CN114590790B - Nitrogen-doped carbon material and preparation method thereof - Google Patents
Nitrogen-doped carbon material and preparation method thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 14
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 238000006053 organic reaction Methods 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 239000011232 storage material Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 3
- 229910017852 NH2NH2 Inorganic materials 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 carbon nitrogen hydroxyl compound Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a nitrogen-doped carbon material, wherein the space group of the nitrogen-doped carbon material is Fd-3c, and the lattice parameter a=b=c= 1.10592nm +/-0.5%. The inventionThe preparation process of the nitrogen doped carbon material is also disclosed. By reacting cyanuric chloride with NH 2 NH 2 The material is set as the main material, and the cost of the material is low, so that the waste liquid generated in the preparation process is less, and the preparation process is simple and is easy for mass production.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a nitrogen-doped carbon material and a preparation method thereof.
Background
Carbon has very important position in electrode materials with excellent physical and chemical properties, the electrode materials are important components for forming the super capacitor, and research and development of the carbon materials are the critical content for the research and development of the super capacitor. As one of the hot research objects in the field of the current base materials, carbon materials have a long way to take in the aspects of design and discovery breakthrough. Among them, doping is one of the main ways to improve the properties of carbon materials. Because the electrochemical performance of the material can be obviously improved by doping nitrogen, the synthesis and preparation of the nitrogen-doped porous carbon material are also receiving more and more attention from researchers.
Diamond is the hardest material currently known in the world, and while it is found that carbon-nitrogen compounds exhibit excellent mechanical properties comparable to diamond, more and more researchers are beginning to be interested in such materials. In 1989, U.S. scientists Liu and Cohen (literature: "Prediction of New Low Compressibility Solids", science,1989, 245, 841) have proposed for the first time that β -C3N4 crystals were used in place of Si under a local density of states approximation (localDensity applications) using β -Si3N4 crystal structures as models, which materials have a hardness comparable to diamond. Recently, huang et al (literature: tuning Nitrogen Species and Content in Carbon Materials through Constructing VariableStructures for Supercapacitors ", journal of Inorganic Materials,2021, 36, 7) have regulated the type and amount of nitrogen incorporation of carbon materials by interaction between the Si-O-Si network and alumina, resulting in nitrogen contents as high as 5.29% at 1000 ℃. However, the raw materials and methods used when doping carbon materials with nitrogen still require more intensive research.
In the Chinese patent publication No. CN109647474A, a nitrogen-doped carbon material, its preparation and application are disclosed. The preparation method is simple, low in energy consumption and low in cost, and the nitrogen-doped carbon material shows high reactivity and can selectively degrade various organic pollutants, so that the technical problems that the preparation method of the nitrogen-doped carbon material in the prior art is complex, high in cost and limited in degradation capability to organic pollutants in the environment are solved.
However, the melamine in the above proposal has higher cost, waste liquid is easy to generate in the process, and the market has the requirements of mass production, further compression production cost and environmental protection.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention provides the nitrogen-doped carbon material which is simple in manufacturing method and easy for mass production and the preparation method thereof.
The technical scheme is as follows: a nitrogen-doped carbon material comprising:
the space group of the nitrogen-doped carbon material is Fd-3c, and the lattice parameter a=b=c= 1.10592nm plus or minus 0.5 percent.
2. A method of preparing the nitrogen-doped carbon material of claim 1, comprising the steps of:
(1) Cyanuric chloride and NH 2 NH 2 Adding into distilled water or alcohol or benzene solvent, and mixing under inert gas atmosphere to obtain mixture A;
(2) Placing the mixture A obtained in the step (1) into a reaction kettle, sealing, performing constant temperature treatment in an oven with the temperature of 700-800K for 8-12 hours, naturally cooling to room temperature, and standing for 2-5 hours to obtain powder B;
(3) And (3) washing and filtering the powder B obtained in the step (2) repeatedly with alcohol, dilute hydrochloric acid and distilled water in sequence, repeating at least 3 times in sequence, and drying for 3-4 hours under the vacuum condition of 350-450K to obtain the nitrogen-doped carbon material as shown in the claim 1.
Further, in the step (1), cyanuric chloride and NH 2 NH 2 And the mass ratio of the solvent is 2:1:10-80.
Further, in the step (1), the mass concentration of alcohol in the mixture A is 50-95%, cyanuric chloride and NH 2 NH 2 The mass ratio of (2) to (1).
Further, in the step (3), the mass concentration of the alcohol is 45-80%, and the volume ratio of the alcohol to the powder B is 2-8:30.
Further, in the step (3), the mass concentration of the dilute hydrochloric acid is 5-20%, and the volume ratio of the dilute hydrochloric acid to the powder B is 2-8:20.
Further, in the step (3), the volume ratio of distilled water to the powder B is 2-8:50.
Further, the nitrogen-doped carbon material is applied to energy storage materials, organic reaction catalysts, photocatalysts and/or sensors.
The beneficial effects are that: the invention uses cyanuric chloride and NH 2 NH 2 Adding the carbon source and the nitrogen source into distilled water, alcohol and benzene solvent, and preparing the novel nitrogen-doped carbon material through hydrothermal treatment, solvothermal treatment and other steps. The method has low waste liquid production rate, the impurities in the process are elements such as hydrogen, chlorine, oxygen and the like, the method is easy to remove, the raw materials are rich, and the cost is low. Process impurities may result from surface oxidation and adsorption during processing or from unavoidable moisture contamination caused by prolonged exposure to air. The powder B was repeatedly washed to remove byproducts and reaction residues therein.
Drawings
FIG. 1 is a diagram of a crystal structure of a nitrogen-doped carbon material of the present invention;
FIG. 2 is an X-ray diffraction pattern of example 1 of the nitrogen-doped carbon material of the present invention;
FIG. 3 is an X-ray diffraction pattern of example 1 of the nitrogen-doped carbon material of the present invention;
fig. 4 is an X-ray diffraction pattern of example 1 of the nitrogen-doped carbon material of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a nitrogen-doped carbon material, in particular, see the following examples:
example 1: in the nitrogen-doped carbon material of this embodiment, the space group of the nitrogen-doped carbon material is Fd-3c, the lattice parameter a=b=c= 1.10592nm, the crystal structure is shown in fig. 1, and the nitrogen-doped carbon material has good stability;
a preparation method of a nitrogen-doped carbon material comprises the following specific steps:
(1) Cyanuric chloride and NH 2 NH 2 Adding the mixture into distilled water, and uniformly mixing the mixture in an inert gas atmosphere to obtain a mixture A; wherein the cyanuric chloride is NH 2 NH 2 And distilled water in a mass ratio of 2:1:80;
(2) Placing the mixture A obtained in the step (1) into a reaction kettle, sealing, performing constant temperature treatment for 12 hours in an oven with a preset temperature of 800K, naturally cooling to room temperature, and standing for 2-5 hours to obtain powder B, wherein the powder B is a carbon nitrogen hydroxyl compound;
(3) Washing the obtained powder B with ethanol, dilute hydrochloric acid and distilled water repeatedly, filtering, repeating for at least 3 times, and drying under 450K vacuum for 3-4 hr to obtainFd-3cNovel nitrogen-doped carbon material of space group, wherein the mass concentration of alcohol45% of the powder B, and the volume ratio of the powder B to the powder B is 30:2-8; the mass concentration of the dilute hydrochloric acid is 5%, and the volume ratio of the dilute hydrochloric acid to the powder B is 20:2-8; the volume ratio of distilled water to powder B is 50:2-8.
This embodimentFd-3cThe X-ray diffraction diagram of the nitrogen-doped carbon material of the space group is shown in figure 2, and the lattice parameter thereofa=b=c=1.10592nm。
This embodimentFd-3cThe density of the nitrogen-doped carbon material of the space group is 4.1675g/cm 3 。
Example 2: a preparation method of a nitrogen-doped carbon material comprises the following specific steps:
(1) Cyanuric chloride and NH 2 NH 2 Adding the mixture into alcohol, and uniformly mixing the mixture in an inert gas atmosphere to obtain a mixture A; wherein the cyanuric chloride is NH 2 NH 2 And alcohol in a mass ratio of 2:1:50;
(2) Placing the mixture A obtained in the step (1) into a reaction kettle, sealing, performing constant temperature treatment in an oven with a preset temperature of 750K for 10 hours, naturally cooling to room temperature, and standing for 3-5 hours to obtain powder B;
(3) Washing the obtained powder B with ethanol, dilute hydrochloric acid and distilled water repeatedly, filtering, repeating for at least 3 times, and drying under 400K vacuum for 3-4 hr to obtainFd-3cThe novel nitrogen-doped carbon material of the space group comprises alcohol with the mass concentration of 75% and powder B with the volume ratio of 30:2-8; the mass concentration of the dilute hydrochloric acid is 15%, and the volume ratio of the dilute hydrochloric acid to the powder B is 20:2-8; the volume ratio of distilled water to powder B is 50:2-8.
This embodimentFd-3cThe X-ray diffraction diagram of the nitrogen-doped carbon material of the space group is shown in figure 3, and the lattice parametera=b=c=1.11043nm；
This embodimentFd-3cThe density of the nitrogen-doped carbon material of the space group is 4.1170g/cm 3 。
Example 3: a preparation method of a nitrogen-doped carbon material comprises the following specific steps:
(1) Cyanuric chloride and NH 2 NH 2 Adding into benzene solution, mixing under inert gas atmosphereEvenly obtaining a mixture A; wherein the cyanuric chloride is NH 2 NH 2 And benzene in a mass ratio of 2:1:10;
(2) Placing the mixture A obtained in the step (1) into a reaction kettle, sealing, performing constant temperature treatment in an oven with a preset temperature of 700K for 8 hours, naturally cooling to room temperature, and standing for 2-5 hours to obtain powder B;
(3) Washing the obtained powder B with ethanol, dilute hydrochloric acid and distilled water repeatedly, filtering, repeating for at least 3 times, and drying under 350K vacuum for 3-4 hrFd-3cThe novel nitrogen-doped carbon material of the space group has the mass concentration of alcohol of 95% and the volume ratio of the alcohol to the powder B of 30:2-8; the mass concentration of the dilute hydrochloric acid is 20%, and the volume ratio of the dilute hydrochloric acid to the powder B is 20:2-8; the volume ratio of distilled water to powder B is 50:2-8.
This embodimentFd-3cThe X-ray diffraction diagram of the nitrogen-doped carbon material of the space group is shown in figure 4, and the lattice parametera=b=c=1.10049nm；
This embodimentFd-3cThe density of the nitrogen-doped carbon material of the space group is 4.2127g/cm 3 。
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (8)
1. A method of making a nitrogen-doped carbon material, comprising the steps of: (1) Adding cyanuric chloride and NH2NH2 into distilled water or alcohol or benzene solvent, and uniformly mixing in inert gas atmosphere to obtain a mixture A; (2) Placing the mixture A obtained in the step (1) into a reaction kettle, sealing, performing constant temperature treatment in an oven with the temperature of 700-800K for 8-12 hours, naturally cooling to room temperature, and standing for 2-5 hours to obtain powder B; (3) And (3) washing and filtering the powder B obtained in the step (2) repeatedly with alcohol, dilute hydrochloric acid and distilled water in sequence, repeating at least 3 times in sequence, and drying for 3-4 hours under the vacuum condition of 350-450K to obtain the nitrogen-doped carbon material, wherein the space group of the nitrogen-doped carbon material is Fd-3c, and the lattice parameter a=b=c= 1.10592nm +/-0.5%.
2. The method of preparing a nitrogen-doped carbon material of claim 1, wherein: in the step (1), the mass ratio of cyanuric chloride to NH2NH2 to the solvent is 2:1:10-80.
3. The method of preparing a nitrogen-doped carbon material of claim 2, wherein: in the step (1), the mass concentration of alcohol in the mixture A is 50-95%, and the mass ratio of cyanuric chloride to NH2NH2 is 2:1.
4. A method of preparing a nitrogen-doped carbon material according to claim 3, wherein: in the step (3), the mass concentration of the alcohol is 45-80%, and the volume ratio of the alcohol to the powder B is 2-8:30.
5. The method of preparing a nitrogen-doped carbon material of claim 1, wherein: in the step (3), the mass concentration of the dilute hydrochloric acid is 5-20%, and the volume ratio of the dilute hydrochloric acid to the powder B is 2-8:20.
6. The method of preparing a nitrogen-doped carbon material of claim 5, wherein: in the step (3), the volume ratio of distilled water to the powder B is 2-8:50.
7. A nitrogen-doped carbon material, characterized in that it is produced by the method according to any one of claims 1-6 and has a space group Fd-3c, lattice parameter a=b=c= 1.10592nm±0.5%.
8. The use of the nitrogen-doped carbon material of claim 7 in energy storage materials, organic reaction catalysts, photocatalysts and/or sensors.
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| CN202111472010.1A CN114590790B (en) | 2021-12-06 | 2021-12-06 | Nitrogen-doped carbon material and preparation method thereof |
| GB2218215.8A GB2616103A (en) | 2021-12-06 | 2022-12-05 | Nitrogen-doped carbon material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008280203A (en) * | 2007-05-10 | 2008-11-20 | National Institute For Materials Science | Nitrogen-doped mesoporous carbon (n-kit-6) and its production method |
| CN106920973A (en) * | 2017-03-02 | 2017-07-04 | 华东师范大学 | A kind of synthetic method of nitrogen-doped carbon non noble metal oxygen reduction electrocatalysis material |
| CN109659148A (en) * | 2018-12-26 | 2019-04-19 | 江南大学 | A kind of nitrogen-doped carbon material and preparation method thereof |
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| US5981094A (en) * | 1996-01-04 | 1999-11-09 | The Carnegie Institution Of Washington | Low compressibility carbon nitrides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008280203A (en) * | 2007-05-10 | 2008-11-20 | National Institute For Materials Science | Nitrogen-doped mesoporous carbon (n-kit-6) and its production method |
| CN106920973A (en) * | 2017-03-02 | 2017-07-04 | 华东师范大学 | A kind of synthetic method of nitrogen-doped carbon non noble metal oxygen reduction electrocatalysis material |
| CN109659148A (en) * | 2018-12-26 | 2019-04-19 | 江南大学 | A kind of nitrogen-doped carbon material and preparation method thereof |
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