CN108134098B - Efficient biomass carbon electrochemical oxygen reduction catalyst and preparation method and application thereof - Google Patents

Efficient biomass carbon electrochemical oxygen reduction catalyst and preparation method and application thereof Download PDF

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CN108134098B
CN108134098B CN201810140565.8A CN201810140565A CN108134098B CN 108134098 B CN108134098 B CN 108134098B CN 201810140565 A CN201810140565 A CN 201810140565A CN 108134098 B CN108134098 B CN 108134098B
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agaric
carbonization
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oxygen reduction
carbonized
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CN108134098A (en
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梁汉璞
王西龙
陈国栋
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8803Supports for the deposition of the catalytic active composition
    • H01M4/8807Gas diffusion layers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8825Methods for deposition of the catalytic active composition
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96Carbon-based electrodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention belongs to the technical field of electrocatalysis, and particularly relates to an electrochemical oxygen reduction catalyst for converting fungus and agaric, and a preparation method and application thereof. Auricularia auricula is used as a biomass raw material, a carbonization treatment mode combining pre-carbonization and complete carbonization is adopted, and then the biomass carbon-based catalyst with good hydrophilicity is obtained by acid cooking. The fungus agaric is cheap, easy to obtain and environment-friendly, the requirement on equipment in the preparation process is low, the preparation process is short, the operation is simple, the preparation process is environment-friendly, no waste is discharged, the large-scale production is facilitated, and the fungus agaric has a wide industrial application prospect.

Description

Efficient biomass carbon electrochemical oxygen reduction catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to an electrochemical oxygen reduction catalyst for converting fungus and agaric, and a preparation method and application thereof.
Background
With the further development of industrial technology and the continuous increase of population, the environment is continuously worsened due to the large amount of ore burned, meanwhile, the contradiction between consumption and supply of energy is increasingly sharp, and the research and development of environment-friendly new energy technology becomes a task which needs to be solved urgently in the field of environmental protection in the world nowadays and is imperative.
The proton exchange membrane fuel cell is a fourth generation fuel cell which takes perfluorinated sulfonic acid resin polymer as electrolyte, hydrogen or reformed gas as fuel, air or oxygen as oxidant and converts chemical energy of the fuel into electric energy rapidly and efficiently, has a working interval of 25-120 ℃, can be rapidly started at room temperature, has the important advantages of long service life, high specific power and energy, no electrolyte loss and the like, and is considered to be one of the most important new energy technologies for replacing the traditional combustion power generation mode and the power of an internal combustion engine of an automobile. In recent years, our country has made a great deal of progress in the research on fuel cells, and exemplary electric vehicles which are independently developed and powered by low-temperature fuel cells are on the market, but one of the obstacles limiting further large-scale commercial production is the low-cost and large-scale preparation of the cathode high-efficiency oxygen reduction catalyst.
Different catalysts have different adsorption capacities on oxygen reduction reaction intermediate products, and can show different oxygen reduction activities, and the platinum catalyst has excellent catalytic activity due to moderate adsorption capacity on reaction intermediate species. In practical application, the current commercialized oxygen reduction catalyst is mainly a platinum/carbon catalyst, namely platinum is dispersed on commercial Vulcan XC-72R, and the electrochemical performance of the catalyst is superior to that of other catalysts. However, the worldwide platinum resource reserves are rare and high in price, and the cost reduction of the fuel cell and further large-scale commercial application are greatly hindered. At the same time, Pt is mixed with CO and SO2And the like, and the fuel is subjected to poisoning and inactivation, and also subjected to catalytic oxidation reaction with the fuel permeated from the anode to form mixed potential, so that the output power of the fuel cell is greatly reduced. Therefore, the development of a cathode catalyst which has high electrocatalytic activity for oxygen reduction reaction, low price, poisoning resistance and good methanol permeability resistance is a key problem to be solved urgently in the research field of fuel cells.
The nano carbon material has at least one dimension reaching nano level, and has the advantages of rich structure and form, good conductivity, large specific surface, environment friendliness, strong corrosion resistance, unique surface property and the like, thus being an ideal metal-free catalyst material. Extensive research shows that the electrochemical performance of the nano carbon can be obviously improved by doping a certain amount of nitrogen and iron in the nano carbon. This is because nitrogen is a neighboring atom of carbon in the periodic table of elements, with an atomic radius (0.80 a) closer to that of carbon (0.86 a), and nitrogen atom doping does not cause a large lattice mismatch in the carbon nanomaterial. Meanwhile, nitrogen has one more electron than carbon, the electronegativity is larger than that of carbon, and the introduction of nitrogen can change the electronic structure of the carbon nano material, improve the density and activity of delocalized pi electrons of the carbon nano material, and further improve the electrochemical activity of the carbon. In 2012, the research of professor davidian at the university of stanford in the united states finds that the oxygen reduction performance of the Fe-N co-doped carbon nanotube is obviously superior to that of a carbon nanotube doped with pure N, which indicates that Fe is also one of important active sites influencing oxygen reduction, and the synergistic effect of the two has important significance for improving the electrochemical performance of carbon.
Disclosure of Invention
The invention aims to solve the problems that the development of a direct fuel cell is limited, the cost of a commercial catalyst of a cathode oxygen reduction electrocatalyst is too high at the present stage, and the catalytic performance of a low-cost catalyst cannot meet the requirements, and develops a brand-new biomass carbon oxygen reduction catalyst, a method for preparing the catalyst with high oxygen reduction electrocatalytic performance and excellent stability by using fungus agaric as a raw material and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the efficient electrochemical oxygen reduction catalyst is prepared by using agaric as biomass material and through carbonization, acid boiling and other steps.
The carbonization treatment mode combining the pre-carbonization and the complete carbonization is as follows: crushing the freeze-dried agaric, performing heat treatment on the crushed agaric at the temperature of 300-400 ℃ in a nitrogen atmosphere for 1-2 hours, cooling to room temperature, and taking out to obtain pre-carbonized agaric; and then completely carbonizing at the carbonization temperature of 700-1000 ℃, wherein the carbonization atmosphere is nitrogen, the carbonization time is 1-3 hours, and after the carbonization, the furnace is cooled to room temperature by air and taken out.
And soaking the pre-carbonized product in excessive acetone for ultrasonic treatment for 2-3 hours, then repeatedly washing with acetone, placing in the air, naturally volatilizing, airing, crushing and completely carbonizing.
And crushing the full-carbonized product, putting the crushed full-carbonized product into a mixed solution with the molar ratio of excess hydrogen peroxide to nitric acid being 1:1, boiling for 12-24 hours at 80-100 ℃, performing hydrophilic treatment, performing suction filtration and washing by using deionized water until the pH value is 7, and drying for 24-30 hours at 60-80 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity.
The preparation method of the high-efficiency electrochemical oxygen reduction catalyst comprises the steps of taking agaric as a biomass raw material, adopting a carbonization treatment mode combining pre-carbonization and complete carbonization, and then carrying out acid cooking to obtain the biomass carbon-based catalyst with good hydrophilicity.
Further, the following steps are carried out:
(1) collecting and purifying fungus plant agaric: collecting fungus plant Auricularia which is wild or artificially planted, and removing impurities and freeze-drying for later use;
(2) pre-carbonizing agaric: crushing the freeze-dried agaric, performing heat treatment on the crushed agaric at the temperature of 300-400 ℃ in a nitrogen atmosphere for 1-2 hours, cooling to room temperature, and taking out to obtain pre-carbonized agaric;
(3) pre-carbonization product treatment: soaking the pre-carbonized product in excessive acetone for ultrasonic treatment for 2-3 hours, then repeatedly washing with acetone, placing in the air, naturally volatilizing, airing and crushing for later use;
(4) and (3) complete carbonization: completely carbonizing the product at 700-1000 ℃, wherein the carbonizing atmosphere is nitrogen, the carbonizing time is 1-3 hours, and after the carbonization is finished, carrying out furnace air cooling to room temperature and taking out;
(5) the hydrophilicity of the catalyst obtained by carbonization is improved: and crushing the full-carbonized product, putting the crushed full-carbonized product into a mixed solution with an excessive molar ratio of hydrogen peroxide to nitric acid of 1:1, boiling for 12-24 hours at 80-100 ℃, performing hydrophilic treatment, performing suction filtration and washing by using deionized water until the pH value is 7, and drying for 24-30 hours at 60-80 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity.
Ultrasonically soaking the collected agaric in deionized water for 12-24 hours for cleaning, wherein the deionized water is replaced every 2 hours, and the cleaning is finished; placing the ultrasonically cleaned agaric in excessive ethanol, ultrasonically soaking for 4-6 hours, taking out, naturally airing in the air, and freezing for 48-72 hours at the temperature of-50 ℃ after airing for later use.
The step 2) is to place the raw materials in a crucible for pre-carbonization treatment;
cleaning the agaric in the step 3) by using acetone, then placing the agaric in the air, naturally volatilizing and airing, crushing the pre-carbonized agaric into powder, and sieving the powder by using a 200-mesh sieve for later use;
and 4) placing the pre-carbonized product in a crucible, and carrying out carbonization treatment by using a tube furnace to obtain the completely carbonized biomass carbon.
The concentrations of the hydrogen peroxide and the nitric acid in the step 5) are both 2 mol/L.
The application of a high-efficiency electrochemical oxygen reduction catalyst in electrochemical oxygen reduction reaction.
Compared with the existing catalyst preparation method, the invention has the following essential characteristics and creativity:
the method obtains the oxygen reduction electrocatalytic nano material which does not contain precious metals, has excellent performance and outstanding stability, has low cost, simple equipment requirement and short preparation flow, and has the advantages of being superior to other precious metal catalysts and biomass catalysts in preparation, and specifically comprises the following steps:
(1) the raw materials used for preparing the catalyst are wild or artificially-planted agarics which can be discarded as biomass waste in many cases, the price is very low, the agarics can be recycled, and the catalyst has an environment-friendly effect and has important significance for purifying the environment and reducing the cost of the catalyst;
(2) the agaric adopted by the invention has natural component advantages, the protein content in 100 g of dry agaric is as high as 10.6 g, the iron content is as high as 185 mg, the agaric belongs to a natural iron-nitrogen doped carbon-based composite material, and meanwhile, iron and nitrogen are dispersed in the agaric at the atomic and molecular level, so that compared with experiment and industrial doping, the dispersion state is obviously improved, the catalytic performance is improved, and the agaric has incomparable advantages compared with artificial doping. The protein content and the iron content of the agaric are obviously higher than those of other biomass materials, and the electrocatalytic performance of a carbon matrix can be obviously improved by uniformly doping high nitrogen and metal elements, so that the agaric has obvious structural and component advantages relative to other biomass materials;
(3) according to the invention, a carbonization process combining pre-carbonization and complete carbonization is adopted in the process of preparing the catalyst, the pre-carbonization can lead a part of molecular groups with lower decomposition temperature to be pyrolyzed firstly, and macromolecular groups with higher decomposition temperature requirements keep the original structure, so that the pre-carbonized agaric is in a porous shrinkage structure, cracked molecular impurities can be effectively removed through dissolving and cleaning with acetone, a porous pre-carbonization structure is formed, meanwhile, the resistance of further pyrolysis and volatilization of later-stage macromolecules can be relieved, the carbonization is easier and more complete, the formed void structure is more uniform and fine, the mass transfer and the conductivity of the catalyst are improved, and the electrocatalytic performance of the catalyst is improved;
(4) the defect of poor hydrophilicity of the carbonized biomass material which is produced for a long time is overcome by acid boiling treatment in the preparation process, the hydrophilicity of the material can be obviously improved by the catalyst which is completely carbonized by acid boiling of the mixed solution of hydrochloric acid and hydrogen peroxide, so that the dispersibility of the carbonized material in ethanol or aqueous solution is improved, the dispersion effect of the catalyst on the surface of a platinum carbon electrode in the subsequent electrochemical measurement process can be obviously improved, the electrocatalytic effect of the catalyst is exerted to the maximum, and the invention is one of the creative characteristics that the electrocatalytic performance of the carbonized biomass material is obviously superior to that of the existing reported biomass material.
(5) The invention uses agaric as biomass raw material, and prepares the biomass carbon-based composite material with self-generated porous microstructure and self-doping effect by a two-step carbonization process. The material has excellent oxygen reduction electrocatalytic performance and good stability. The fungus agaric is cheap, easy to obtain and environment-friendly, the requirement on equipment in the preparation process is low, the preparation process is short, the operation is simple, the preparation process is environment-friendly, no waste is discharged, the large-scale production is facilitated, and the fungus agaric has a wide industrial application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of an oxygen reduction catalyst prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction spectrum of an oxygen-reducing catalyst prepared in example 1 of the present invention.
FIG. 3 shows the oxygen reduction electrocatalytic performance of the catalyst prepared in example 1 of the present invention.
FIG. 4 is a transmission electron microscope image of the oxygen reduction catalyst prepared in example 2 of the present invention.
FIG. 5 is an X-ray diffraction spectrum of an oxygen-reducing catalyst prepared in example 2 of the present invention.
FIG. 6 shows the oxygen reduction electrocatalytic performance of the catalyst prepared in example 2 of the present invention.
FIG. 7 is a scanning electron microscope image of the oxygen-reducing catalyst prepared in example 3 of the present invention.
FIG. 8 is an X-ray diffraction spectrum of an oxygen-reducing catalyst prepared in example 3 of the present invention.
FIG. 9 shows the oxygen reduction electrocatalytic performance of the catalyst prepared in example 3 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The preparation method is simple in preparation process, high in effective product yield, and the prepared biomass carbon material has excellent oxygen reduction electrocatalytic performance and stability. Firstly, repeatedly cleaning edible fungus collected in the field or purchased edible fungus by using deionized water and absolute ethyl alcohol to remove surface impurities, and freeze-drying the purified raw material; secondly, carrying out pre-carbonization and acetone combined cleaning on the freeze-dried sample to remove partial organic matters; and finally, finally carbonizing the pre-carbonized raw material and obtaining the carbon-based composite material catalyst with a pure phase and a porous particle structure by an acid washing treatment method. The method has the advantages of simple process steps, short flow, adjustable morphology and structure and the like in the aspect of preparing the nano porous carbon material, the prepared carbon material has large specific surface area and low price, the catalytic performance can almost be compared with that of the commercial catalyst Pt/C with high price at the present stage, the performance is more stable, the activation time is shorter, the requirement on equipment in the whole route is low, the process stability is good, and the method has important industrial popularization and application values.
Example 1
Collecting wild fungus, soaking the collected fungus in excessive deionized water under ultrasonic wave at 45 Hz for 12 hr, and replacing the deionized water every 2 hr until the cleaning is completed. Placing the ultrasonically cleaned agaric in excessive ethanol, ultrasonically soaking for 4 hours at 45 Hz, taking out, and naturally airing in the air. And finally, placing the naturally dried agaric into a freeze drying device, and further removing residual water in the agaric, wherein the freeze drying temperature is 50 ℃ below zero, and the freezing time is 48 hours. And (3) putting the freeze-dried edible fungus into a grinder for grinding and powdering, and sieving by using a 200-mesh sieve to obtain edible fungus biomass powder. Placing the powder in a corundum crucible, wherein the volume of the powder is about one fifth of that of the crucible, then carrying out heat treatment at 300 ℃ for 1 hour in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the pre-carbonized agaric. Soaking the pre-carbonized agaric prepared in the step by using excessive acetone, carrying out ultrasonic treatment on the pre-carbonized agaric by using 45 Hz for 2 hours, washing the pre-carbonized agaric by using acetone for 3 times, placing the pre-carbonized agaric in the air, naturally volatilizing and airing the pre-carbonized agaric, crushing the pre-carbonized agaric into powder by using artificial grinding, and sieving the powder by using a 200-mesh sieve; and then placing the pre-carbonized powder in a corundum crucible, and carrying out final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 700 ℃, the carbonization atmosphere is nitrogen, the carbonization time is 1 hour, and after the carbonization is finished, the biomass carbon is taken out along with furnace air cooling to room temperature to obtain the completely carbonized biomass carbon. Finally, the obtained completely carbonized agaric is crushed into nano-particle powder with the particle size of less than 100nm again, and the concentration of hydrogen peroxide and nitric acid is 2mol L-1The mixed solution is subjected to hydrophilic treatment and unnecessary metal elements in the subsequent electrochemical catalytic reaction process are removed, namely, the mixed solution is boiled for 12 hours at 80 ℃, then is filtered and washed by deionized water until the pH value is 7, and is dried for 24 hours at 60 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity, the tissue morphology is shown in figure 1, the prepared biomass carbon is amorphous granular carbon, the phase composition is shown in figure 2, only a carbon peak appears, and no diffraction peak of other elements appears.
The pure platinum nanocrystalline obtained by the method is subjected to electrocatalysisPerforming performance test by taking 0.1 mol/L potassium hydroxide solution as electrolyte, loading the catalyst on the surface of a platinum-carbon electrode with the load density of 100 micrograms/square centimeter and the effective working area of the surface of the electrode of 0.1256 square centimeters to perform oxygen reduction electrocatalysis reaction, wherein the scanning rate of linear voltammetry is 0.01V s-1The reference electrode is an Ag/AgCl electrode, the counter electrode is a platinum wire, the specific oxygen reduction catalytic performance is shown in figure 3, and the current density reaches 3mA cm-2As the rotational speed increases, the current density increases significantly. The potential range from the initial potential to the limit diffusion current is less than 0.3V, and the catalyst has good electronic conduction and oxygen reduction catalytic performance.
Example 2
Collecting wild fungus, soaking collected fungus in deionized water for 18 hours in an ultrasonic mode, and replacing the deionized water every 2 hours until the cleaning is finished. Placing the ultrasonically cleaned agaric in excessive ethanol, ultrasonically soaking for 5 hours at 45 Hz, taking out, and naturally airing in the air. And finally, placing the naturally dried agaric in a freeze drying device, and further removing residual water in the agaric, wherein the freeze drying temperature is 50 ℃ below zero, and the freezing time is 60 hours. And (3) putting the freeze-dried edible fungus into a grinder for grinding and powdering, and sieving by using a 200-mesh sieve to obtain edible fungus biomass powder. Placing the powder in a corundum crucible, wherein the volume of the powder is about one fifth of that of the crucible, then carrying out heat treatment at 350 ℃ for 1.5 hours in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the pre-carbonized agaric. Soaking the pre-carbonized agaric prepared in the step in excessive acetone for ultrasonic treatment for 2.5 hours, washing with acetone for 4 times, placing in the air, naturally volatilizing and airing, crushing the pre-carbonized agaric into powder by artificial grinding, and sieving with a 200-mesh sieve; and (2) placing the pre-carbonized powder in a corundum crucible, performing final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 850 ℃, the carbonization atmosphere is nitrogen, the carbonization time is 1.5 hours, and after the carbonization is finished, performing air cooling along with the furnace to room temperature and taking out the biomass carbon to obtain the completely carbonized biomass carbon. And finally, crushing the obtained completely carbonized agaric into nano powder below 100nm again, performing hydrophilic treatment in a mixed solution with the concentration ratio of hydrogen peroxide to nitric acid being 1:1, removing useless metal elements in the subsequent electrochemical catalytic reaction process, namely boiling for 18 hours at 90 ℃, then performing suction filtration and washing by using deionized water until the pH value is 7, and drying for 27 hours at 70 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity, wherein the tissue morphology is shown in figure 4, and the prepared biomass carbon is amorphous granular carbon and has a nano-pore structure inside. The composition of the phase is shown in FIG. 5, from which only carbon peaks appear and no diffraction peaks of other elements appear.
Carrying out electrocatalysis performance test on the obtained pure platinum nanocrystal, adopting 0.1 mol/liter potassium hydroxide as electrolyte, carrying out oxygen reduction electrocatalysis reaction on the platinum carbon electrode surface with the loading density of 100 micrograms/square centimeter of the catalyst and the effective working area of the electrode surface of 0.1256 square centimeters, wherein the linear volt-ampere scanning rate is 0.01V s-1The reference electrode is an Ag/AgCl electrode, the counter electrode is a platinum wire, the specific oxygen reduction catalytic performance is shown in figure 6, and the current density reaches 5 mA-cm-2. The current density at the potential of-0.3V vs. Ag/AgCl reaches the limit diffusion current region, and meanwhile, the potential range from the initial potential to the limit diffusion current is less than 0.3V, which indicates that the obtained catalyst has excellent electron conduction and oxygen reduction catalytic performance.
Example 3
Collecting wild fungus, ultrasonically soaking the collected fungus in deionized water at 45 Hz for 24 hours, and replacing the deionized water every 2 hours until the cleaning is finished. Placing the agaric cleaned by ultrasonic in ethanol, soaking for 6 hours by ultrasonic, taking out, placing in the air, and naturally drying. And finally, placing the naturally dried agaric into a freeze drying device, and further removing residual water in the agaric, wherein the freeze drying temperature is 50 ℃ below zero, and the freezing time is 72 hours. And (3) putting the freeze-dried edible fungus into a grinder for grinding and powdering, and sieving by using a 200-mesh sieve to obtain edible fungus biomass powder. And placing the powder in a corundum crucible, wherein the volume of the corundum crucible is about one fifth of the volume of the crucible, then carrying out heat treatment at 400 ℃ for 2 hours in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the pre-carbonized agaric. Soaking the pre-carbonized agaric prepared in the step in excessive acetone for ultrasonic treatment for 3 hours, washing the pre-carbonized agaric with acetone for 5 times, placing the pre-carbonized agaric in the air, naturally volatilizing and airing, crushing the pre-carbonized agaric into powder by artificial grinding, and sieving the powder with a 200-mesh sieve; and (2) placing the pre-carbonized powder in a corundum crucible, performing final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 1000 ℃, the carbonization atmosphere is nitrogen, the carbonization time is 3 hours, and after the carbonization is finished, performing air cooling along with the furnace to room temperature and taking out to obtain the completely carbonized biomass carbon. Finally, crushing the obtained completely carbonized agaric into nano-particle powder below 100nm again, performing hydrophilic treatment in a mixed solution with the concentration ratio of hydrogen peroxide to nitric acid being 1:1, removing useless metal elements in the subsequent electrochemical catalytic reaction process, namely boiling for 24 hours at 100 ℃, then performing suction filtration and washing by using deionized water until the pH value is 7, and drying for 30 hours at 80 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity, wherein the tissue morphology is shown in figure 7, the prepared biomass carbon is amorphous granular carbon, and each particle has a nano pore. The composition of the phase is shown in fig. 8, and it can be seen from the figure that the main phase of the obtained material is a carbon phase, and no diffraction peak of other structural phases exists.
And (2) carrying out an electrocatalysis performance test on the obtained pure platinum nanocrystal, adopting 0.1 mol/liter potassium hydroxide as an electrolyte, carrying out an oxygen reduction electrocatalysis reaction stability test on the platinum-carbon electrode with the loading density of the catalyst on the surface of the platinum-carbon electrode of 100 micrograms/square centimeter and the effective working area of the surface of the electrode of 0.1256 square centimeters, wherein the reference electrode is an Ag/AgCl electrode, the counter electrode is a platinum wire, the test potential is-0.3V vs. Ag/AgCl, the specific stability is shown in figure 9, and the current attenuation is extremely slow in the test of more than 10 hours, which indicates that the prepared biomass-carbon composite material has excellent electrocatalysis stability.

Claims (10)

1. A high efficiency electrochemical oxygen reduction catalyst, characterized by: auricularia auricula is used as a biomass raw material, a carbonization treatment mode combining pre-carbonization and complete carbonization is adopted, and then the biomass carbon-based catalyst with good hydrophilicity is obtained by acid cooking.
2. The high efficiency electrochemical oxygen reduction catalyst according to claim 1, wherein: the carbonization treatment mode combining the pre-carbonization and the complete carbonization is as follows: crushing the freeze-dried agaric, performing heat treatment on the crushed agaric at the temperature of 300-400 ℃ in a nitrogen atmosphere for 1-2 hours, cooling to room temperature, and taking out to obtain pre-carbonized agaric; and then completely carbonizing at the carbonization temperature of 700-1000 ℃, wherein the carbonization atmosphere is nitrogen, the carbonization time is 1-3 hours, and after the carbonization, the furnace is cooled to room temperature by air and taken out.
3. The high efficiency electrochemical oxygen reduction catalyst according to claim 2, wherein: and soaking the pre-carbonized agaric in excessive acetone for ultrasonic treatment for 2-3 hours, then repeatedly washing the agaric with acetone, placing the agaric in the air, naturally volatilizing and airing the agaric, and completely carbonizing the agaric after crushing.
4. The high efficiency electrochemical oxygen reduction catalyst according to claim 1, wherein: and crushing the full-carbonized product, putting the crushed full-carbonized product into a mixed solution with the molar ratio of excess hydrogen peroxide to nitric acid being 1:1, boiling for 12-24 hours at 80-100 ℃, performing hydrophilic treatment, performing suction filtration and washing by using deionized water until the pH value is 7, and drying for 24-30 hours at 60-80 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity.
5. A method of preparing the high efficiency electrochemical oxygen reduction catalyst of claim 1, wherein: auricularia auricula is used as a biomass raw material, a carbonization treatment mode combining pre-carbonization and complete carbonization is adopted, and then the biomass carbon-based catalyst with good hydrophilicity is obtained by acid cooking.
6. The method of preparing a high efficiency electrochemical oxygen reduction catalyst according to claim 5, wherein:
(1) collecting and purifying fungus plant agaric: collecting fungus plant Auricularia which is wild or artificially planted, and removing impurities and freeze-drying for later use;
(2) pre-carbonizing agaric: crushing the freeze-dried agaric, performing heat treatment on the crushed agaric at the temperature of 300-400 ℃ in a nitrogen atmosphere for 1-2 hours, cooling to room temperature, and taking out to obtain pre-carbonized agaric;
(3) pre-carbonization product treatment: soaking the pre-carbonized product in excessive acetone for ultrasonic treatment for 2-3 hours, then repeatedly washing with acetone, placing in the air, naturally volatilizing, airing and crushing for later use;
(4) and (3) complete carbonization: completely carbonizing the product at 700-1000 ℃, wherein the carbonizing atmosphere is nitrogen, the carbonizing time is 1-3 hours, and after the carbonization is finished, carrying out furnace air cooling to room temperature and taking out;
(5) the hydrophilicity of the catalyst obtained by carbonization is improved: and crushing the full-carbonized product, putting the crushed full-carbonized product into a mixed solution with an excessive molar ratio of hydrogen peroxide to nitric acid of 1:1, boiling for 12-24 hours at 80-100 ℃, performing hydrophilic treatment, performing suction filtration and washing by using deionized water until the pH value is 7, and drying for 24-30 hours at 60-80 ℃ to obtain the biomass carbon-based catalyst with good hydrophilicity.
7. The method of preparing a high efficiency electrochemical oxygen reduction catalyst according to claim 6, wherein: and in the step 1), ultrasonically soaking the collected agaric in deionized water for 12-24 hours for cleaning, placing the ultrasonically cleaned agaric in excessive ethanol, ultrasonically soaking for 4-6 hours, taking out, naturally airing in the air, and after airing, freezing at the temperature of minus 50 ℃ for 48-72 hours for later use.
8. The method of preparing a high efficiency electrochemical oxygen reduction catalyst according to claim 6, wherein: the step 2) is to place the raw materials in a crucible for pre-carbonization treatment;
cleaning the agaric in step 3) by using acetone, then placing the agaric in the air, naturally volatilizing and airing, crushing the pre-carbonized agaric into powder, and sieving the powder by using a 200-mesh sieve for later use;
and 4) placing the pre-carbonized product in a crucible, and carrying out carbonization treatment by using a tube furnace to obtain the completely carbonized biomass carbon.
9. The method of preparing a high efficiency electrochemical oxygen reduction catalyst according to claim 6, wherein: the concentrations of the hydrogen peroxide and the nitric acid in the step 5) are both 2 mol/L.
10. Use of a high efficiency electrochemical oxygen reduction catalyst according to claim 1, wherein: the catalyst is used in electrochemical oxygen reduction reaction.
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