CN106684396A - Method for preparing bifunctional catalyst from peanut hull - Google Patents
Method for preparing bifunctional catalyst from peanut hull Download PDFInfo
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- CN106684396A CN106684396A CN201611192600.8A CN201611192600A CN106684396A CN 106684396 A CN106684396 A CN 106684396A CN 201611192600 A CN201611192600 A CN 201611192600A CN 106684396 A CN106684396 A CN 106684396A
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/9041—Metals or alloys
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
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Abstract
The invention discloses a method for preparing a bifunctional electro-catalyst from peanut hull, and belongs to the technical field of electro-catalysis. The method comprises the steps of adding an active agent, a carbon source and a nitrogen source into waste peanut hull biomass serving as a raw material to obtain exotic atom-doped porous carbon; adding a certain amount of metal doping agent, and performing secondary carbonization to obtain a metal and nitrogen co-doped porous carbon material, wherein the material has excellent oxygen reduction and oxygen evolution electro-catalysis performance. By adopting the cheap, readily available and environment-friendly peanut hull biomass as a raw material, the preparation process is innocuous and harmless. The bifunctional electro-catalyst can be applied to oxygen reduction and oxygen evolution.
Description
Technical field
The present invention is the new method that bifunctional catalyst is prepared on a kind of peanut shell, belongs to electro-catalysis technical field.
Background technology
Since 21st century, lack of energy and environmental degradation are that the mankind have to 21 century the great difficulty for facing
Topic.Due to the burning of fossil fuel, global warming, many The Surroundings in Cities quality in the world increasingly decline.Therefore, Ren Menyi
A kind of straight alternative energy source for attempting to look for and developing green, environmental protection and sustainable development.Fuel cell is used as a kind of new energy
Source, is a kind of TRT that chemical energy is converted into electric energy by electrochemical reaction, and it has high conversion efficiency, without dirt
Dye, noise is low and high reliability, gets more and more people's extensive concerning.
The reaction rate of cathodic oxygen reduction (ORR) several orders of magnitude smaller than the speed of anode hydroxide reaction (HOR), so
Oxygen reduction reaction on negative electrode is the core for researching and developing fuel cell.But hydrogen reduction needs noble metal platinum as catalyst, hinders
Its business development.At present, fuel cell car of 100kW about needs the Pt of 100g, and the reserves of Pt are only in the earth's crust
39000t.Platinum scarcity causes the high cost of fuel cell car.Therefore, non-precious metal catalyst is developed to replace noble metal
Platinum is the research hot topic of fuel cell.Current research is roughly divided into both direction：First, develop low-platinum catalyst, such as metal
Alloy structure, core shell structure；Second, noble metal platinum, such as exotic atom doping carbon material are replaced using base metal.Exotic atom is mixed
Miscellaneous carbon material has low cost, performance good and the good characteristic such as methanol tolerance, since Jasinski in 1964 has found that cobalt phthalocyanine exists
Since the reduction of oxygen can be catalyzed in alkaline electrolyte, exotic atom doping carbon material is developed rapidly in electrochemistry.Recently
The research of several years finds that exotic atom doping carbon material can compare favourably in electro-catalysis ability with platinum, and in stability and
Business platinum is exceeded on methanol tolerance.Doping carbon material is generally divided into two classes, and a class is that have metal-doped carbon material, a class
It is without metal-doped carbon material.
Hydrogen is new as one kind in petrochemical industry because its energy density is high, product is cleaned without CO2 emission
Clean energy resource, increasingly obtain the attention of people, in current technology of preparing, water electrolysis hydrogen production transformation efficiency is high, technique
Simply, technology maturation, but due to anode oxygen evolution reaction conventional catalyst noble metal ruthenium-oxide or yttrium oxide, price is held high
Expensive, material is rare and less stable, hinders the commercial applications of water electrolysis hydrogen production.So in order to extensive using electrolysis
Aquatic products hydrogen, now Research Thinking generally be with base metal (non-noble metal oxide) come instead of Precious metal oxidation ruthenium or
Yttrium oxide, so that reduces cost.
Peanut shell as a kind of biomass cheap and easy to get, with high high-temp stability, good pore performance, abundant
The advantages of carbon, nitrogen, sulfur content, add activator as presoma in peanut shell, further carbonization obtains nanoporous carbon, makes
Standby catalyst out shows excellent performance in hydrogen reduction and oxygen evolution reaction.
The content of the invention
First technical problem to be solved by this invention is directed to the current situation and electrochemistry bottleneck of fuel cell
Problem and propose a kind of method that brand-new presoma prepares elctro-catalyst, i.e., prepare double-function catalyzing by presoma of peanut shell
Agent.
Second technical problem to be solved by this invention is that activating agent (pore creating material), secondary nitrogen source are added in biomass
Or carbon source, obtain the big nanoporous carbon of specific surface area by high temperature cabonization.
3rd technical problem to be solved by this invention be on the basis of without metal-doped porous C catalyst, plus
Entering the metal dopant of different content carries out secondary carbonization to improve hydrogen reduction and oxygen precipitation performance.
The present invention in order to solve the above technical problems, the technical scheme for being used is with peanut shell as raw material, add activator,
Secondary carbon source, nitrogen source, are carbonized in temperature programming tube furnace, the ratio of the different metal of addition and different metal, secondary carbon
Change, finally obtain metal, nitrogen co-doped porous carbon.
Specific synthesis step of the invention is as follows：
(1) certain peanut shell ultrasonic disperse is dissolved in water；
(2) activator or pore creating material, secondary nitrogen source, carbon source are added, stirring is dried, and is denoted as product 1；
(3) product 1 is put into the tube furnace high temperature carbonization of procedural intensification, and pickling, washing is dried；
(4) a certain amount of metal-doped agent solution is added, stirring, filtering is dried, and is denoted as product 2；
(5) product 2 is put into secondary high-temperature carbonization in the tube furnace of procedural intensification.
By ESEM, transmission electron microscope, Raman spectrum, x-ray photoelectron power spectrum, X-ray diffraction spectra, inductive
A series of signs such as plasma mass, organic element analysis, complete analysis demonstrate prepared material for high dispersive metal,
Nitrogen co-doped porous carbon materials.
Further, the raw material of peanut shell are pre-processed before step (1), and the method for pretreatment includes following step
Suddenly：1. directly peanut shell is simply polished；2. peanut shell carries out hydro-thermal method and synthesizes carbon aerogels；Or carry out pre- carbonization etc. side
Method.The method of wherein pre- carbonization preferentially selects peanut shell hydrothermal synthesis of carbon aeroge, is put into the temperature heated in reactor
50-200 DEG C of scope, the heat time is 6-48 hours.
Peanut shell and the proportion of water are (1-12) g in step (1)：(1-12)ml.
Further, the activator or pore creating material selected in step (2) can be selected from：Potassium hydroxide, zinc chloride, hydroxide
Sodium, potassium chloride etc..The secondary carbon source that step (2) is added can be selected from：Glucose, shitosan, furfural, sucrose etc..Step
(2) the secondary nitrogen source for adding can be selected from：Urea, melamine, thiophene, thiocarbamide, acetonitrile, graphitic nitralloy carbon, dicyandiamide, contracting two
The mixture of one or more of urea etc..Peanut shell, activator or pore creating material, secondary carbon source, the quality of secondary nitrogen source compare scope
For：(1-20)：(1-20)：(1-20)：(1-20), preferably 1:1:2:2, mixing time is 6-48 hours in aqueous.
Further, step (3) is passed through inert gas as protection gas before being heated up to tube furnace, first, during holding
Between 1-3 hours, inert gas may be selected from nitrogen, argon gas, helium, neon, Krypton, xenon or radon gas etc..The intensification of carbonisation
Speed is 0.5-30 DEG C/min.The temperature of carbonization is 600-1200 DEG C (preferably 800-1000 DEG C), and 0.5- is incubated at such a temperature
8h, naturally cools to room temperature.Wherein preferably during the intensification that is carbonized, when being heated to 180-240 DEG C, 1-3 hours is incubated；Step
Suddenly the acid of pickling may be selected from nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid etc. in (3).
From nitrogen as protection gas, 2 hours retention times, with 2 DEG C per minute of speed still more preferably in step (3)
Degree rises, and is kept at 200 DEG C 2 hours, and 950 DEG C are kept for 2 hours.Hydrochloric acid is preferentially selected in pickling.Preferred steps (4) are metal-doped
Agent is metal water-soluble salt, and metal water-soluble salt is selected from one or more in molysite, manganese salt, cobalt salt, nickel salt, preferably
One or more and molysite in manganese salt, cobalt salt, nickel salt；One kind in further preferred molysite and manganese salt, cobalt salt, nickel salt or
The various mass ratio of person is 1:1.
Peanut shell and the mass ratio of slaine after carbonization are (1-20)：(1-20), mixing time is 6-48 hours.
Further, step (5) carbonisation is identical with step (3), and the programming rate of carbonisation is 0.5-30 DEG C/min.
The temperature of carbonization is 600-1200 DEG C (preferably 800-1000 DEG C), and 0.5-8h is incubated at such a temperature, naturally cools to room temperature, its
In preferably be carbonized heat up during, when being heated to 180-240 DEG C, be incubated 1-3 hours.
From nitrogen as protection gas, 2 hours retention times, with 2 DEG C per minute of speed still more preferably in step (5)
Degree rises, and is kept at 200 DEG C 2 hours, and 950 DEG C are kept for 2 hours.
The catalyst of preparation is applied in hydrogen reduction and oxygen evolution reaction.
Beneficial effects of the present invention are as follows：
1) the porous C catalyst that is adulterated with the exotic atom that is prepared as raw material of peanut shell discarded replaces noble metal platinum work
It is electrochemical catalyst, cost is substantially reduced, it might even be possible to ignored.But hydrogen reduction performance is similar to platinum in electrochemistry,
The chemical property that oxygen is separated out is more much better than platinum, and stability will have with methanol tolerance than business platinum stabilization, this catalyst
Hope and break through electrochemistry bottleneck problem, for the commercial applications of electrochemistry provide a kind of new approaches, there is wide in electrochemistry
Application prospect.
2) compared with prior art, this method preparation process is simple, easy to operate.Porous carbon materials have excellent conduction
Property, high-specific surface area and there is the grade pore structure that micropore, mesoporous and macropore coexist, be more beneficial for the transmission of mass transfer and electric charge.
The porous carbon of exotic atom doping provides substantial amounts of avtive spot, promotes the electrocatalysis characteristic of product.
3) with peanut shell as raw material, add activator, carbon source, nitrogen source to be carbonized and obtain the porous carbon of N doping, in order to enter one
Step improves chemical property, adds the metal of variety classes and different proportion, i.e., add metal in peanut shell in the carbonized
Dopant, makes metal adsorption in the hole of porous carbon, and secondary carbonization, so that the Metal Distribution for obtaining doping is uniform, activity
The easy exposed porous C catalyst in position.
4) preparation process of the present invention avoids the synthesis technique using toxic reagent and complexity, and preparation process is simple, operation
It is convenient, easily realize large-scale production.
5), using biomass peanut shell as raw material, storage capacity is abundant, with low cost, be conveniently easy to get, environment for the present invention
Close friend, meets the requirement of sustainable development.
Brief description of the drawings
Fig. 1 is that the synthetic method schematic diagram of bifunctional electrocatalyst is prepared with peanut shell in embodiment 1
Fig. 2 is the electron scanning micrograph of peanut shell catalyst after being carbonized in embodiment 1.
Fig. 3 is the transmission electron microscope photo of peanut shell catalyst after being carbonized in embodiment 1.
Fig. 4 is the distribution diagram of element of peanut shell catalyst after being carbonized in embodiment 1.
Fig. 5 is the X-ray diffraction spectra of peanut shell catalyst after being carbonized in embodiment 1.
Fig. 6 is the hydrogen reduction catalysis LSV comparison diagrams of elctro-catalyst and business Pt/C in embodiment 1.
Fig. 7 separates out performance and ruthenium-oxide comparison diagram for the elctro-catalyst and the oxygen of business Pt/C in embodiment 1.
Fig. 8 is the transmission electron microscope photo of peanut shell catalyst after being carbonized in embodiment 2.
Fig. 9 is the transmission electron microscope photo of peanut shell catalyst after being carbonized in embodiment 3.
LSV curve maps under elctro-catalyst hydrogen reduction catalysis different rotating speeds in Figure 10 embodiments 2.
LSV curve maps under elctro-catalyst hydrogen reduction catalysis different rotating speeds in Figure 11 embodiments 3.
Specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to following reality
Apply example.
Experimental drug derives from commercial channel (An Naiji, Chinese medicines group, Beijing Chemical Plant, Du Pont, AlfaAesar), except spy
Bright outer do not purify further is not mentionleted alone.
Embodiment 1：The method for preparing bifunctional electrocatalyst as raw material with biomass peanut shell
1) peanut shell is polished with pulverizer and crushed, and weighs 6g peanut shells, is dissolved in 80ml water, ultrasound 30 minutes, stirring 2
Hour.
2) transfer the solution into 100ml reactors, heat 150 DEG C 30 hours.
3) carbon aerogels in reactor are taken out, is filtered, repeatedly washed with water, dried.Filter cake 1g is taken to be transferred in beaker,
1g potassium hydroxide is added, 60ml water, 2g glucose, 2g melamines, magnetic agitation 12 hours is dried, and is denoted as powder 1.
4) powder 1 is carbonized in being put into tube furnace, and temperature is raised to 950 DEG C and (is risen with 2 DEG C per minute of speed, in 200 DEG C of guarantors
Hold 2 hours, 950 DEG C are kept for 2 hours), to be soaked 12 hours with 1MHCl 5ml, filtering is rinsed, with substantial amounts of water until PH=7 is
Only, product 1 is denoted as, N-PC is further denoted as.
5) 0.2g of carbonized product 1 is taken, FeCl is added2 4H2O 0.015g, NiCl2 6H2O 0.015g, magnetic agitation 12
Individual hour, dry, be denoted as product 2.
6) 2 two carbonizations of product, carburizing temperature is 900 DEG C (small in 200 DEG C of holdings 2 with 2 DEG C per minute of speed rising
When, 950 DEG C are kept for 2 hours), you can obtain high dispersive Fe, Ni of black, N codope porous carbon materials and be designated as NFeNi-PC-S
(wherein PC represents porous carbon, and S is represented and added a small amount of Fe, Ni).
Embodiment 2：The method for preparing bifunctional electrocatalyst as raw material with biomass peanut shell
1) peanut shell is polished with pulverizer and crushed, and weighs 6g peanut shells, is dissolved in 80ml water, ultrasound 30 minutes, stirring 2
Hour.
2) transfer the solution into 100ml reactors, heat 150 DEG C 30 hours.
3) carbon aerogels in reactor are taken out, is filtered, repeatedly washed with water, dried.Filter cake 1g is taken to be transferred in beaker,
1g potassium hydroxide is added, 60ml water, 2g glucose, 2g melamines, magnetic agitation 12 hours is dried, and is denoted as powder 1.
4) powder 1 is carbonized in being put into tube furnace, and temperature is raised to 950 DEG C and (is risen with 2 DEG C per minute of speed, in 200 DEG C of guarantors
Hold 2 hours, 950 DEG C are kept for 2 hours), to be soaked 12 hours with 1MHCl 5ml, filtering is rinsed, with substantial amounts of water until PH=7 is
Only, product 1 is denoted as, N-PC is further denoted as.
5) 0.2g of carbonized product 1 is taken, FeCl is added2 4H2O 0.03g, NiCl2 6H2O 0.03g, magnetic agitation 12
Hour, dry, it is denoted as product 2.
6) 2 two carbonizations of product, carburizing temperature is 900 DEG C (small in 200 DEG C of holdings 2 with 2 DEG C per minute of speed rising
When, 950 DEG C are kept for 2 hours), you can obtain high dispersive Fe, Ni of black, N codope porous carbon materials and be designated as NFeNi-PC-M
(wherein PC represents porous carbon, and M represents Fe, the Ni measured in adding).
Embodiment 3：The method for preparing bifunctional electrocatalyst as raw material with biomass peanut shell
1) peanut shell is polished with pulverizer and crushed, and weighs 6g peanut shells, is dissolved in 80ml water, ultrasound 30 minutes, stirring 2
Hour.
2) transfer the solution into 100ml reactors, heat 150 DEG C 30 hours.
3) carbon aerogels in reactor are taken out, is filtered, repeatedly washed with water, dried.Filter cake 1g is taken to be transferred in beaker,
1g potassium hydroxide is added, 60ml water, 2g glucose, 2g melamines, magnetic agitation 12 hours is dried, and is denoted as powder 1.
4) powder 1 is carbonized in being put into tube furnace, and temperature is raised to 950 DEG C and (is risen with 2 DEG C per minute of speed, in 200 DEG C of guarantors
Hold 2 hours, 950 DEG C are kept for 2 hours), to be soaked 12 hours with 1MHCl 5ml, filtering is rinsed, with substantial amounts of water until PH=7 is
Only, product 1 is denoted as, N-PC is further denoted as.
5) 0.2g of carbonized product 1 is taken, FeCl is added2 4H2O 0.075g, NiCl2 6H2O 0.075g, magnetic agitation 12
Individual hour, dry, be denoted as product 2.
6) 2 two carbonizations of product, carburizing temperature is 900 DEG C (small in 200 DEG C of holdings 2 with 2 DEG C per minute of speed rising
When, 950 DEG C are kept for 2 hours), you can obtain high dispersive Fe, Ni of black, N codope porous carbon materials and be designated as NFeNi-PC-L
(wherein PC represents porous carbon, and L is represented and added substantial amounts of Fe, Ni).
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Implementation method restriction, for those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms, cannot be exhaustive to all of implementation method here, every to belong to skill of the invention
Obvious change that art scheme is extended out changes row still in protection scope of the present invention.
Fig. 3 is the transmission electron microscope photo of peanut shell catalyst after embodiment 1 is carbonized, as can be seen from the figure after carbonization
Peanut shell catalyst in add metal Fe, Ni form the diameter about metallic particles of 80nm, by Fig. 4 (elements of embodiment 1
Distribution map) metallic particles that further illustrates this 80nm or so has Fe, Ni to be collectively forming.
Fig. 5 is the X-ray diffraction spectra of peanut shell catalyst after embodiment 1 is carbonized, the flower after being carbonized as seen from the figure
Raw shell becomes unformed porous carbon structure, there are 002 crystal face and 101 crystal faces, is spectrally occurred in that after metal is added
Three sharp peaks, the two sharp peaks may further determine that the existence form of the material of Fe, Ni metal composition, control
PDF cards, it will be seen that this Fe, Ni composition is the one kind in metal alloy structure.
Claims (10)
1. a kind of method that peanut shell prepares bifunctional catalyst, it is characterised in that comprise the following steps：
(1) certain peanut shell ultrasonic disperse is dissolved in water；
(2) activator or pore creating material, secondary nitrogen source, carbon source are added, stirring is dried, and is denoted as product 1；
(3) product 1 is put into the tube furnace high temperature carbonization of procedural intensification, and pickling, washing is dried；
(4) a certain amount of metal-doped agent solution is added, stirring, filtering is dried, and is denoted as product 2；
(5) product 2 is put into secondary high-temperature carbonization in the tube furnace of procedural intensification.
2. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that in step
(1) raw material of peanut shell are pre-processed before, and the method for pretreatment is comprised the following steps：1. directly peanut shell is simply beaten
Mill；2. peanut shell carries out hydro-thermal method and synthesizes carbon aerogels；Or carry out pre- carbonization；The method of wherein pre- carbonization：From peanut shell
Hydrothermal synthesis of carbon aeroge, is put into 50-200 DEG C of the temperature range heated in reactor, and the heat time is 6-48 hours.
3. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that step (1)
Middle peanut shell is (1-20) g with the proportion of water：(1-200)ml.
4. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that step (2)
The activator or pore creating material of middle selection are selected from：Potassium hydroxide, zinc chloride, NaOH, potassium chloride；Step (2) added two
Secondary carbon source is selected from：Glucose, shitosan, furfural, sucrose；The secondary nitrogen source that step (2) is added is selected from：Urea, melamine, thiophene
The mixture of one or more of fen, thiocarbamide, acetonitrile, graphitic nitralloy carbon, dicyandiamide, biuret etc..
5. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that peanut shell,
Activator or pore creating material, secondary carbon source, the quality of secondary nitrogen source are than scope：(1-20)：(1-20)：(1-20)：(1-20),
Mixing time is 6-48 hours in the aqueous solution.
6. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that peanut shell,
Activator or pore creating material, secondary carbon source, the mass ratio of secondary nitrogen source are 1:1:2:2.
7. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that step (3)
Before being heated up to tube furnace, inert gas is first passed through as protection gas, retention time 1-3 hours, inert gas was selected from
Nitrogen, argon gas, helium, neon, Krypton, xenon or radon gas；The programming rate of carbonisation is 0.5-30 DEG C/min；The temperature of carbonization
It is 600-1200 DEG C to spend, and 0.5-8h is incubated at such a temperature, naturally cools to room temperature；Wherein during the intensification that is carbonized,
When being heated to 180-240 DEG C, 1-3 hours is incubated；The acid of pickling is selected from nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid in step (3).
8. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that step (4)
Metal dopant is metal water-soluble salt, metal water-soluble salt be selected from one kind in molysite, manganese salt, cobalt salt, nickel salt or
Various, peanut shell and the mass ratio of slaine after carbonization are (1-20)：(1-20), mixing time is 6-48 hours.
9. the method for preparing bifunctional catalyst according to a kind of peanut shell described in claim 1, it is characterised in that step (3)
It is identical with step (5) carbonization, 2 hours retention times, risen with 2 DEG C per minute of speed as protection gas from nitrogen,
200 DEG C are kept for 2 hours, and 950 DEG C are kept for 2 hours.
10. the bifunctional catalyst for being prepared using claim 1-9 any one methods.
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| CN107486152A (en) * | 2017-08-23 | 2017-12-19 | 江苏大学 | A kind of preparation method and application of leaf based biomass carbon aerogels |
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| CN110148735A (en) * | 2019-06-03 | 2019-08-20 | 河南师范大学 | A kind of preparation method of self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode |
| CN114836787A (en) * | 2022-04-27 | 2022-08-02 | 东南大学 | Preparation method of molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst |
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