CN113800509A - Method for preparing high-nitrogen-doped graphitized porous carbon material by metal nitrate catalytic carbonization method - Google Patents
Method for preparing high-nitrogen-doped graphitized porous carbon material by metal nitrate catalytic carbonization method Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910001960 metal nitrate Inorganic materials 0.000 title claims abstract description 17
- 238000003763 carbonization Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 21
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000000126 substance Substances 0.000 claims description 21
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000001704 evaporation Methods 0.000 abstract description 8
- 238000005087 graphitization Methods 0.000 abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
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- 238000000354 decomposition reaction Methods 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
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- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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Abstract
The invention discloses a method for preparing a high-nitrogen-doped graphitized porous carbon material by a metal nitrate catalytic carbonization method, and belongs to the technical field of preparation of nitrogen-doped porous carbon materials. The method comprises the following specific steps: adding dicyandiamide and metal nitrate into constant-temperature distilled water according to a certain proportion in sequence to be dissolved and stirred, heating and evaporating the solution to dryness, grinding to obtain a solid powdery mixture, placing the powdery mixture into a tubular furnace for high-temperature treatment, and performing acid treatment, drying and grinding on a carbonized product to obtain the high-nitrogen-doped graphitized porous carbon material. The method has simple and convenient synthetic route, can realize the regulation and control of the shape, structure and composition of the carbon material by regulating and controlling the type and the dosage of the nitrate, and the prepared carbon product has high nitrogen doping content, good thermal stability at high temperature, high graphitization degree, very good hydrophilicity, excellent supercapacitor performance and good industrial application prospect.
Description
The technical field is as follows:
the invention belongs to the technical field of preparation of nitrogen-doped porous carbon materials, and particularly relates to a method for preparing a high-nitrogen-doped graphitized porous carbon material by a metal nitrate catalytic carbonization method.
Background art:
the carbon-based material has large specific surface area, good mechanical property, thermal stability and the like, and is widely applied to the fields of catalysis, adsorption, energy sources and the like. The element composition of the carbon material can be changed by doping the heteroatom B, N, P, S and the like into the carbon nano material, the charge structure of the material can be adjusted, and the carbon nano material has important application in the field of energy storage and conversion. The N atoms are doped into the carbon material, so that reactive functional groups in the carbon material can be increased, the wettability and the chemical adsorption of the surface of the carbon material are enhanced, the effect between the surface of the carbon material and an electrolyte is enhanced, the transmission of electrons and the diffusion of ions are facilitated, the specific capacitance of the material is improved, more active sites and defect sites can be generated, the conductivity and the electrochemical performance of the material are improved, and the carbon material has a very large industrial application prospect in the field of energy.
At present, the preparation of nitrogen-doped carbon materials at home and abroad mainly comprises a post-treatment method and a direct synthesis method. The post-treatment process is complicated and the nitrogen content of the product is relatively low, typically less than 5 wt%. Direct synthesis methods nitrogen-containing substances, such as nitrogen-containing ionic liquids, nitrogen-containing MOFs, nitrogen-containing resins, and the like, are mixed with a carbon source or a carbon nitrogen precursor is prepared in advance, and then subjected to pyrolysis at high temperature to prepare a nitrogen-doped carbon material. The method can improve the nitrogen doping amount in the product, but the preparation steps are complicated, the preparation cost is high, the nitrogen in the product is easy to decompose at high temperature, the nitrogen doping content is low, the graphitization degree is low, and the application of the nitrogen-doped carbon material in the energy field is greatly limited. Therefore, it is important to design and develop a novel and simple strategy for preparing the nitrogen-doped porous carbon material with high nitrogen doping amount and high graphitization degree.
The invention content is as follows:
the invention provides a method for preparing a high-nitrogen-doped graphitized porous carbon material by a metal nitrate catalytic carbonization method, aiming at the technical problems in the preparation of the existing porous carbon material. According to the method, dicyandiamide is used as a carbon source and a nitrogen source, and nitrate is used for catalyzing and carbonizing dicyandiamide to prepare the high-nitrogen-doped graphitized porous carbon material for the high-performance supercapacitor in situ.
The method for preparing the high-nitrogen-doped graphitized porous carbon material by the metal nitrate catalytic carbonization method comprises the following specific steps:
(1) weighing 5-20 g of dicyanodiamide, and dissolving in 50-200 ml of distilled water with constant temperature of 70-90 ℃ to obtain solution A with constant temperature of 70-90 ℃.
(2) Weighing 2-10 g of metal nitrate, adding the metal nitrate into the solution A with the constant temperature of 70-90 ℃, and dynamically stirring for 5-10 min to obtain a uniformly mixed solution B with the constant temperature of 70-90 ℃.
(3) And (3) placing the solution B with the constant temperature of 70-90 ℃ in a constant-temperature oil bath pan with the constant temperature of 70-90 ℃ for dynamic stirring until water is evaporated and dried, and fully grinding the dried solid into a powdery substance. This step is beneficial to promote the metal ions to be uniformly dispersed in the dicyanodiamine, and the solid grinding further improves the dispersibility of the metal nitrate in the dicyanodiamine.
(4) And (3) placing the powdery substance in a tube furnace, introducing nitrogen at the speed of 5-20 ml/min, heating to 200-300 ℃ at the heating rate of 5-20 ℃/min, keeping at 200-300 ℃ for 0.5h, then continuously heating to 800-1000 ℃ and carbonizing at constant temperature for 1-3 h, and then washing, drying and grinding the solid product to obtain the nitrogen-doped graphitized porous carbon material.
The metal nitrate is any one of zinc nitrate hexahydrate, nickel nitrate hexahydrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate and zinc nitrate hexahydrate. The metal nitrate plays an important role in high-temperature pyrolysis and carbonization of dicyandiamide, not only catalyzes dicyandiamide to form a stable carbon-nitrogen polymer intermediate in the early heat treatment stage, but also can effectively inhibit the decomposition of a nitrogen-containing intermediate at the carbonization temperature of 800-1000 ℃, and improve the nitrogen doping content in a final product. Meanwhile, the carbonization temperature of 800-1000 ℃ improves the graphitization degree of the porous carbon.
The method comprises the steps of uniformly dispersing metal nitrate in dicyandiamide, catalyzing dicyandiamide to form a stable carbon-nitrogen polymer intermediate at a certain temperature, further carbonizing the intermediate at a high temperature to obtain the high-nitrogen-doped graphitized porous carbon material, omitting the step of preparing a nitrogen-containing precursor in advance in the synthesis, effectively catalyzing dicyandiamide polymerization by using the nitrate, and finally forming the nitrogen-doped porous carbon material. The invention solves the problems of easy decomposition of nitrogen-containing precursors, low nitrogen doping content, low graphitization degree, poor hydrophilicity and the like in the preparation of the conventional nitrogen-doped hierarchical porous carbon material. The porous carbon material prepared by the invention is used for an electrode material for a supercapacitor. The method is simple and convenient, the preparation cost is low, the prepared carbon material has high nitrogen doping content, rich active nitrogen species, good thermal stability at high temperature, high graphitization degree and good hydrophilicity, contains rich nitrogen species such as pyridine, pyrrole nitrogen and the like, has ultrahigh hydrophilicity, shows excellent performance of a super capacitor, can realize the control of the shape, the structure and the nitrogen content of the product by changing the type and the dosage of nitrate, and provides a feasible route for the large-scale industrial preparation of the nitrogen-doped hierarchical porous carbon material.
Description of the drawings:
fig. 1 is a Scanning Electron Microscope (SEM) image of the highly nitrogen-doped graphitized porous carbon material prepared in example 1 of the present invention;
fig. 2 is a Transmission Electron Micrograph (TEM) of the highly nitrogen-doped graphitized porous carbon material prepared in example 1 of the present invention;
FIG. 3 is an X-ray photoelectron spectroscopy survey (XPS) of a highly nitrogen-doped multi-level pore carbon material prepared in example 1 of the present invention;
fig. 4(a) is a schematic water contact angle of a highly nitrogen doped graphitized porous carbon material of commercial activated carbon;
fig. 4(B) is a schematic water contact angle diagram of the highly nitrogen-doped graphitized porous carbon material prepared in example 1 of the present invention;
fig. 5 is a Scanning Electron Microscope (SEM) image of the highly nitrogen-doped graphitized porous carbon material prepared in example 2 of the present invention;
fig. 6 is a Transmission Electron Micrograph (TEM) of the highly nitrogen-doped graphitized porous carbon material prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following detailed description, but the present invention is not limited thereto.
Example 1: weighing 10g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 5g of zinc nitrate hexahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, putting the solution in a 70 ℃ constant-temperature oil bath kettle, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, putting the powder into a porcelain boat, putting the porcelain boat in a tubular furnace, introducing nitrogen at a speed of 10ml/min, raising the temperature of the tubular furnace to 250 ℃ at a temperature raising speed of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 900 ℃ and carbonizing at the constant temperature for 1 hour to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material. The prepared nitrogen-doped porous carbon material is subjected to electrochemical performance test, 6mol/L potassium hydroxide is used as electrolyte, and 5Ag is added-1The current density of (2) still has a retention rate of 96.6% after 10000 cycles.
Fig. 1 is an SEM image of the highly nitrogen-doped graphitized porous carbon material prepared in example 1, and it can be seen that the surface of the highly nitrogen-doped graphitized porous carbon material contains abundant pores, and the pores are tightly connected to each other, thereby showing a honeycomb-shaped morphology. The TEM image of fig. 2 clearly shows the graphitized stripes of the porous carbon, indicating a higher degree of graphitization of the product. Fig. 3 is an X-ray photoelectron spectroscopy full spectrum characterization (XPS) of the porous carbon prepared in example 1, from which it can be seen that the sample is rich in nitrogen, with an atomic percentage of nitrogen up to 20.14%. Fig. 4(a) is a schematic view of the water contact angle of a commercial activated carbon material (purchased, chinese medicine reagent) showing that the contact angle of the commercial activated carbon is 136.7 °, greater than 90 °, and has a hydrophobic characteristic, whereas the contact angle of the nitrogen-doped porous carbon material prepared in example 1 is 22.4 ° at a contact time of 0 second, has become 6.7 ° at an extended contact time of 2 seconds, is close to a completely wetted state, and has very high hydrophilicity.
Example 2: weighing 10g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 5g of nickel nitrate hexahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, putting the solution in a 70 ℃ constant-temperature oil bath kettle, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, putting the powder into a porcelain boat, putting the porcelain boat in a tubular furnace, introducing nitrogen at a speed of 10ml/min, raising the temperature of the tubular furnace to 250 ℃ at a temperature raising speed of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 900 ℃ and carbonizing at the constant temperature for 2 hours to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material.
FIG. 5 is an SEM image of the porous carbon material prepared in example 2, from which it can be seen that the product has a tubular morphology. Fig. 6 is a TEM image of the porous carbon material prepared in example 2, and it can be seen that the material is a bamboo-like carbon nanotube with a hollow middle.
Example 3: weighing 10g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 5g of ferric nitrate nonahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, putting the solution in a 70 ℃ constant-temperature oil bath, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, putting the powder into a porcelain boat, putting the porcelain boat in a tubular furnace, introducing nitrogen at a speed of 10ml/min, raising the temperature of the tubular furnace to 250 ℃ at a temperature raising speed of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 900 ℃ and carbonizing at the constant temperature for 1 hour to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material.
Example 4: weighing 10g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 5g of cobalt nitrate hexahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, putting the solution in a 70 ℃ constant-temperature oil bath kettle, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, putting the powder into a porcelain boat, putting the porcelain boat in a tubular furnace, introducing nitrogen at a speed of 10ml/min, raising the temperature of the tubular furnace to 250 ℃ at a temperature raising speed of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 900 ℃ and carbonizing at the constant temperature for 2 hours to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material.
Example 5: weighing 15g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 10g of zinc nitrate hexahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, putting the solution in a 70 ℃ constant-temperature oil bath kettle, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, putting the powder into a porcelain boat, putting the porcelain boat in a tube furnace, introducing nitrogen at a speed of 10ml/min, raising the temperature of the tube furnace to 250 ℃ at a temperature raising speed of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 1000 ℃ and carbonizing at the constant temperature for 1 hour to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material.
Example 6: weighing 15g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 10g of zinc nitrate hexahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, placing the solution in a 80 ℃ constant-temperature oil bath, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, placing the solid substance in a porcelain boat, placing the porcelain boat in a tubular furnace, and introducing the liquid at a speed of 10ml/minAnd introducing nitrogen, simultaneously raising the temperature of the tubular furnace to 250 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 1000 ℃ and carbonizing at the constant temperature for 1 hour to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material. The prepared nitrogen-doped porous carbon material is subjected to electrochemical performance test, 6mol/L potassium hydroxide is used as electrolyte, and 5Ag is added-1Has a retention of 94.8% after 10000 cycles at the current density of (1).
Example 7: weighing 20g of dicyanodiamine, dissolving in 100ml of 70 ℃ constant-temperature distilled water, weighing 14g of zinc nitrate hexahydrate, dissolving in the dicyanodiamine constant-temperature solution, dynamically stirring, stirring for 5min, putting the solution in an 80 ℃ constant-temperature oil bath kettle, dynamically stirring and evaporating until water is evaporated and dried to obtain a solid substance, fully grinding the solid substance to powder, putting the powder into a porcelain boat, putting the porcelain boat in a tube furnace, introducing nitrogen at a speed of 10ml/min, raising the temperature of the tube furnace to 250 ℃ at a temperature raising speed of 10 ℃/min, keeping the temperature at 250 ℃ for 0.5h, then continuously raising the temperature to 800 ℃ and carbonizing at constant temperature for 2 hours to obtain a solid product, and finally washing, drying and grinding to obtain the nitrogen-doped graphitized porous carbon material.
Claims (2)
1. The method for preparing the high-nitrogen-doped graphitized porous carbon material by the metal nitrate catalytic carbonization method is characterized by comprising the following specific steps of:
(1) weighing 5-20 g of dicyanodiamide, and dissolving in 50-200 ml of distilled water with constant temperature of 70-90 ℃ to obtain solution A with constant temperature of 70-90 ℃;
(2) weighing 2-10 g of metal nitrate, adding the metal nitrate into the solution A with the constant temperature of 70-90 ℃, and dynamically stirring for 5-10 min to obtain a uniformly mixed solution B with the constant temperature of 70-90 ℃;
(3) placing the solution B with the constant temperature of 70-90 ℃ in a constant-temperature oil bath pan with the constant temperature of 70-90 ℃ for dynamic stirring until water is evaporated and dried, and fully grinding the dried solid into a powdery substance;
(4) and (3) placing the powdery substance in a tube furnace, introducing nitrogen at the speed of 5-20 ml/min, heating to 200-300 ℃ at the heating rate of 5-20 ℃/min, keeping at 200-300 ℃ for 0.5h, then continuously heating to 800-1000 ℃ and carbonizing at constant temperature for 1-3 h, and then washing, drying and grinding the solid product to obtain the nitrogen-doped graphitized porous carbon material.
2. The method according to claim 1, wherein the metal nitrate is any one of zinc nitrate hexahydrate, nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate, and zinc nitrate hexahydrate.
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| CN103950924A (en) * | 2014-05-12 | 2014-07-30 | 上海交通大学 | Synthesis method of damascene metal nanoparticle graphene |
| WO2019113993A1 (en) * | 2017-12-14 | 2019-06-20 | 中国科学院大连化学物理研究所 | Carbon nanotube and method for fabrication thereof |
| CN112661729A (en) * | 2020-12-23 | 2021-04-16 | 东莞理工学院 | Application of nitrate-assisted carbon catalytic system in preparation of 2, 5-furandicarboxaldehyde by catalytic conversion of 5-hydroxymethylfurfural |
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| CN103950924A (en) * | 2014-05-12 | 2014-07-30 | 上海交通大学 | Synthesis method of damascene metal nanoparticle graphene |
| WO2019113993A1 (en) * | 2017-12-14 | 2019-06-20 | 中国科学院大连化学物理研究所 | Carbon nanotube and method for fabrication thereof |
| CN109956463A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of carbon nanotube and preparation method thereof |
| CN112661729A (en) * | 2020-12-23 | 2021-04-16 | 东莞理工学院 | Application of nitrate-assisted carbon catalytic system in preparation of 2, 5-furandicarboxaldehyde by catalytic conversion of 5-hydroxymethylfurfural |
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