CN111908443A - Preparation method of self-doped porous carbon - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- 241000512259 Ascophyllum nodosum Species 0.000 claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000001994 activation Methods 0.000 claims abstract description 18
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000010790 dilution Methods 0.000 claims abstract description 7
- 239000012895 dilution Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 15
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
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- 229910052717 sulfur Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a preparation method of self-doped porous carbon, which comprises the following steps: putting the pretreated kelp powder into a crucible for carbonization to obtain carbide; mixing and grinding carbide and potassium hydroxide powder according to the proportion of 1: 2-1: 4, and then placing the mixture in a crucible for activation treatment to obtain porous carbon; soaking the porous carbon by adopting HCL solution, and adding deionized water for dilution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and finally, adding deionized water for centrifugal separation and drying to obtain the self-doped graded porous carbon material. The method is simple to operate, economical and environment-friendly, and the obtained self-doped graded porous carbon material has high specific surface area and excellent conductivity and has wide application prospect when being used as an electrode material of a super capacitor.
Description
Technical Field
The invention belongs to the technical field of preparation methods of adsorption materials, and relates to a preparation method of self-doped porous carbon.
Background
The porous carbon has good thermodynamic stability and high chemical stability, can keep chemical inertia in acid and alkali, has developed pore structure, high specific surface area and strong surface activity, can be conveniently subjected to functional modification, and has wide application in various fields such as catalysis, separation, energy, environment and the like. The synthesis method of the porous carbon material includes a gel method, a template method, an activation method, and the like. Although the gel method can conveniently control the process to obtain porous carbon with different pore diameters, the preparation period is long, the process is complex, and the porous carbon cannot be used on a large scale. The template method can be used for large-scale production, the process is stable, the prepared porous carbon has uniform aperture and ordered structure, but the template needs to be removed, the process is complex, and the prepared porous carbon has single aperture, so that the application of the porous carbon is limited. The activation method has wide raw material sources and simple preparation process, and is suitable for large-scale industrial production, but the prepared porous carbon mainly has micropores and wider pore size distribution, thereby limiting the application of the porous carbon in the aspects of catalysis, adsorption, lithium battery and the like. Porous materials can be classified by pore size into micropores (diameter less than 2nm), mesopores (diameter greater than 2nm and less than 50nm) and macropores (diameter greater than 50 nm). The microporous carbon material cannot be applied to industries such as adsorption, catalysis and the like because the pore channel is too small, molecules with larger diameters cannot enter the pore channel to react and macromolecules in reaction products in the pore channel cannot escape in time; the mesoporous carbon material has moderate aperture, high thermal stability and chemical stability, so that the mesoporous carbon material is widely applied to various aspects of separation, extraction, catalysis and adsorption, but has insufficient solution circulation; the macroporous carbon material can provide an effective channel for the circulation of a solution, but the macroporous carbon material has poor mechanical stability and too low specific surface area and is limited in the field of electrochemical application.
A large number of researches show that the surface functional group of the porous carbon has a remarkable influence on the electrochemical performance of the porous carbon, and other miscellaneous elements are easily introduced into the porous carbon for modification due to strong surface activity, so that the functional group is formed. N, P, S, F, B, etc., can improve the wettability and the reaction catalytic activity of the porous carbon, and can also generate an additional pseudocapacitance and improve the capacitance, so the research of the heteroatom doped porous carbon has attracted interest in recent years. The main sources of the heteroatoms are two, one is the heteroatoms doped by adding a material containing the heteroatoms to react in the preparation process, and the other is the heteroatoms carried by the raw material precursor. The raw materials for preparing the porous carbon mainly comprise petroleum, asphalt, coal, waste high polymer materials, biomass materials and the like. The biomass resource is rich, the cost is low, the biomass material is rich in various miscellaneous elements and belongs to renewable resources, the biomass material is used as a precursor to prepare the self-doped porous carbon, the method is simple, the cost is saved, and the problems of shortage of fossil fuel and environmental pollution can be relieved. In addition, plants in the nature have developed hierarchical porous structures due to respiration and metabolism, so that life activities such as gas exchange and nutrient circulation are guaranteed, and the hierarchical porous carbon material is favorably formed. At present, the biomass commonly used for preparing porous carbon comprises straws, agricultural waste residues, wood, fruit peels, fruit shells and the like. In contrast, few reports have been made of marine organisms as the porous carbon raw material. As is known, the sea has huge algae plant resources, but the algae products have low processing utilization rate and serious excess productivity.
Disclosure of Invention
The invention aims to provide a preparation method of self-doped porous carbon, which solves the problem of low processing utilization rate of seaweed products in the prior art.
The invention adopts the technical scheme that the preparation method of the self-doped porous carbon comprises the following steps:
step 1, putting the pretreated kelp powder into a crucible for carbonization treatment to obtain carbide;
step 2, mixing and grinding the carbide and potassium hydroxide powder according to the proportion of 1: 2-1: 4, and then placing the mixture in a crucible for activation treatment to obtain porous carbon;
step 3, soaking the porous carbon by adopting HCL solution, and adding deionized water for dilution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and finally, adding deionized water for centrifugal separation and drying to obtain the self-doped graded porous carbon material.
The invention is also characterized in that:
the pretreatment process of the step 1 comprises the following steps: drying the kelp powder in an oven at the temperature of 80-100 ℃ for 30-60 min.
The carbonization process in the step 1 comprises the following steps: and (3) placing the crucible in a tube furnace, heating to 600-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen gas flow of 100-300 ml/min, preserving heat for 90-120 min, and naturally cooling to room temperature.
The activation process of the step 2 is as follows: and covering the crucible, putting the crucible into a tube furnace, heating to 600-800 ℃ at the speed of 5-10 ℃/min under the protection of 100-300 ml/min nitrogen gas flow, preserving heat for 60-120 min, and naturally cooling to room temperature.
The concentration of the HCL solution in the step 3 is 0.5-1 mol/L.
The diluent is a mixture of deionized water and ethanol.
The parameters of the centrifugation process were: the rotation speed is 5000-1000 rpm, and the time is 10-15 min.
The invention has the beneficial effects that:
according to the preparation method of the self-doped porous carbon, the kelp is selected as a precursor of carbon, and as the kelp is low in price, wide in source, high in yield and fast in propagation, and the kelp contains nitrogen, phosphorus and sulfur heteroatoms, the hierarchical porous carbon material containing nitrogen, phosphorus and sulfur can be directly obtained after carbonization and activation treatment, and other reagents are not required to be added for doping the heteroatoms; the method is simple to operate, economical and environment-friendly, and the obtained self-doped graded porous carbon material has high specific surface area and excellent conductivity and has wide application prospect when being used as an electrode material of a super capacitor; the utilization rate of the kelp product can be improved, higher added value is given to the kelp product, and the problem of energy shortage can be effectively relieved.
Drawings
FIG. 1 is a scanning electron microscope image of a self-doped graded-pore carbon material obtained in example 1 in a preparation method of self-doped porous carbon according to the present invention;
FIG. 2 is a scanning electron microscope image of a self-doped graded-pore carbon material obtained in example 2 in a preparation method of self-doped porous carbon according to the present invention;
fig. 3 is a scanning electron microscope image of the self-doped graded porous carbon material obtained in example 3 in the preparation method of the self-doped porous carbon of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
A method for preparing self-doped porous carbon, as shown in fig. 1, comprising the steps of:
step 1, firstly, drying kelp powder in an oven at the temperature of 80-100 ℃ for 30-60 min, then placing the kelp powder in a crucible, covering the crucible, placing the crucible in a tubular furnace for carbonization treatment, heating the kelp powder to 600-1000 ℃ at the speed of 5-10 ℃/min under the protection of 100-300 ml/min nitrogen gas flow, preserving heat for 90-120 min, and naturally cooling the kelp powder to room temperature to obtain carbide; the cost of selecting nitrogen as the protective gas is lower compared with other protective gases such as argon; the carbonization temperature is selected to be 600-1000 ℃, because the carbonization product needs to be activated subsequently, if the carbonization temperature in the step 1 is too low, the pores formed by the carbonization product are less and the pore diameter is small, the full contact between the activating agent and the carbon material is not facilitated, and a good activation effect cannot be achieved; if the carbonization temperature is too high, the graphitization degree of the carbonized product is higher, which is not beneficial to the reaction of an activating agent and a carbon material, so that a new pore structure is difficult to create; in addition, the carbide structure is broken and collapsed due to the over-high temperature, and if the activator is further reacted with the carbide structure to corrode, the original pore structure is further damaged;
step 2, mixing and grinding the carbide and potassium hydroxide powder according to the ratio of 1: 2-1: 4, then placing the mixture into a crucible, covering the crucible, placing the crucible into a tubular furnace for activation treatment, heating to 600-800 ℃ at the speed of 5-10 ℃/min under the protection of 100-300 ml/min nitrogen gas flow, preserving heat for 60-120 min, and naturally cooling to room temperature to obtain porous carbon;
step 3, soaking the porous carbon by adopting a solution with the concentration of 0.5-1 mol/LHCL, magnetically stirring for 2-5 h, and adding deionized water for dilution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and then adding deionized water to carry out centrifugal separation at the rotating speed of 5000-10000 rpm for 10-15 min, and finally placing the centrifuged product in an oven to dry for 12h at the temperature of 80-100 ℃ to obtain the self-doped graded porous carbon material. Hydrochloric acid solution, deionized water and ethanol are used for washing away impurities in the porous carbon material.
The dried kelp is used as a carbon source and also as a source of nitrogen, phosphorus and sulfur heteroatoms, and self-doped carbide is obtained by carbonization; KOH is used as an activating agent, the reaction activity of the KOH and carbonized products is high, more pores are generated, the KOH activation method is the most effective method for preparing the porous carbon with high specific surface area, potassium hydroxide activating agents with different proportions have different activation effects, and the optimal mass ratio of the carbon materials to the KOH during activation is 1: 2-1: 4. Therefore, potassium hydroxide powder is used as an activating agent, the mass ratio of the carbon material to KOH is 1: 2-1: 4, and the self-doped hierarchical porous carbon is obtained after activation.
Through the mode, the preparation method of the self-doped porous carbon selects the kelp as the precursor of the carbon, and the kelp is low in price, wide in source, high in yield and fast in propagation, and nitrogen, phosphorus and sulfur heteroatoms in the kelp are contained in the kelp, so that the hierarchical porous carbon material containing nitrogen, phosphorus and sulfur can be directly obtained after carbonization and activation treatment, and other reagents are not required to be added for doping the heteroatoms; the method is simple to operate, economical and environment-friendly, and the obtained self-doped graded porous carbon material has high specific surface area and excellent conductivity and has wide application prospect when being used as an electrode material of a super capacitor; the utilization rate of the kelp product can be improved, higher added value is given to the kelp product, and the problem of energy shortage can be effectively relieved.
Example 1
Step 1, firstly, drying 4g of kelp powder in an oven at the temperature of 80 ℃ for 60min, then placing the kelp powder in a crucible, covering the crucible, placing the crucible in a tubular furnace for carbonization treatment, heating the kelp powder to 600 ℃ at the speed of 5 ℃/min under the protection of 100ml/min nitrogen gas flow, preserving the temperature for 120min, and then naturally cooling the kelp powder to room temperature to obtain carbide;
step 2, mixing and grinding the carbide and potassium hydroxide powder according to the ratio of 1:4, then placing the mixture into a crucible, covering the crucible, placing the crucible into a tubular furnace for activation treatment, heating to 800 ℃ at the speed of 5 ℃/min under the protection of 200ml/min nitrogen gas flow, preserving heat for 120min, and then naturally cooling to room temperature to obtain porous carbon;
step 3, soaking the porous carbon by adopting a solution with the concentration of 1mol/LHCL, magnetically stirring for 5 hours, and adding deionized water for dilution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and then adding deionized water for centrifugal separation at the rotating speed of 6000rpm for 15min, and finally placing the centrifuged product in an oven for drying for 12h at the temperature of 80 ℃ to obtain the self-doped graded porous carbon material. Fig. 1 shows a scanning electron microscope image of the self-doped hierarchical porous carbon material in this embodiment, and it can be seen from fig. 1 that the hierarchical porous carbon obtained in this embodiment is in an irregular bulk loose structure, has a very developed pore structure, has a pore diameter of several to several hundred nanometers, and is mostly a micropore and a smaller mesopore structure.
Example 2
Step 1, firstly, placing 6g of kelp powder in an oven at the temperature of 90 ℃ for drying for 45min, then placing the kelp powder in a crucible, covering the crucible, placing the crucible in a tubular furnace for carbonization treatment, heating to 800 ℃ at the speed of 6 ℃/min under the protection of 200ml/min nitrogen gas flow, preserving heat for 120min, and then naturally cooling to room temperature to obtain carbide;
step 2, mixing and grinding the carbide and potassium hydroxide powder according to the proportion of 1:3, then placing the mixture into a crucible, covering the crucible, placing the crucible into a tubular furnace for activation treatment, heating the mixture to 700 ℃ at the speed of 6 ℃/min under the protection of 200ml/min nitrogen gas flow, preserving the heat for 90min, and then naturally cooling the mixture to room temperature to obtain porous carbon;
step 3, soaking the porous carbon by adopting a solution with the concentration of 0.8mol/LHCL, magnetically stirring for 4 hours, and adding deionized water for dilution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and then adding deionized water for centrifugal separation at the rotating speed of 7000rpm for 10min, and finally placing the centrifuged product in an oven for drying for 12h at the temperature of 90 ℃ to obtain the self-doped graded porous carbon material.
As shown in fig. 2, it can be seen from the scanning electron microscope image of the self-doped hierarchical porous carbon material of the present embodiment that the hierarchical porous carbon obtained in the present embodiment is still an irregular block honeycomb structure and has a rich pore structure. The average pore diameter of the hierarchical porous carbon obtained in this example was increased compared to the product obtained in example 1.
Example 3
Step 1, firstly, placing 8g of kelp powder in an oven at the temperature of 100 ℃ for drying for 30min, then placing the kelp powder in a crucible, covering the crucible, placing the crucible in a tubular furnace for carbonization treatment, heating the kelp powder to 1000 ℃ at the speed of 8 ℃/min under the protection of 300ml/min nitrogen gas flow, preserving the temperature for 90min, and then naturally cooling the kelp powder to room temperature to obtain carbide;
step 2, mixing and grinding the carbide and potassium hydroxide powder according to the ratio of 1:2, then placing the mixture into a crucible, covering the crucible, placing the crucible into a tubular furnace for activation treatment, heating the mixture to 600 ℃ at the speed of 8 ℃/min under the protection of 200ml/min nitrogen gas flow, preserving the heat for 120min, and then naturally cooling the mixture to room temperature to obtain porous carbon;
step 3, soaking the porous carbon by adopting a solution with the concentration of 0.5mol/LHCL, magnetically stirring for 2 hours, and then adding deionized water for dilution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and then adding deionized water for centrifugal separation at the rotating speed of 7000rpm for 10min, and finally placing the centrifuged product in an oven for drying for 12h at the temperature of 90 ℃ to obtain the self-doped graded porous carbon material.
The scanning electron microscope image of the self-doped hierarchical porous carbon material of the embodiment is shown in fig. 3, and it can be seen from the image that the hierarchical porous carbon obtained in the embodiment has a honeycomb structure, developed pores but a large number of large pores, thinned inner walls of pore channels, communicated adjacent pores and even broken channels.
Claims (7)
1. The preparation method of the self-doped porous carbon is characterized by comprising the following steps:
step 1, putting the pretreated kelp powder into a crucible for carbonization treatment to obtain carbide;
step 2, mixing and grinding the carbide and potassium hydroxide powder according to the proportion of 1: 2-1: 4, and then placing the mixture in a crucible for activation treatment to obtain porous carbon;
step 3, adding deionized water for dilution after soaking the porous carbon by adopting HCL solution; then carrying out suction filtration, and adding a diluent for multiple times to wash the mixture to be neutral; and finally, adding deionized water for centrifugal separation and drying to obtain the self-doped graded porous carbon material.
2. The method for preparing self-doped porous carbon according to claim 1, wherein the pretreatment process in the step 1 is as follows: drying the kelp powder in an oven at the temperature of 80-100 ℃ for 30-60 min.
3. The method for preparing self-doped porous carbon according to claim 1, wherein the carbonization process in step 1 is as follows: and placing the crucible in a tube furnace, heating to 600-1000 ℃ at the speed of 5-10 ℃/min under the protection of 100-300 ml/min nitrogen gas flow, preserving heat for 90-120 min, and naturally cooling to room temperature.
4. The method for preparing self-doped porous carbon according to claim 1, wherein the activation process in the step 2 is as follows: and covering the crucible, putting the crucible into a tube furnace, heating to 600-800 ℃ at the speed of 5-10 ℃/min under the protection of 100-300 ml/min nitrogen gas flow, preserving heat for 60-120 min, and naturally cooling to room temperature.
5. The method for preparing self-doped porous carbon according to claim 1, wherein the concentration of the HCL solution in the step 3 is 0.5-1 mol/L.
6. The method for preparing self-doped porous carbon according to claim 1, wherein the diluent is a mixture of deionized water and ethanol.
7. The method for preparing self-doped porous carbon according to claim 1, wherein the parameters of the centrifugal separation process are as follows: the rotation speed is 5000-1000 rpm, and the time is 10-15 min.
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CN113845115A (en) * | 2021-10-12 | 2021-12-28 | 西安理工大学 | Preparation method and application of heteroatom self-doped biomass porous carbon |
CN113845115B (en) * | 2021-10-12 | 2024-04-05 | 西安理工大学 | Preparation method and application of heteroatom self-doped biomass porous carbon |
CN115116756A (en) * | 2022-07-15 | 2022-09-27 | 东华理工大学 | Preparation method of honeycomb porous carbon based on high-temperature activation method |
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