CN108134098A - A kind of efficient biomass carbon electrochemical oxygen reduction catalyst and its preparation method and application - Google Patents
A kind of efficient biomass carbon electrochemical oxygen reduction catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to electro-catalysis technical field, specifically a kind of electrochemical oxygen reduction catalyst for converting fungi agaric and its preparation method and application.Using agaric as biomass material, using the carbonization treatment mode that is combined with carbonization of being carbonized in advance, and after boiled through acid and obtain the good biomass carbon-supported catalysts of hydrophily.The present invention uses cheap and easy to get, environmental-friendly Mycophyta agaric as raw material, and than relatively low, preparation flow is short and easy to operate for requirement of the preparation process to equipment; preparation process is environmental-friendly; no waste discharge is especially advantageous for large-scale production, has wide prospects for commercial application.
Description
Technical field
The invention belongs to electro-catalysis technical field, specifically a kind of electrochemical oxygen reduction for converting fungi agaric is urged
Agent and its preparation method and application.
Background technology
With the further development of industrial technology, the continuous growth of population, a large amount of calcined ores cause continuing for environment
Deteriorate, while cause the consumption of the energy and be becoming increasingly acute with supplying contradiction, research and develop environmental-friendly new energy technology with
Become one task in the urgent need to address of world today's field of environment protection, it is imperative.
Proton Exchange Membrane Fuel Cells is a kind of using perfluorinated sulfonic resin polymer as electrolyte, with hydrogen or reformation
Gas is as fuel, using air or oxygen as oxidant, by the chemical energy of fuel rapidly and efficiently the transform into electric energy the 4th
Replacing fuel battery, operation interval are 25~120 DEG C, can quickly be started at room temperature, have long lifespan, specific power and energy
Height, electroless mass flow such as lose at the important advantages, it is considered to be replace current traditional combustion generation mode and automobile internal mechanomotive force
One of mostly important new energy technology.In recent years, China achieves considerable progress, and have successively to the research of fuel cell
Exemplary motor automobile using low-temperature fuel cell as the independent research of power emerges, but limits its further large-scale commercial
One of obstacle of production is exactly the low cost of the efficient oxygen reduction catalyst of cathode, prepare with scale.
Different catalysts are different to the adsorption capacity of oxygen reduction reaction intermediate product, can show different hydrogen reduction and live
Property, and platinum catalyst has excellent catalytic activity due to the adsorption capacity to reaction intermediates kind is moderate.In practical applications,
Platinum still based on platinum/C catalyst, i.e., is distributed to the Vulcan XC-72R of business by current commercialized oxygen reduction catalyst
On, there is the chemical property better than other catalyst.But global platinum resource reserve rareness, and it is at high price, greatly hinder
The reduction of fuel cell cost and further large-scale commercial application are hindered.Meanwhile Pt and CO, SO2The effects that and occur
Poison inactivation also can occur catalytic oxidation with the fuel that anode is permeated, form mixed potential, substantially reduce fuel cell
Output power.So developing has oxygen reduction reaction high electrocatalytic active, cheap, anti-poisoning, while have good
The cathod catalyst of good methanol tolerant permeance property is the critical issue of fuel cell studies field urgent need to resolve.
Nano-carbon material is the carbon material that at least one dimension dimensionally reaches nanometer scale, with structure and shape
State is enriched, and good conductivity, specific surface is big, environmental-friendly, and corrosion resistance is strong, and the advantages such as surface nature uniqueness are ideal nothings
Metal catalyst materials.Widely research shows that, nano-sized carbon adulterates a certain amount of nitrogen and iron, can be obviously improved its electrochemistry
Energy.This is because nitrogen is adjacent atom of the carbon in the periodic table of elements, atomic radius (0.80 angstrom) and carbon atom radius (0.86
Angstrom) be closer to, nitrogen atom doping will not cause larger lattice mismatch in carbon nanomaterial.Meanwhile nitrogen is one more than carbon
A electronics, electronegativity is bigger than carbon, the electronic structure of the changeable carbon nanomaterial of introducing of nitrogen, improve its delocalization pi-electron it is close
Degree and activity, so as to improve the electro-chemical activity of carbon.2012, Stanford Univ USA Dai Hongjie was taught the study found that Fe-N
The hydrogen reduction performance of codope carbon nanotube will be substantially better than the carbon nanotube of simple N doping, and it is also to influence oxygen also to illustrate Fe
One of former important activity site, the two synergistic effect have great significance for promoting the chemical property of carbon.
Invention content
The problem to be solved in the present invention is for the development restriction of direct fuel cell and cathodic oxygen reduction elctro-catalyst
The problem of commercial catalysts cost is excessively high at this stage, and inexpensive catalyst catalytic performance is not met by requiring and develop one
It plants completely new biomass carbon oxygen reduction catalyst and its fungi agaric is used to prepare hydrogen reduction electrocatalysis characteristic height for raw material, stablize
The methods and applications of the excellent catalyst of property.
To achieve the above object, the present invention use technical solution for：
A kind of high-efficiency electrochemical oxygen reduction catalyst, using agaric as biomass material, using pre- carbonization and carbonization
The carbonization treatment mode being combined, and after boiled through acid and obtain the good biomass carbon-supported catalysts of hydrophily.
The pre- carbonization treatment mode being combined with carbonization that is carbonized：Agaric after freeze-drying is crushed in 300~400
DEG C, be heat-treated 1~2 hour under nitrogen atmosphere, be cooled to room temperature taking-up, obtain pre- carbonization agaric；It is then at carburizing temperature then
700~1000 DEG C of progress carbonizations, carburizing atmosphere are nitrogen, and carbonization time is 1~3 hour, air-cooled with stove after the completion of carbonization
It is taken out to room temperature.
The pre- carbonized product is soaked in excessive acetone and is ultrasonically treated 2~3 hours, is then rushed repeatedly using acetone
It washes, is placed in air, volatilization naturally is dried, and carbonization is carried out after crushing.
It is 1 that full carbonized product is placed in excessive hydrogen peroxide after crushing with nitric acid molar ratio:In 1 mixed liquor, 80~
Boiling is boiled 12~24 hours at 100 DEG C, carries out hydrophilic treated, is then 7 with deionized water filtering and washing to pH, in 60~80 DEG C of temperature
The lower drying of degree 24~30 hours, obtains the good biomass carbon-supported catalysts of hydrophily.
A kind of preparation method of high-efficiency electrochemical oxygen reduction catalyst, using agaric as biomass material, using pre- carbonization
With the carbonization treatment mode that carbonization is combined, and after boiled through acid and obtain the good biomass carbon-supported catalysts of hydrophily.
Further：
(1) it acquires and purifies fungi plant agaric：Wild or artificial growth fungi plant agaric is collected, then
It is cleaned to it and freeze-drying process, for use；
(2) the pre- carbonization treatment of agaric：Agaric after freeze-drying is crushed and is heat-treated 1 under 300~400 DEG C, nitrogen atmosphere
~2 hours, taking-up is cooled to room temperature, obtains pre- carbonization agaric；
(3) pre- carbonized product processing：Pre- carbonized product is soaked in excessive acetone and is ultrasonically treated 2~3 hours, then adopts
It is rinsed, is placed in air repeatedly with acetone, volatilization naturally is dried, and is crushed for use；
(4) carbonization：Above-mentioned product is subjected to carbonizations in 700~1000 DEG C, carburizing atmosphere is nitrogen, during carbonization
Between for 1~3 hour, after the completion of carbonization, be air-cooled to room temperature with stove and take out；
(5) the catalyst hydrophily that carbonization obtains improves：By full carbonized product be placed in after crushing excessive hydrogen peroxide with
Nitric acid molar ratio is 1:In 1 mixed liquor, boil and boil 12~24 hours at 80~100 DEG C, carry out hydrophilic treated, then spend from
Sub- water filtering and washing is 7 to pH, is dried 24~30 hours at a temperature of 60~80 DEG C, it is carbon-based to obtain the good biomass of hydrophily
Catalyst.
The step 1) by the agaric of acquisition, clean for 12-24 hours in deionized water by ultrasound immersion, wherein, every
A deionized water is replaced within 2 hours, cleaning is completed；The agaric being cleaned by ultrasonic is placed in excessive ethyl alcohol, then ultrasound is impregnated
After 4-6 hours, taking-up is placed in naturally dry in air, and it is subzero 50 DEG C to dry after freeze-drying temperature, cooling time 48-
72 hours, for use.
Raw material is placed in crucible and carries out pre- carbonization treatment by the step 2)；
The step 3) is described to be placed on through acetone cleaning in air, and volatilization naturally is dried, and the agaric that will then be carbonized in advance is broken
Powder is broken into, crosses 200 mesh sieve, for use；
The step 4) is placed in crucible pre- carbonized product, carries out carbonization treatment using tube furnace, it is complete to obtain carbonization
Biomass carbon.
The concentration of the step 5) hydrogen peroxide and nitric acid is 2mol/L.
A kind of application of high-efficiency electrochemical oxygen reduction catalyst, the catalyst answering in electrochemical oxygen reduction reaction
With.
Compared with existing method for preparing catalyst, essential feature of the invention and creativeness are embodied in：
The hydrogen reduction electro-catalysis nanometer material that the method for the present invention obtains without precious metal but function admirable, stability protrudes
Material, this method is at low cost, and equipment requirement is simple, and preparation flow is short, has better than other noble metal catalysts and biomass catalyzing
The advantages of prepared by agent, specially：
(1) present invention prepares raw material used in catalyst as wild or artificial growth agaric, many feelings of these agarics
It can be abandoned under condition as biomass waste material, price is very cheap, is recycled the effect that can also play environmental protection, for
Environment purification reduces catalyst cost and is respectively provided with important meaning；
(2) agaric that uses of the present invention, itself has a natural ingredient advantage, protein in every 100 grams of dry product agarics
Content is up to 10.6 grams, and iron content is up to 185 milligrams, belongs to natural iron-nitrogen-doped carbon based composites, while iron and nitrogen exist
Disperseed in agaric with atom and molecule rank, adulterated relative to experiment and industry, dispersity is obviously improved, to catalytic performance
Raising, have and manually adulterate incomparable advantage.Protein content and iron content are all apparently higher than other biological in agaric
Material, high nitrogen and metallic element Uniform Doped can be obviously improved the electrocatalysis characteristic of carbon base body, so that agaric has
Relative to the apparent structure of other biological material and component advantage；
(3) present invention employs the pre- carbonization technique for being carbonized and being combined with carbonization in catalyst process is prepared, in advance
The molecular radical that being carbonized can cause a part of decomposition temperature relatively low takes the lead in being pyrolyzed, and the macromolecular base that decomposition temperature is more demanding
Group then keeps original structure, this allows for the agaric after pre- carbonization and porous contraction structure is presented, and is cleaned by acetone solution, can be with
Cracking molecular impurity is effectively removed, forms porous pre- carbonized structure, while the further pyrolysis devolatilization of later stage macromolecular can be alleviated
Resistance so that carbonization be easier, more completely, the gap structure of formation is evenly fine and closely woven, improves the mass transfer and conduction of catalyst
Ability, so as to promote the electrocatalysis characteristic of catalyst；
(4) difference of biomass carbonization material hydrophilic for a long time is solved by Acid treatment in preparation process of the present invention
Drawback boils the catalyst after carbonization by hydrochloric acid and hydrogen peroxide mixed solution acid, can be obviously improved the hydrophily of material,
So as to promote dispersibility of the char-forming material in ethyl alcohol or aqueous solution, it can be obviously improved in subsequent electrochemical measurement process and be catalyzed
Agent is in the dispersion effect of platinum carbon electrode surface, so that the electro-catalysis effect of catalyst performs to maximum, this is also the present invention
The electrocatalysis characteristic of carbonization biological material is substantially better than one of creative feature of existing report biological material.
(5) present invention, by two-step method carbonization technique, is prepared with self-generating by the use of agaric as biomass material
The biomass carbon based composites of porous microstructure and auto-dope effect.The material has excellent hydrogen reduction electro-catalysis
Performance and good stability.The present invention uses cheap and easy to get, environmental-friendly Mycophyta agaric, and for raw material, preparation process pair is set
Standby requirement is than relatively low, and preparation flow is short and easy to operate, and preparation process is environmental-friendly, no waste discharge, is especially advantageous for advising
Modelling produces, and has wide prospects for commercial application.
Description of the drawings
The oxygen reduction catalyst scanning electron microscopic picture that Fig. 1 embodiment of the present invention 1 is prepared.
The oxygen reduction catalyst X-ray diffraction spectrum that Fig. 2 embodiment of the present invention 1 is prepared.
The catalyst oxygen reduction electrocatalysis characteristic that Fig. 3 embodiment of the present invention 1 is prepared.
The oxygen reduction catalyst transmission electron microscope picture that Fig. 4 embodiment of the present invention 2 is prepared.
The oxygen reduction catalyst X-ray diffraction spectrum that Fig. 5 embodiment of the present invention 2 is prepared.
The catalyst oxygen reduction electrocatalysis characteristic that Fig. 6 embodiment of the present invention 2 is prepared.
The oxygen reduction catalyst scanning electron microscopic picture that Fig. 7 embodiment of the present invention 3 is prepared.
The oxygen reduction catalyst X-ray diffraction spectrum that Fig. 8 embodiment of the present invention 3 is prepared.
The catalyst oxygen reduction electrocatalysis characteristic that Fig. 9 embodiment of the present invention 3 is prepared.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiments.Institute
It is conventional method unless otherwise instructed to state method.The raw material can obtain unless otherwise instructed from open commercial sources.
The biomass carbon material that preparation flow of the present invention is simple, effective products collection efficiency is high, prepared has superior oxygen also
Former electrocatalysis characteristic and stability.First deionized water and anhydrous second are used by field acquisition or by buying the agaric obtained
Alcohol carries out cleaning removal surface impurity repeatedly, and frozen dried is carried out to purified raw material；Secondly, freeze-drying sample is carried out pre-
Carbonization combines acetone and cleans, and removes partial organic substances；Finally, it is finally carbonized to the raw material that are carbonized in advance and passes through pickling processes
Method obtains that object is mutually pure, C-base composte material catalyst of porous particle structure.The present invention is preparing nanoporous carbon materials
Aspect has the advantages such as processing step is simple, flow is short, appearance structure is adjustable, carbon-based material large specific surface area, the price of preparation
Cheap, catalytic performance can almost compare favourably with expensive commercial catalysts Pt/C at this stage, and performance is more stablized, living
The change time is shorter, and whole route equipment requirement is low, technology stability is good, has important commercial introduction application value.
Embodiment 1
Wild fungi agaric is acquired, ultrasound immersion 12 is small in excessive deionized water and under 45 hertz by the agaric of acquisition
When, it is intermediate to replace a deionized water every 2 hours, until cleaning is completed.The agaric being cleaned by ultrasonic is placed in excessive second
In alcohol, after ultrasound is impregnated 4 hours under 45 hertz, taking-up is placed in naturally dry in air.Finally, the agaric of naturally dry is placed in
In freeze drying equipment, the moisture of agaric internal residual is further removed, freeze-drying temperature is subzero 50 DEG C, and cooling time is
48 hours.Agaric after freeze-drying is placed in pulverizer and carries out broken powdered processing, and crosses 200 mesh sieve, obtains agaric biological
Matter powder.Powder is placed in corundum crucible, powder volume is about 1/5th of crucible volume, then in 300 DEG C, nitrogen atmosphere
Lower heat treatment 1 hour is enclosed, taking-up is cooled to room temperature, obtains pre- carbonization agaric.The pre- carbonization agaric that above-mentioned steps are prepared
It is impregnated using excessive propanone and uses 45 hertz to be ultrasonically treated 2 hours, then using acetone rinsing 3 times, be placed in air, it is natural
Volatilization is dried, and pre- carbonization agaric finally is broken into powder using underhand polish, crosses 200 mesh sieve；Pre- carbonized powder is placed in again
In corundum crucible, final carbonization treatment is carried out using tube furnace, carburizing temperature is 700 DEG C, and carburizing atmosphere is nitrogen, carbonization time
It is 1 hour, after the completion of carbonization, is air-cooled to room temperature with stove and takes out, obtain the complete biomass carbon that is carbonized.Finally by the complete of acquisition
Carbonization agaric is broken into the powder of nanometric particles of below 100nm again, and is 2mol L in hydrogen peroxide and concentration of nitric acid-1It is mixed
It closes and hydrophilic treated is carried out in solution and removes the useless metallic element in subsequent electrochemical catalytic reaction process, i.e., boiled at 80 DEG C
It boils 12 hours, is then 7 with deionized water filtering and washing to pH, is dried 24 hours at a temperature of 60 DEG C, it is good to obtain hydrophily
Good biomass carbon-supported catalysts, tissue topography is as shown in Figure 1, as can be seen from the figure prepared biomass carbon is unformed
Granulated carbon, object phase composition is shown in Fig. 2, only carbon peak occurs, and the diffraction maximum of other elements does not occur.
The pure Pt nanocrystal of above-mentioned acquisition is subjected to electrocatalysis characteristic test, using 0.1 mol/L concentration potassium hydroxide solution
As electrolyte, catalyst is 100 micro- grams/cm in the load density of platinum carbon electrode surface, and electrode surface effectively works
Area is 0.1256 square centimeter, carries out hydrogen reduction electrocatalytic reaction, and linear voltammetric scan rate is 0.01V s-1, reference electrode
It is platinum filament to electrode, specific hydrogen reduction catalytic performance is as shown in figure 3, current density reaches as seen from the figure for Ag/AgCl electrodes
3mA·cm-2, with the promotion of rotating speed, current density significantly increases.Limiting diffusion current, institute's electricity consumption are reached from take-off potential
Gesture range is less than 0.3V, has the conduction of good electronics and hydrogen reduction catalytic performance.
Embodiment 2
Wild fungi agaric is acquired, ultrasound is impregnated 18 hours in deionized water by the agaric of acquisition, and centre was every 2 hours
A deionized water is replaced, until cleaning is completed.The agaric being cleaned by ultrasonic is placed in excess ethyl alcohol, 45 hertz of ultrasounds are impregnated
After 5 hours, taking-up is placed in naturally dry in air.Finally, the agaric of naturally dry is placed in freeze drying equipment, further
The moisture of agaric internal residual is removed, freeze-drying temperature is subzero 50 DEG C, and cooling time is 60 hours.By the agaric after freeze-drying
It is placed in pulverizer and carries out broken powdered processing, and cross 200 mesh sieve, obtain agaric biological matter powder.Powder is placed in corundum
In crucible, powder volume is about 1/5th of crucible volume, is then heat-treated 1.5 hours under 350 DEG C, nitrogen atmosphere, cold
But it is taken out to room temperature, obtains pre- carbonization agaric.By the pre- carbonization agaric that above-mentioned steps prepare using excessive acetone soak
It is ultrasonically treated 2.5 hours, then using acetone rinsing 4 times, is placed in air, volatilize and dry naturally, finally using underhand polish
Pre- carbonization agaric is broken into powder, crosses 200 mesh sieve；Pre- carbonized powder is placed in corundum crucible, is carried out most using tube furnace
Whole carbonization treatment, carburizing temperature are 850 DEG C, and carburizing atmosphere is nitrogen, and carbonization time is 1.5 hours, after the completion of carbonization, with stove sky
It is cooled to room temperature taking-up, obtains the complete biomass carbon that is carbonized.Finally by the carbonization agaric of acquisition be broken into again 100nm with
Under nanometer powder, and be 1 in hydrogen peroxide and concentration of nitric acid ratio:Hydrophilic treated is carried out in 1 mixed solution and is removed follow-up
Useless metallic element in electrochemical catalysis reaction process is boiled that is, at 90 DEG C and is boiled 18 hours, then with deionized water filtering and washing
It is 7 to pH, is dried 27 hours at a temperature of 70 DEG C, obtain the good biomass carbon-supported catalysts of hydrophily, tissue topography is such as
Shown in Fig. 4, as can be seen from the figure prepared biomass carbon is amorphous pellets carbon, and inside has nano-pore structure.Object phase
It forms as shown in Fig. 5, as can be seen from the figure only carbon peak occurs, the diffraction maximum of no other elements.
The pure Pt nanocrystal of above-mentioned acquisition is subjected to electrocatalysis characteristic test, using 0.1 mol/L concentration potassium hydroxide conduct
Electrolyte, catalyst are 100 micro- grams/cm in the load density of platinum carbon electrode surface, the effective work area of electrode surface
It is 0.1256 square centimeter, carries out hydrogen reduction electrocatalytic reaction, linear voltammetric scan rate is 0.01V s-1, reference electrode is
Ag/AgCl electrodes are platinum filament to electrode, and specific hydrogen reduction catalytic performance is as shown in fig. 6, current density reaches as seen from the figure
5mA·cm-2.Current potential has just reached limiting diffusion current area for current density at -0.3V vs.Ag/AgCl, meanwhile, from starting electricity
Position reaches limiting diffusion current, and potential range used is less than 0.3V, illustrates that there is the catalyst obtained excellent electronics to conduct
With hydrogen reduction catalytic performance.
Embodiment 3
Wild fungi agaric is acquired, 45 hertz of ultrasounds are impregnated 24 hours in deionized water by the agaric of acquisition, intermediate every
A deionized water was replaced every 2 hours, until cleaning is completed.The agaric being cleaned by ultrasonic is placed in ethyl alcohol, it is small that ultrasound impregnates 6
Shi Hou, taking-up are placed in naturally dry in air.Finally, the agaric of naturally dry is placed in freeze drying equipment, further removed
The moisture of agaric internal residual is removed, freeze-drying temperature is subzero 50 DEG C, and cooling time is 72 hours.Agaric after freeze-drying is put
Broken powdered processing is carried out in pulverizer, and crosses 200 mesh sieve, obtains agaric biological matter powder.Powder is placed in corundum earthenware
In crucible, volume is about 1/5th of crucible volume, is then heat-treated 2 hours, is cooled to room temperature under 400 DEG C, nitrogen atmosphere
It takes out, obtains pre- carbonization agaric.The pre- carbonization agaric that above-mentioned steps prepare is ultrasonically treated 3 using excessive acetone soak
Hour, it then using acetone rinsing 5 times, is placed in air, volatilizees and dry naturally, will be finally carbonized in advance agaric using underhand polish
Powder is broken into, crosses 200 mesh sieve；Pre- carbonized powder is placed in corundum crucible, final carbonization treatment, carbon are carried out using tube furnace
It is 1000 DEG C to change temperature, and carburizing atmosphere is nitrogen, and carbonization time is 3 hours, after the completion of carbonization, is air-cooled to room temperature with stove and takes out,
Obtain the complete biomass carbon that is carbonized.The carbonization agaric of acquisition is finally broken into below 100nm nanoparticle powders again
End, and be 1 in hydrogen peroxide and concentration of nitric acid ratio:It carries out hydrophilic treated in 1 mixed solution and removes to be catalyzed in subsequent electrochemical
Useless metallic element in reaction process boils that is, at 100 DEG C and boils 24 hours, is then 7 with deionized water filtering and washing to pH,
It is dried 30 hours at a temperature of 80 DEG C, obtains the good biomass carbon-supported catalysts of hydrophily, tissue topography is as shown in fig. 7, from figure
In it can be seen that prepared biomass carbon is amorphous pellets carbon, again with nanoaperture on each particle.Object phase composition is
Shown in Fig. 8, the material main phase that is as can be seen from the figure obtained is carbon phase, the diffraction maximum of no other structures object phase.
The pure Pt nanocrystal of above-mentioned acquisition is subjected to electrocatalysis characteristic test, using 0.1 mol/L concentration potassium hydroxide conduct
Electrolyte, catalyst are 100 micro- grams/cm in the load density of platinum carbon electrode surface, the effective work area of electrode surface
It is 0.1256 square centimeter, carries out hydrogen reduction electrocatalytic reaction stability test, reference electrode is Ag/AgCl electrodes, to electrode
For platinum filament, test potential is -0.3V vs.Ag/AgCl, and specific stability as shown in figure 9, have passed through up to 10 as seen from the figure
Hour or more test in, current attenuation is extremely slow, illustrates that there is prepared biomass carbon composite material excellent electricity to urge
Change stability.
Claims (10)
1. a kind of high-efficiency electrochemical oxygen reduction catalyst, it is characterised in that：Using agaric as biomass material, using pre- carbonization with
The carbonization treatment mode that carbonization is combined, and after boiled through acid and obtain the good biomass carbon-supported catalysts of hydrophily.
2. high-efficiency electrochemical oxygen reduction catalyst as described in claim 1, it is characterised in that：The pre- carbonization and carbonization
The carbonization treatment mode being combined：Agaric after freeze-drying is crushed and is heat-treated 1~2 hour under 300~400 DEG C, nitrogen atmosphere,
Taking-up is cooled to room temperature, obtains pre- carbonization agaric；It is then 700~1000 DEG C of progress carbonizations then at carburizing temperature, is carbonized
Atmosphere is nitrogen, and carbonization time is 1~3 hour, after the completion of carbonization, is air-cooled to room temperature with stove and takes out.
3. high-efficiency electrochemical oxygen reduction catalyst as described in claim 2, it is characterised in that：The pre- carbonized product is soaked in
It is ultrasonically treated 2~3 hours in excessive acetone, is then rinsed, be placed in air repeatedly using acetone, volatilization naturally is dried, powder
Carbonization is carried out after broken.
4. high-efficiency electrochemical oxygen reduction catalyst as described in claim 1, it is characterised in that：By full carbonized product after crushing
It is 1 that excessive hydrogen peroxide, which is placed in, with nitric acid molar ratio:It in 1 mixed liquor, boils and boils 12~24 hours at 80~100 DEG C, carry out parent
Then water process is 7 with deionized water filtering and washing to pH, dries 24~30 hours, obtain hydrophilic at a temperature of 60~80 DEG C
The good biomass carbon-supported catalysts of property.
5. a kind of preparation method of high-efficiency electrochemical oxygen reduction catalyst described in claim 1, it is characterised in that：Made with agaric
For biomass material, using the carbonization treatment mode that is combined with carbonization of being carbonized in advance, and after boiled through acid and obtain hydrophily
Good biomass carbon-supported catalysts.
6. the preparation method of high-efficiency electrochemical oxygen reduction catalyst as described in claim 5, it is characterised in that：
(1) it acquires and purifies fungi plant agaric：Wild or artificial growth fungi plant agaric is collected, then to it
It is cleaned and freeze-drying process, for use；
(2) the pre- carbonization treatment of agaric：It is small that agaric after freeze-drying is crushed into the heat treatment 1~2 under 300~400 DEG C, nitrogen atmosphere
When, taking-up is cooled to room temperature, obtains pre- carbonization agaric；
(3) pre- carbonized product processing：Pre- carbonized product is soaked in excessive acetone and is ultrasonically treated 2~3 hours, then using third
Ketone rinses repeatedly, is placed in air, and volatilization naturally is dried, and crushes for use；
(4) carbonization：Above-mentioned product is subjected to carbonization in 700~1000 DEG C, carburizing atmosphere is nitrogen, and carbonization time is
It 1~3 hour, after the completion of carbonization, is air-cooled to room temperature with stove and takes out；
(5) the catalyst hydrophily that carbonization obtains improves：Full carbonized product is placed in excessive hydrogen peroxide and nitric acid after crushing
Molar ratio is 1:It in 1 mixed liquor, boils and boils 12~24 hours at 80~100 DEG C, carry out hydrophilic treated, then use deionized water
Filtering and washing is 7 to pH, is dried 24~30 hours at a temperature of 60~80 DEG C, obtains the carbon-based catalysis of the good biomass of hydrophily
Agent.
7. the preparation method of high-efficiency electrochemical oxygen reduction catalyst as described in claim 6, it is characterised in that：The step 1)
By the agaric of acquisition, ultrasound immersion is cleaned for 12-24 hours in deionized water, and the agaric being cleaned by ultrasonic is placed in excess
Ethyl alcohol in, then ultrasound impregnate 4-6 hour after, taking-up be placed in naturally dry in air, dry after be freeze-dried temperature be zero
Lower 50 DEG C, cooling time is 48-72 hours, for use.
8. the preparation method of high-efficiency electrochemical oxygen reduction catalyst as described in claim 6, it is characterised in that：The step 2)
Raw material is placed in crucible and carries out pre- carbonization treatment；
The step 3) is described to be placed on through acetone cleaning in air, and volatilization naturally is dried, and is then broken into pre- carbonization agaric
Powder crosses 200 mesh sieve, for use；
The step 4) is placed in crucible pre- carbonized product, carries out carbonization treatment using tube furnace, obtains the complete life that is carbonized
Substance carbon.
9. the preparation method of high-efficiency electrochemical oxygen reduction catalyst as described in claim 6, it is characterised in that：The step 5)
The concentration of hydrogen peroxide and nitric acid is 2mol/L.
10. a kind of application of high-efficiency electrochemical oxygen reduction catalyst described in claim 1, it is characterised in that：The catalyst
Application in electrochemical oxygen reduction reaction.
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