CN110627048A - Method for preparing graphene by taking plants as raw materials and graphene prepared by method - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- 239000002994 raw material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- -1 amine compound Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 238000001035 drying Methods 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- FCLPGDSITYLYCH-UHFFFAOYSA-N 2,2,2-trichloroethanamine Chemical compound NCC(Cl)(Cl)Cl FCLPGDSITYLYCH-UHFFFAOYSA-N 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
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- 238000010000 carbonizing Methods 0.000 claims description 2
- 229910052751 metal Chemical group 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- 239000000463 material Substances 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 229910002804 graphite Inorganic materials 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- 240000004670 Glycyrrhiza echinata Species 0.000 description 1
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- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940010454 licorice Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing graphene by taking plants as raw materials, which comprises the following steps: (1) mixing raw materials: drying and grinding the plant raw materials, and mixing the ground plant raw materials with an amine compound to obtain a mixture; (2) carbonization and heating: and heating the mixture in a high-temperature furnace to obtain the graphene. According to the method, plants are used as raw materials, so that the raw material cost of graphene is greatly reduced. The raw material also comprises amine compounds, and metal residues caused by adding the metal-containing catalyst can be avoided. The method can carry out solid phase synthesis in a common high-temperature furnace, the highest synthesis temperature is about 900 ℃, the requirement on high temperature resistance of equipment is low, no waste gas and waste residue are generated, the method has no pollution to the environment, and the controllability is strong. The invention also provides graphene prepared by the method.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a method for preparing graphene by taking plants as raw materials and the graphene prepared by the method.
Background
Graphene, an advanced carbon material, is recognized by meckentin as one of twelve revolutionary technologies that will change the world's future. The graphene has excellent optical, electrical and mechanical properties, and has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, pharmaceutical delivery and the like. Industrial mass production of graphene is one of the important challenges in this field. A common powder production method includes: mechanical lift-off, redox, SiC epitaxial growth and chemical vapor deposition. The above method can obtain high-quality graphene, but has the following defects, which makes the graphene difficult to be produced in large quantities: (1) the raw material selection range is narrow, and mainly the cost of graphite is high; (2) the synthesis requires high temperature, which leads to expensive synthesis equipment; (3) preparing graphene by using biomass as a raw material, wherein a metal salt catalyst needs to be added, so that metal ions are remained in the graphene; (4) the reaction conditions are mainly synthesized by liquid phase, and some mainstream methods use strong acid and strong base, so that the requirements on production equipment are high, and the discharge amount of industrial wastewater is large; (5) the synthesis process steps are complex.
On the basis of the prior art, patent CN103274393A proposes mixing and drying carbon-containing saccharide molecules (such as glucose or sucrose) and carbon-nitrogen-containing small molecules (such as melamine, cyanamide, dicyanamide, urea, biuret, and trichloroethylamine), heating to 450-. Patent CN108793131A proposes that a mixture of cellobiose and glucose is used as a carbon source, melamine, cyanamide, dicyanamide, urea, biuret and trichloroethylamine are used as a nitrogen source, the mixture is heated in a high-temperature furnace after being mixed, the temperature is raised to 580-620 ℃ in a protective gas atmosphere, the temperature is kept for 2.5-3.5 h, then the temperature is raised to 880-920 ℃ at the speed of 5 ℃/min, the temperature is kept for 0.8-1.2 h, and the graphene is obtained after natural cooling. Compared with the prior art, the two patents have lower preparation temperature, but need to use a sugar monomer with higher price as a carbon source, and still cannot realize the industrialization of the graphene.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing graphene by taking plants as raw materials.
The second purpose of the invention is to provide the graphene prepared by the method.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a method for preparing graphene by taking plants as raw materials, which comprises the following steps:
(1) mixing raw materials: drying and grinding the plant raw materials, and mixing the ground plant raw materials with an amine compound to obtain a mixture;
(2) carbonization and heating: and heating the mixture in a high-temperature furnace to obtain the graphene.
Preferably, in the step (1), the plant raw material is at least one selected from plant stems and leaves, roots, plant processing waste materials and traditional Chinese medicine residues.
Preferably, in the step (1), the amine compound is at least one selected from urea, dicyandiamide, biuret, melamine, cyanamide, and trichloroethylamine.
Preferably, in the step (1), the mass ratio of the plant raw material to the amine compound is 1 (10-30).
Preferably, said step (2) is carried out in an inert gas atmosphere, said inert gas preferably being nitrogen or argon.
Preferably, the carbonization heating comprises the steps of:
(i) first-stage heating: heating the mixture to 550-650 ℃, and keeping the temperature for more than or equal to 2 hours;
(ii) and (3) second-stage heating: and heating the mixture to 850-950 ℃, and keeping the temperature for more than or equal to 1 h.
Preferably, in the step (i), the heat preservation time is 2.5-3.5 h.
Preferably, in the step (ii), the heat preservation time is 1-2 h.
Preferably, during the reaction in step (ii), the gas generated by the reaction is introduced into water, diluted acid solution is added to generate ammonium salt solution, and the ammonium salt solution is concentrated and crystallized.
The invention also relates to nitrogen-doped graphene, which is prepared by adopting the method.
The invention has the beneficial effects that:
the invention provides a method for preparing graphene by taking plants as raw materials, which takes the plants as the raw materials, can utilize stem leaves and roots of the plants (including herbaceous and woody plants), plant processing waste materials and traditional Chinese medicine residues, and greatly reduces the raw material cost of the graphene. The raw material also comprises amine compounds, and metal residues caused by adding the metal-containing catalyst can be avoided. The method can carry out solid phase synthesis in a common high-temperature furnace, the highest synthesis temperature is about 900 ℃, the requirement on high temperature resistance of equipment is low, no waste gas and waste residue are generated, the method has no pollution to the environment, and the controllability is strong.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of graphene prepared in example 1 of the present invention;
FIG. 2 is an enlarged view of a portion of FIG. 1;
fig. 3 is a raman spectrum of graphene prepared in example 12 of the present invention;
fig. 4 is a raman spectrum of graphene prepared in example 13 of the present invention;
fig. 5 is a raman spectrum of graphene prepared in example 14 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a method for preparing graphene by taking plants as raw materials, which comprises the following steps:
(1) mixing raw materials: drying and grinding the plant raw materials, and mixing the ground plant raw materials with an amine compound to obtain a mixture.
In the present invention, both woody and herbaceous plants can be used as raw materials. Further, the plant material is selected from at least one of plant (including herbaceous and woody plant) stem and leaf, root, plant processing waste, and Chinese medicinal residue. Specifically, the plant material can be bagasse, rice hull, corn stalk, radix Glycyrrhizae residue, radix Linderae, rhizoma Zingiberis, pericarpium Citri Reticulatae, rhizoma Atractylodis Macrocephalae, rhizoma Pinelliae Preparata, hemp stalk (peeled stalk), poplar wood shavings, wheat stalk, etc. The invention preferably takes rice hulls, bagasse, licorice residues and poplar wood shavings as plant raw materials.
The plant material is used for providing carbon source, which contains lignin, polysaccharide, aldehyde, ketone, lipid compound and other substances with complex components. However, at temperatures above 400 ℃, the entire plant component is carbonized.
In one embodiment of the invention, the plant material is ground to a particle size of 100-200 mesh. It is generally considered that the smaller the particle size, the more favorable the reaction, and in the laboratory, the grinding to a particle size of less than 200 mesh is relatively easy to achieve, and generally 100 mesh is sufficient industrially.
In one embodiment of the present invention, the amine compound is selected from at least one of urea, dicyanodiamine, biuret, melamine, cyanamide, and trichloroethylamine.
The principle of the reaction is as follows: during the first stage of temperature rise, the amine compounds will form graphite phase carbon nitride (g-C)3N4) In g-C3N4Under the catalytic action of (2), high molecular compounds of plants, such as saccharides and proteins, can be decomposed into small molecular compounds, and the small molecular compounds can be expressed as g-C3N4An aromatic ring compound is generated as a template. When the temperature rises to more than 750 ℃, g-C3N4Will decompose and ultimately form a single graphene product. This is considered to be a multi-stage reduction process and therefore requires the provision of an inert gas blanket. In the invention, the preparation of graphene from plant raw materials is carried out in one step, and no other catalyst is added, namely no other metal elements are introduced.
Patents CN103274393A and CN108793131A mentioned in the background art only emphasize g-C3N4Catalysis of graphene carbonization of mono-and disaccharides. However, applicants have discovered that the graphite phase carbon nitride (g-C)3N4) Has catalytic effect on the graphene carbonization process of lipid, lignin, alkaloids, polysaccharide, amino acid, protein and the like.
The idea of predecessors is mainly a step method, namely: the method comprises the steps of firstly decomposing a plant raw material (such as acidolysis, alkalization, enzymolysis and the like) to form a single component, then carbonizing the single component serving as the raw material, and forming graphene at a high temperature. Compared with the method for preparing graphene by using simple graphite or saccharides, such as monosaccharide and disaccharide compounds in the prior art, the method provided by the invention has the advantage that the industrial cost of the graphene is obviously reduced. It should be noted that, the graphene synthesized by the above method is a crude graphene, and the element content and structural defects thereof are influenced by the content of elements and various compounds in the plant raw material. But does not interfere with applications for graphene such as in the fields of rubber, automotive interior materials, lubricants, coatings, and the like.
In one embodiment of the invention, the mass ratio of the plant raw materials to the amine compounds is 1 (10-30). If the adding amount of the amine compound is too much, excessive ammonia gas can be generated, the environment is polluted, the subsequent treatment pressure of the process is increased, and the production cost is also increased; the adding amount of the amine compound is too small, the using amount of the template agent is insufficient, the yield of the graphene is reduced, the carbon content of non-graphene in the product is increased, and the product purity is reduced.
(2) Carbonization and heating: and heating the mixture in a high-temperature furnace to obtain the graphene.
In one embodiment of the invention, the carbonization heating is carried out in an inert gas atmosphere, preferably nitrogen or argon.
Further, the carbonization heating comprises the following steps:
(i) first-stage heating: heating the mixture to 550-650 ℃, and keeping the temperature for more than or equal to 2 hours, preferably 2.5-3.5 hours. The process mainly realizes the carbonization of plant raw materials and amine compounds to form aromatic ring carbon intermediates and g-C3N4(carbon nitride of graphite-like structure).
(ii) And (3) second-stage heating: heating the mixture to 850-950 ℃, and keeping the temperature for more than or equal to 1 hour, preferably 1-2 hours. The process mainly realizes the decomposition of the carbon nitride, so that only graphene exists in the product. With further increase in temperature, g-C is formed3N4And decomposing to obtain the pure graphene phase.
The reaction process needs to be filled with inert gas and generate ammonia gas. After the reaction is finished, the product can be collected into a high-temperature resistant vessel (such as corundum, quartz and other materials), and the industrial production can adopt blast collection and then carry out extraction separation to obtain a pure product. And (3) in the reaction process of the step (ii), introducing the gas from which the solid-phase product is removed into water, neutralizing with a dilute acid solution to form an ammonium salt solution, and concentrating and crystallizing the ammonium salt solution for resource utilization.
The invention also relates to nitrogen-doped graphene prepared by the method.
Example 1
(1) Mixing raw materials: the bagasse is dried and ground to 100-200 mesh granularity, and then mixed with urea in a mass ratio of 1:10 to obtain a mixture.
(2) First-stage heating: the mixture was warmed to 600 ℃ and held for 3 h.
(3) And (3) second-stage heating: the mixture was warmed to 900 ℃ and held for 1 h.
Fig. 1 and 2 are Transmission Electron Microscope (TEM) images of the product in example 1, which confirm that the method can prepare single-layer graphene.
The raw materials and reaction conditions in examples 2 to 11 and comparative example were changed, and the specific settings are shown in table 1. The yield and purity of graphene in the product are shown in table 2.
TABLE 1
The other parameter settings for each example and comparative example were the same as example 1, except for the parameters in table 1.
TABLE 2
The yield of the graphene is defined as the mass of graphene/(mass of plant material + mass of amine compound) × 100% in the product, and the purity of the graphene in the product is determined by measuring the carbon content in the graphene.
As can be seen from the data in table 2, the graphene prepared by the embodiment of the present invention has better yield and purity, and the yield and purity of the graphene are equivalent to those of the comparative example using the saccharide compound as the raw material, but the preparation cost of the graphene can be obviously reduced by adopting the scheme of the present invention.
The Raman spectra of the products of examples 12 to 14 are shown in FIGS. 3 to 5. The raman spectrum is one of the criteria for judging graphene, and basically judges whether a graphene structure is generated or not through raman and electron microscope results. The most prominent Raman features of graphene are a G peak and a 2D peak which are respectively located at 1580cm-1And 2700cm-1The raman peak of graphene obtained by different preparation methods can be shifted.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A method for preparing graphene by taking plants as raw materials is characterized by comprising the following steps:
(1) mixing raw materials: drying and grinding the plant raw materials, and mixing the ground plant raw materials with an amine compound to obtain a mixture;
(2) carbonization and heating: and heating the mixture in a high-temperature furnace to obtain the graphene.
2. The method according to claim 1, wherein in the step (1), the plant raw material is at least one selected from plant stems and leaves, roots, plant processing waste materials and traditional Chinese medicine residues.
3. The method according to claim 1, wherein in step (1), the amine compound is at least one selected from urea, dicyanodiamine, biuret, melamine, cyanamide, and trichloroethylamine.
4. The method according to claim 1, wherein in the step (1), the mass ratio of the plant raw material to the amine compound is 1 (10-30).
5. The method according to claim 1, wherein the step (2) is performed in an inert gas atmosphere.
6. The method of claim 1, wherein the carbonizing heating comprises the steps of:
(i) first-stage heating: heating the mixture to 550-650 ℃, and keeping the temperature for more than or equal to 2 hours;
(ii) and (3) second-stage heating: and heating the mixture to 850-950 ℃, and keeping the temperature for more than or equal to 1 h.
7. The method according to claim 6, wherein in step (i), the holding time is 2.5-3.5 h.
8. The method according to claim 6, wherein in step (ii), the holding time is 1-2 h.
9. The method of claim 6, wherein during the reaction in step (ii), the gas generated by the reaction is introduced into water, a dilute acid solution is added to form the ammonium salt solution, and the ammonium salt solution is concentrated and crystallized.
10. The nitrogen-doped graphene is characterized by being prepared by the method of any one of claims 1-9.
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| CN113956057A (en) * | 2021-12-01 | 2022-01-21 | 辽宁中科星光新材料有限公司 | Biological graphene silicon carbide material and preparation method thereof |
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| CN104724696A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene by taking biomass as raw material |
| CN108793131A (en) * | 2018-07-18 | 2018-11-13 | 南方医科大学 | The method for preparing graphene as raw material with glucose mixture using cellobiose or cellobiose |
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| CN104724696A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene by taking biomass as raw material |
| CN108793131A (en) * | 2018-07-18 | 2018-11-13 | 南方医科大学 | The method for preparing graphene as raw material with glucose mixture using cellobiose or cellobiose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113956057A (en) * | 2021-12-01 | 2022-01-21 | 辽宁中科星光新材料有限公司 | Biological graphene silicon carbide material and preparation method thereof |
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