/min, and carrying out heat preservation treatment for 1-2h to prepare the Co-doped carbon nano-particles3O4A composite oxygen reduction catalyst loaded with hollow carbon microspheres.
Preferably, the reaction heating box comprises a heat insulation layer, a base is arranged below the inner portion of the heat insulation layer, a support is fixedly connected to the upper portion of the base, a constant temperature heater is fixedly connected to the upper portion of the support, the constant temperature heater is fixedly connected with a heating ring, a heating box is fixedly connected to the upper portion of the base, the upper portion of the inner portion of the heating box is fixedly connected with an objective table, and a high-pressure reaction kettle is arranged above the objective table.
Preferably, the mass ratio of the m-diphenol, the ethyl orthosilicate, the formaldehyde and the hexadecyl trimethyl ammonium bromide is 1:5-8:0.4-0.6: 0.8-1.5.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
such a Co3O4The composite oxygen reduction catalyst of the load hollow carbon microsphere uses cetyl trimethyl ammonium bromide as a surfactant and is prepared by in-situ polymerization method on nano SiO2The surface of the hollow carbon nano microsphere is generated into phenolic resin nano microspheres, and then the hollow carbon nano microsphere is prepared by high-temperature carbonization and hydrofluoric acid etching, has good small-size effect and huge specific surface area, and can accelerate Co3O4In the oxygen adsorption process of the oxygen reduction reaction, a large number of oxygen vacancies are generated in the carbon nano-microsphere in the high-temperature heat treatment process, and the introduction of the oxygen vacancies can optimize the electronic structure distribution of the carbon nano-microsphere, so that the oxygen reduction catalytic performance of the catalyst is enhanced.
Such a Co3O4The composite oxygen reduction catalyst loaded with hollow carbon microspheres takes hollow carbon nanospheres as carriers, and the Co with petal shape is prepared by a high-pressure hydrothermal method3O4Nanorod structure, larger specific surface area, and Co3O4The nano rods are uniformly distributed on the surface of the hollow carbon nano microsphere, thereby effectively inhibiting Co3O4The aggregation of the nano-rods exposes a large amount of electrochemical active centers, and the carbon nano-microspheres have good electronic conductivity and electron mobility, and are Co3O4A multi-level conductive network is formed between the two layers, so that the conductive performance of the catalyst is enhanced, the diffusion and the transmission of electrons are promoted, and Co is enabled3O4The composite oxygen reduction catalyst loaded with the hollow carbon microspheres shows lower reduction peak potential and overpotential and has excellent oxygen reduction catalytic activity.
Drawings
FIG. 1 is a schematic cross-sectional view of a reaction heating chamber.
1. A thermal insulation layer; 2. a base; 3. a support; 4. a constant temperature heater; 5. heating a ring; 6. a heating box; 7. an object stage; 8. and (4) a high-pressure reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: co3O4The composite oxygen reduction catalyst loading the hollow carbon microspheres comprises the following raw materials and components: the hollow carbon nano-microsphere, the cobalt nitrate, the urea, the ammonium fluoride and the hydrogen peroxide in a mass ratio of 15-35:100:150-200:40-50: 120-180.
Co3O4The preparation method of the composite oxygen reduction catalyst loaded with the hollow carbon microspheres comprises the following steps:
(1) adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the ethanol to the distilled water is 2.5-3.5:1, adding ammonia water to adjust the pH value of the solution to 8-10, adding resorcinol, stirring and dissolving, slowly dropwise adding ethyl orthosilicate, stirring uniformly, adding an aqueous solution of formaldehyde and a surfactant cetyl trimethyl ammonium bromide, wherein the mass ratio of the resorcinol, the ethyl orthosilicate, the formaldehyde and the cetyl trimethyl ammonium bromide is 1:5-8:0.4-0.6:0.8-1.5, placing the mixture into a constant-temperature water bath kettle, heating to 30-40 ℃, stirring at a constant speed for reaction for 20-30 hours, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a reaction heating box, wherein the reaction heating box comprises a heat insulation layer, a base is arranged below the inner part of the heat insulation layer, a support is fixedly connected above the base, a constant-temperature heater is fixedly connected, Fixedly connecting a constant temperature heater with a heating ring, fixedly connecting a heating box above a base, fixedly connecting an object stage with the upper part inside the heating box, arranging a high-pressure reaction kettle above the object stage, heating to 130-2。
(2) Coating phenolic resin nano-microspheres with nano-SiO2Placing the mixture in an atmosphere furnace, heating to 750-20% hydrofluoric acid solution at a heating rate of 5-10 ℃/min and 850 ℃ in a nitrogen atmosphere, keeping the temperature and calcining for 4-6h, and etching to remove SiO2The solid product was washed with distilled water and ethanol and dried thoroughly,preparing the hollow carbon nano-microsphere.
(3) Adding distilled water solvent, hollow carbon nano-microspheres, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, adding aqueous solution of hydrogen peroxide after uniform ultrasonic dispersion, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box, heating to 140 ℃ for reaction for 4-8h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating to 300 ℃ at the heating rate of 2-5 ℃/min, and carrying out heat preservation treatment for 1-2h to prepare the Co-doped carbon nano-particles3O4A composite oxygen reduction catalyst loaded with hollow carbon microspheres.
Example 1
(1) Preparation of phenolic resin nano-microsphere coated nano SiO2Component 1: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 2.5:1, adding ammonia water to adjust the pH value of the solution to 8, adding m-diphenol, stirring and dissolving, slowly dropwise adding ethyl orthosilicate, stirring uniformly, adding an aqueous solution of formaldehyde and a surfactant cetyl trimethyl ammonium bromide, wherein the mass ratio of the m-diphenol, the ethyl orthosilicate, the formaldehyde and the cetyl trimethyl ammonium bromide is 1:5:0.4:0.8, placing the solution into a constant-temperature water bath, heating to 30 ℃, stirring at a constant speed for reaction for 20 hours, pouring the solution into a high-pressure reaction kettle, placing the solution into a reaction heating box, wherein the reaction heating box comprises a heat insulation layer, a base is arranged below the inner part of the heat insulation layer, a support is fixedly connected above the base, a constant-temperature heater is fixedly connected above the support, the constant-temperature heater is fixedly connected with a heating ring, a heating box, A high-pressure reaction kettle is arranged above the objective table, the temperature is raised to 130 ℃, the reaction is carried out for 20 hours, the solution is centrifugally separated to remove the solvent, the solid product is washed by distilled water and ethanol, the solid product is fully dried and ground into fine powder, and the nano SiO coated phenolic resin microspheres are prepared2And (3) component 1.
(2) Preparing a hollow carbon nano microsphere component 1: coating phenolic resin nano-microspheres with nano-SiO2Placing the component 1 in an atmosphere furnace, heating to 750 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and carrying out heat preservation calcination4h, placing the calcined product in hydrofluoric acid solution with the mass fraction of 10%, and etching to remove SiO2And washing the solid product by using distilled water and ethanol and fully drying to prepare the hollow carbon nano microsphere component 1.
(3) Preparation of Co3O4Composite oxygen reduction catalyst material loaded with hollow carbon microspheres 1: adding distilled water solvent, hollow carbon nano microsphere component 1, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, adding aqueous solution of hydrogen peroxide after ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box to heat to 100 ℃ for 4 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating to 250 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation treatment for 1 hour to prepare Co3O4A composite oxygen reduction catalyst material 1 carrying hollow carbon microspheres.
Example 2
(1) Preparation of phenolic resin nano-microsphere coated nano SiO2And (2) component: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 3.5:1, adding ammonia water to adjust the pH value of the solution to 8, adding m-diphenol, stirring and dissolving, slowly dropwise adding ethyl orthosilicate, stirring uniformly, adding an aqueous solution of formaldehyde and a surfactant cetyl trimethyl ammonium bromide, wherein the mass ratio of the m-diphenol, the ethyl orthosilicate, the formaldehyde and the cetyl trimethyl ammonium bromide is 1:5.5:0.45:1, placing the solution into a constant-temperature water bath, heating to 30 ℃, stirring at a constant speed for reaction for 30 hours, pouring the solution into a high-pressure reaction kettle, placing the solution into a reaction heating box, wherein the reaction heating box comprises a heat insulation layer, a base is arranged below the inner part of the heat insulation layer, a support is fixedly connected above the base, a constant-temperature heater is fixedly connected above the support, the constant-temperature heater is fixedly connected with a heating ring, a heating box, A high-pressure reaction kettle is arranged above the objective table, the high-pressure reaction kettle is heated to 160 ℃, the reaction is carried out for 25 hours, and the solution is centrifugally separated to remove the solvent, so that the solvent is removedWashing the solid product with distilled water and ethanol, fully drying and grinding into fine powder to prepare the phenolic resin nano microsphere coated nano SiO2And (3) component 2.
(2) Preparing a hollow carbon nano microsphere component 2: coating phenolic resin nano-microspheres with nano-SiO2Placing the component 2 in an atmosphere furnace, heating to 850 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, keeping the temperature and calcining for 4h, placing the calcined product in 20 mass percent hydrofluoric acid solution, and etching to remove SiO2And washing the solid product by using distilled water and ethanol and fully drying to prepare the hollow carbon nano microsphere component 2.
(3) Preparation of Co3O4Composite oxygen reduction catalyst material loaded with hollow carbon microspheres 2: adding distilled water solvent, hollow carbon nano microsphere component 2, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, adding aqueous solution of hydrogen peroxide after ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box to heat to 140 ℃ for reaction for 8 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating to 250 ℃ at the heating rate of 5 ℃/min, and carrying out heat preservation treatment for 2 hours to prepare Co-based catalyst3O4A composite oxygen reduction catalyst material 2 carrying hollow carbon microspheres.
Example 3
(1) Preparation of phenolic resin nano-microsphere coated nano SiO2And (3) component: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the ethanol to the distilled water is 3:1, adding ammonia water to adjust the pH of the solution to 9, adding m-diphenol, stirring for dissolving, slowly dropwise adding ethyl orthosilicate, stirring uniformly, adding an aqueous solution of formaldehyde and a surfactant cetyl trimethyl ammonium bromide, wherein the mass ratio of the m-diphenol to the ethyl orthosilicate to the formaldehyde to the cetyl trimethyl ammonium bromide is 1:6:0.5:1.2, placing the mixture into a constant-temperature water bath, heating to 35 ℃, stirring at a constant speed for reaction for 25 hours, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a reaction heating box, and heating for reactionThe box comprises a heat insulation layer, a base is arranged below the inner part of the heat insulation layer, a support is fixedly connected with the upper part of the base, a constant temperature heater is fixedly connected with the upper part of the support, the constant temperature heater is fixedly connected with a heating ring, a heating box is fixedly connected with the upper part of the base, the upper part of the inner part of the heating box is fixedly connected with an objective table, a high-pressure reaction kettle is arranged above the objective table, the solution is heated to 150 ℃ for reaction for 25 hours, the solution is centrifugally separated to remove the solvent, the solid product is washed by distilled water and ethanol, the solid2And (3) component.
(2) Preparing a hollow carbon nano microsphere component 3: coating phenolic resin nano-microspheres with nano-SiO2Placing the component 3 in an atmosphere furnace, heating to 800 ℃ at a heating rate of 8 ℃/min under the nitrogen atmosphere, keeping the temperature and calcining for 5h, placing the calcined product in a hydrofluoric acid solution with the mass fraction of 15%, and etching to remove SiO2And washing the solid product by using distilled water and ethanol and fully drying to prepare the hollow carbon nano microsphere component 3.
(3) Preparation of Co3O4Composite oxygen reduction catalyst material supporting hollow carbon microspheres 3: adding distilled water solvent, hollow carbon nano microsphere component 3, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, adding aqueous solution of hydrogen peroxide after ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box to heat to 120 ℃ for 6 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating to 280 ℃ at the heating rate of 3 ℃/min, performing heat preservation treatment for 1.5 hours to prepare Co3O4A composite oxygen reduction catalyst material 3 carrying hollow carbon microspheres.
Example 4
(1) Preparation of phenolic resin nano-microsphere coated nano SiO2And (4) component: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the ethanol to the distilled water is 3.2:1, adding ammonia water to adjust the pH value of the solution to 10, adding m-diphenol, and stirringStirring and dissolving, slowly dropwise adding tetraethoxysilane, stirring uniformly, adding a formaldehyde aqueous solution and a surfactant cetyl trimethyl ammonium bromide, wherein the mass ratio of resorcinol, tetraethoxysilane, formaldehyde and cetyl trimethyl ammonium bromide is 1:7:0.55:1.3, placing in a constant-temperature water bath kettle, heating to 30 ℃, stirring at a constant speed for reaction for 30 hours, pouring the solution into a high-pressure reaction kettle, placing in a reaction heating box, wherein the reaction heating box comprises a heat insulation layer, a base is arranged below the inner part of the heat insulation layer, a support is fixedly connected above the base, a constant-temperature heater is fixedly connected above the support, the constant-temperature heater is fixedly connected with a heating ring, a heating box is fixedly connected above the base, a high-pressure reaction kettle is arranged above a carrying platform, heating to 160 ℃, reacting for 30 hours, centrifuging the solution to remove the solvent, washing the solid product with distilled water and ethanol, fully drying and grinding into fine powder to prepare the phenolic resin nano microsphere coated nano SiO2And (4) component.
(2) Preparing a hollow carbon nano microsphere component 4: coating phenolic resin nano-microspheres with nano-SiO2Placing the component 4 in an atmosphere furnace, heating to 850 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, keeping the temperature and calcining for 6h, placing the calcined product in a hydrofluoric acid solution with the mass fraction of 15%, and etching to remove SiO2And washing the solid product by using distilled water and ethanol and fully drying to prepare the hollow carbon nano microsphere component 4.
(3) Preparation of Co3O4Composite oxygen reduction catalyst material loaded with hollow carbon microspheres 4: adding distilled water solvent, hollow carbon nano microsphere component 4, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, adding aqueous solution of hydrogen peroxide after ultrasonic dispersion is uniform, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box to heat to 110 ℃ for reaction for 8 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating to 260 ℃ at the heating rate of 2 ℃/min, performing heat preservation treatment for 2 hours, and preparing the nano-particle-containing catalystTo obtain Co3O4A composite oxygen reduction catalyst material 4 carrying hollow carbon microspheres.
Example 5
(1) Preparation of phenolic resin nano-microsphere coated nano SiO2And (5) component: adding a mixed solvent of ethanol and distilled water into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the distilled water is 3.5:1, adding ammonia water to adjust the pH value of the solution to 10, adding m-diphenol, stirring and dissolving, slowly dropwise adding ethyl orthosilicate, stirring uniformly, adding an aqueous solution of formaldehyde and a surfactant cetyl trimethyl ammonium bromide, wherein the mass ratio of the m-diphenol to the ethyl orthosilicate to the formaldehyde to the cetyl trimethyl ammonium bromide is 1:8:0.6:1.5, placing the solution into a constant-temperature water bath, heating to 40 ℃, stirring at a constant speed for reaction for 30 hours, pouring the solution into a high-pressure reaction kettle, placing the solution into a reaction heating box, wherein the reaction heating box comprises a heat insulation layer, a base is arranged below the inner part of the heat insulation layer, a support is fixedly connected above the base, a constant-temperature heater is fixedly connected above the support, the constant-temperature heater is fixedly connected with a heating ring, a heating box, A high-pressure reaction kettle is arranged above the objective table, the temperature is increased to 160 ℃, the reaction is carried out for 30 hours, the solution is centrifugally separated to remove the solvent, the solid product is washed by distilled water and ethanol, the solid product is fully dried and ground into fine powder, and the nano SiO coated phenolic resin microspheres are prepared2And (5) component.
(2) Preparing a hollow carbon nano microsphere component 5: coating phenolic resin nano-microspheres with nano-SiO2Placing the component 5 in an atmosphere furnace, heating to 850 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, keeping the temperature and calcining for 6h, placing the calcined product in 20 mass percent hydrofluoric acid solution, and etching to remove SiO2And washing the solid product by using distilled water and ethanol and fully drying to prepare the hollow carbon nano microsphere component 5.
(3) Preparation of Co3O4Composite oxygen reduction catalyst material loaded with hollow carbon microspheres 5: adding distilled water solvent, hollow carbon nano microsphere component 5, cobalt nitrate, urea and ammonium fluoride into a reaction bottle, ultrasonically dispersing uniformly, and adding aqueous solution of hydrogen peroxide, wherein the hollow carbon nano microsphere component isPouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a reaction heating box, heating the high-pressure reaction kettle to 140 ℃ for reaction for 8 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying the solid product, placing the solid product into a resistance furnace, heating the solid product to 300 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation treatment for 2 hours to prepare the Co microsphere component 5, cobalt nitrate, urea, ammonium fluoride and hydrogen peroxide in the mass ratio of 35:100:200:50:1803O4A composite oxygen reduction catalyst material 5 carrying hollow carbon microspheres.
Co obtained in respective examples3O4Placing the composite oxygen reduction catalyst material 1-5 loaded with the hollow carbon microspheres in an ethanol solvent, adding acetylene black and a Nafion solution serving as conductive agents, uniformly coating slurry on foamed nickel, drying and tabletting to prepare an anode working electrode material, and performing electrochemical performance test on a CHI760 electrochemical workstation by taking a platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode and a 0.1 mol/L potassium hydroxide solution as an electrolyte.
Figure BDA0002487465080000101
In summary, the one Co3O4The composite oxygen reduction catalyst of the load hollow carbon microsphere uses cetyl trimethyl ammonium bromide as a surfactant and is prepared by in-situ polymerization method on nano SiO2The surface of the hollow carbon nano microsphere is generated into phenolic resin nano microspheres, and then the hollow carbon nano microsphere is prepared by high-temperature carbonization and hydrofluoric acid etching, has good small-size effect and huge specific surface area, and can accelerate Co3O4In the oxygen adsorption process of the oxygen reduction reaction, a large number of oxygen vacancies are generated in the carbon nano-microsphere in the high-temperature heat treatment process, and the introduction of the oxygen vacancies can optimize the electronic structure distribution of the carbon nano-microsphere, so that the oxygen reduction catalytic performance of the catalyst is enhanced.
Preparing petal-shaped Co by taking hollow carbon nano microspheres as carriers through a high-pressure hydrothermal method3O4Nanorod structure, larger specific surface area, and Co3O4Nano meterThe rods are uniformly distributed on the surface of the hollow carbon nano microsphere, thereby effectively inhibiting Co3O4The aggregation of the nano-rods exposes a large amount of electrochemical active centers, and the carbon nano-microspheres have good electronic conductivity and electron mobility, and are Co3O4A multi-level conductive network is formed between the two layers, so that the conductive performance of the catalyst is enhanced, the diffusion and the transmission of electrons are promoted, and Co is enabled3O4The composite oxygen reduction catalyst loaded with the hollow carbon microspheres shows lower reduction peak potential and overpotential and has excellent oxygen reduction catalytic activity.

Claims (4)

1. Co3O4The composite oxygen reduction catalyst loaded with the hollow carbon microspheres comprises the following raw materials and components, and is characterized in that: the hollow carbon nano-microsphere, the cobalt nitrate, the urea, the ammonium fluoride and the hydrogen peroxide in a mass ratio of 15-35:100:150-200:40-50: 120-180.
2. Co according to claim 13O4The composite oxygen reduction catalyst loaded with the hollow carbon microspheres is characterized in that: the Co3O4The preparation method of the composite oxygen reduction catalyst loaded with the hollow carbon microspheres comprises the following steps:
(1) adding ammonia water into a mixed solvent of ethanol and distilled water with a volume ratio of 2.5-3.5:1 to adjust the pH value of the solution to 8-10, adding m-diphenol and ethyl orthosilicate, adding aqueous solution of formaldehyde and cetyl trimethyl ammonium bromide serving as a surfactant, heating to 30-40 ℃, reacting for 20-30h, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a reaction heating box, heating to 160 ℃ for 20-30h, centrifugally separating, washing, drying and grinding to prepare the nano SiO coated phenolic resin nano microsphere2；
(2) Coating phenolic resin nano-microspheres with nano-SiO2Placing the mixture in an atmosphere furnace, heating to 750-20% hydrofluoric acid solution at a heating rate of 5-10 ℃/min and 850 ℃ in a nitrogen atmosphere, keeping the temperature and calcining for 4-6h, and etching to remove SiO2Washed and dried to prepare the hollow carbonNano-microspheres;
(3) adding hollow carbon nano microspheres, cobalt nitrate, urea and ammonium fluoride into a distilled water solvent, adding an aqueous solution of hydrogen peroxide after uniform ultrasonic dispersion, pouring the solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a reaction heating box, heating to 140 ℃ for reaction for 4-8h, filtering, washing and drying, placing a solid product into a resistance furnace, heating to 300 ℃ at the heating rate of 2-5 ℃/min, and carrying out heat preservation treatment for 1-2h to obtain Co3O4A composite oxygen reduction catalyst loaded with hollow carbon microspheres.
3. Co according to claim 23O4The composite oxygen reduction catalyst loaded with the hollow carbon microspheres is characterized in that: the reaction heating box comprises a heat insulation layer, a base is arranged below the inner portion of the heat insulation layer, a support is fixedly connected to the upper portion of the base, a constant temperature heater is fixedly connected to the upper portion of the support, the constant temperature heater is fixedly connected with a heating ring, a heating box is fixedly connected to the upper portion of the base, the upper portion of the inner portion of the heating box is fixedly connected with an objective table, and a high-pressure reaction kettle is arranged above the objective table.
4. Co according to claim 23O4The composite oxygen reduction catalyst loaded with the hollow carbon microspheres is characterized in that: the mass ratio of the m-diphenol, the ethyl orthosilicate, the formaldehyde and the hexadecyl trimethyl ammonium bromide is 1:5-8:0.4-0.6: 0.8-1.5.
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