CN109956463B - Carbon nano tube and preparation method thereof - Google Patents
Carbon nano tube and preparation method thereof Download PDFInfo
- Publication number
- CN109956463B CN109956463B CN201711339359.1A CN201711339359A CN109956463B CN 109956463 B CN109956463 B CN 109956463B CN 201711339359 A CN201711339359 A CN 201711339359A CN 109956463 B CN109956463 B CN 109956463B
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- carbon nanotubes
- nano tube
- nanotubes according
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/166—Preparation in liquid phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a diameter-controllable carbon nanotube and a preparation method thereof. Compared with the prior art, the invention has the following advantages: in the preparation process, the diameters of the carbon nano tubes can be controlled by simply changing synthesis conditions such as a solvent, reaction temperature and the like to obtain metal organic frameworks with different particle sizes; the preparation process is simple, and the traditional carbon nanotube preparing apparatus including arc discharge, chemical vapor deposition and other steps is not needed. Meanwhile, the prepared carbon nano tube is doped with a large amount of N in situ, the electronic structure on the surface of the carbon nano tube is changed, the electrochemical performance of the carbon nano tube is further improved, and the carbon nano tube has a larger potential application prospect in the fields of energy conversion and storage.
Description
Technical Field
The invention relates to the field of preparation and application of carbon materials, in particular to preparation and application of a carbon nanotube.
Background
The carbon nano tube is a novel carbon nano material consisting of carbon atoms, has a unique one-dimensional structure, high graphitization degree and excellent electrical and mechanical properties, arouses wide interest of scientific researchers, and particularly has wide application prospects in the field of electrochemical energy storage and conversion. As a one-dimensional material, the diameter is an important structural parameter of carbon nanotubes, and studies have shown that the electrochemical performance of carbon nanotubes can be significantly affected by changing the diameter of the carbon nanotubes.
The currently common methods for preparing carbon nanotubes mainly comprise: arc discharge, laser evaporation, CVD, solid phase pyrolysis, and the like. In 1991, the carbon nanotubes were first discovered by Nippon physicist Iijima through an arc discharge method, which is technically simpler, but the resulting carbon nanotubes were compared with C60And the products are mixed and have low purity. The CVD method has simple requirements on equipment and lower cost, and is the most feasible and most economical and practical method for synthesizing the carbon nano tube at present. Recently, a method of directly carbonizing a solid phase precursor (e.g., fullerene black, organic metal compound, polymer) at a high temperature is used to prepare carbon nanotubes, which can be modified by adding N, S, B compound to the precursor to dope the precursor in situ into carbon nanotubes during heating, in addition to the simplicity of operationThe electrochemical performance of the carbon nanotube can be further improved by changing the surface electronic structure of the carbon nanotube. However, the behavior of the precursor during pyrolysis is difficult to control, the morphology of the finally formed carbon nanotube is usually not uniform, and the preparation of the carbon nanotube with controllable diameter through pyrolysis still has a challenge.
Disclosure of Invention
The invention provides a method for preparing carbon nanotube gas with controllable diameter aiming at the problem that the morphology of carbon nanotubes prepared by pyrolyzing precursors is uncontrollable, which is realized by adopting the following specific scheme:
a carbon nanotube characterized by: the carbon nano tubes are in a bamboo-like shape, namely each carbon nano tube is formed by sequentially connecting more than 2 bamboo-like tube sections, the carbon nano tubes contain N elements, and one end of each carbon nano tube is wrapped with metal nano particles; the outer diameter of the carbon nano tube is 50-300 nm. The N element exists in a form of one or more than two of pyridine N, pyrrole N, graphitized N and oxidized N, and the mass content of the nitrogen element is 2-8%. The carbon nanotube of claim 1, wherein: the metal nano particles are iron and/or cobalt, and the diameter of the metal nano particles is 50-300 nm. The metal nano-particles account for 1% -10% of the total mass of the carbon nano-tubes. The outer diameter of the carbon nanotube is preferably 300 nm; the diameter of the metal nanoparticles is preferably 300 nm.
The preparation method of the carbon nano tube comprises the following steps:
(1) synthesis of metal organic framework: preparing a mixed solution of zinc salt and an organic ligand; reacting at 30-120 ℃, and then separating to obtain a metal organic framework;
(2) preparing a precursor: dissolving metal salt and an amino compound in a solvent, adding the metal organic framework prepared in the step (1), dispersing uniformly, and removing the solvent to obtain a precursor;
(3) preparing the carbon nano tube: and (3) carrying out heat treatment on the precursor obtained in the step (2) in an inert atmosphere to obtain the carbon nano tube with the tail end wrapped by the metal nano particles.
In the step (1), the zinc salt is one or more of zinc nitrate, zinc chloride and zinc sulfate, and the concentration of zinc ions in the mixed solution is 0.0125-0.1 mol/L.
In the step (1), the organic ligand is 2-methylimidazole, and the concentration of the organic ligand in the mixed solution is 0.1-0.8 mol/L.
The solvent in the mixed solution in the step (1) is one of methanol, ethanol, water and DMF.
In the step (2), the metal salt is one or more than two of cobalt or iron chloride, nitrate and acetate.
In the step (2), the amino compound is one or more than two of urea, dicyandiamide and melamine.
In the step (2), the solvent is one or a mixed solution of more than two of methanol, ethanol and water.
The mass ratio of the metal salt to the amino compound in the step (2) is 1:1-1: 5.
The method for removing the solvent in the step (2) is rotary evaporation and/or vacuum drying.
The heat treatment process in the step (3) is to heat up to 800-1100 ℃ and keep for 0.5-3h, and then cool down to room temperature; the heating rate of heating from room temperature to heat treatment temperature in the heating process is 2-5 ℃/min; the cooling rate is 1-10 ℃/min in the cooling process.
And (3) the inert atmosphere is one or a mixture of nitrogen and argon.
The catalyst is an electrocatalyst for the oxygen reduction reaction of the cathode of the polymer electrolyte membrane fuel cell and the metal air cell.
Compared with the prior art, the invention has the following advantages: the diameter of the carbon nano tube can be directly controlled by controlling the particle size of the metal organic framework in the preparation process; the diameter of the carbon nano tube is uniform and controllable, and the control range is between 50 and 300 nm; the preparation process is simple, and the traditional equipment for preparing the carbon nano tube, such as arc discharge, chemical vapor deposition and the like, is not needed. Meanwhile, the prepared carbon nano tube is doped with a large amount of N in situ, the electronic structure on the surface of the carbon nano tube is changed, the electrochemical performance of the carbon nano tube is further improved, and the carbon nano tube has a larger potential application prospect in the fields of energy conversion and storage.
Drawings
FIG. 1: low-magnification SEM photograph of metal organic framework
FIG. 2: carbon nanotube low power SEM photograph
FIG. 3: carbon nanotube low power SEM photograph
FIG. 4: carbon nanotube XRD patterns.
Detailed Description
Comparative example 1
2g of dicyandiamide and 1g of cobalt acetate are dissolved in 60ml of ethanol, heated and stirred at 80 ℃ for 5h, and then evaporated to dryness to obtain solid powder. Putting the solid powder into a corundum boat, heating to 800 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, cooling to room temperature at the cooling rate of 5 ℃/min, and taking out the product.
The carbon nano tube with uniform diameter distribution can not be formed without a metal organic framework as a template
Comparative example 2
1.436g of cobalt nitrate hexahydrate and 3.244g of 2-methylimidazole were dissolved in 100ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then, standing was carried out for 20 h. And (3) carrying out centrifugal separation, washing for three times, and carrying out vacuum drying for 8h at the temperature of 150 ℃ to obtain ZIF-67-300. 0.2g of ZIF-67-300 and 1g of cobalt acetate were dissolved in 60ml of ethanol, heated and stirred at 80 ℃ for 5 hours, stirred at room temperature for 48 hours, and then evaporated to dryness at 60 ℃ to obtain a solid powder. Putting the solid powder into a corundum boat, heating to 800 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, cooling to room temperature at the cooling rate of 5 ℃/min, and taking out the product.
Without an amino compound (e.g., dicyandiamide) as a carbon nitrogen source, carbon nanotubes cannot be grown.
Example 1
1.436g of cobalt nitrate hexahydrate and 3.244g of 2-methylimidazole were dissolved in 100ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then the mixture was allowed to stand for 20 h. And (3) carrying out centrifugal separation, washing for three times, and carrying out vacuum drying for 8h at the temperature of 150 ℃ to obtain ZIF-67-300. Dissolving 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heating and stirring at 80 ℃ for 5h, adding 0.2g of ZIF-67-300, stirring at room temperature for 48h, and evaporating at 60 ℃ to dryness to obtain solid powder. And (3) putting the solid powder into a corundum boat, heating to 800 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, cooling to room temperature at a cooling rate of 5 ℃/min, and taking out the carbon nano tube.
And preparing the carbon nano tube with the outer diameter of about 200nm by using 300nm ZIF-67 as a template.
Example 2
1.436g of cobalt nitrate hexahydrate and 3.244g of 2-methylimidazole were dissolved in 200ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then, standing was carried out for 20 h. Centrifugally separating, washing for three times, and vacuum drying at 150 ℃ for 8h to obtain ZIF-67-150. Dissolving 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heating and stirring at 80 ℃ for 5h, adding 0.2g of ZIF-67-150, stirring at room temperature for 48h, and evaporating at 60 ℃ to dryness to obtain solid powder. And (3) putting the solid powder into a corundum boat, heating to 800 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, cooling to room temperature at a cooling rate of 5 ℃/min, and taking out the carbon nano tube.
And preparing the carbon nano tube with the outer diameter of about 100nm by using 150nm ZIF-67 as a template.
Example 3
1.470g of zinc nitrate hexahydrate and 3.260 of 2-methylimidazole were dissolved in 50ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then the mixture was allowed to stand for 20 h. Centrifugally separating, washing for three times, and drying for 8 hours in vacuum at the temperature of 150 ℃ to obtain ZIF-8-80. Dissolving 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heating and stirring at 80 ℃ for 5h, adding 0.2g of ZIF-8-80, stirring at room temperature for 48h, and evaporating at 60 ℃ to dryness to obtain solid powder. Putting the solid powder into a corundum boat, heating to 800 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, cooling to room temperature at the cooling rate of 5 ℃/min, and taking out the carbon nano tube.
And preparing the carbon nano tube with the outer diameter of about 50nm by using 100nm ZIF-8 as a template.
Example 4
1.436g of cobalt nitrate hexahydrate and 3.244g of 2-methylimidazole were dissolved in 100ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then, standing was carried out for 20 h. And (3) carrying out centrifugal separation, washing for three times, and carrying out vacuum drying for 8h at the temperature of 150 ℃ to obtain ZIF-67-300. Dissolving 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heating and stirring at 80 ℃ for 5h, adding 0.2g of ZIF-67-300, stirring at room temperature for 48h, and evaporating at 60 ℃ to dryness to obtain solid powder. Placing the solid powder in a corundum boat, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 1h, cooling to room temperature at a cooling rate of 5 ℃/min, and taking out the carbon nano tube.
Example 5
1.436g of cobalt nitrate hexahydrate and 3.244g of 2-methylimidazole were dissolved in 100ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then, standing was carried out for 20 h. Centrifugally separating, washing for three times, and drying for 8h under vacuum at 150 ℃ to obtain ZIF-67-300. Dissolving 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heating and stirring at 80 ℃ for 5h, adding 0.2g of ZIF-67-300, stirring at room temperature for 48h, and evaporating at 60 ℃ to dryness to obtain solid powder. Putting the solid powder into a corundum boat, heating to 800 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 2h, cooling to room temperature at the cooling rate of 5 ℃/min, and taking out the carbon nano tube.
Example 6
1.436g of cobalt nitrate hexahydrate and 3.244g of 2-methylimidazole were dissolved in 100ml of methanol at 20 ℃ respectively, the former was slowly added to the latter with stirring, stirring was continued for 12min, and then, standing was carried out for 20 h. And (3) carrying out centrifugal separation, washing for three times, and carrying out vacuum drying for 8h at the temperature of 150 ℃ to obtain ZIF-67-300. Dissolving 2g of dicyandiamide and 1g of cobalt acetate in 60ml of ethanol, heating and stirring at 80 ℃ for 5h, adding 0.1g of ZIF-67-300, stirring at room temperature for 48h, and evaporating at 60 ℃ to dryness to obtain solid powder. And (3) placing the solid powder in a corundum boat, heating to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, preserving heat for 1h, cooling to room temperature at a cooling rate of 5 ℃/min, and taking out the carbon nano tube.
Claims (14)
1. A method for preparing carbon nanotubes is characterized in that: the carbon nano tubes are in a bamboo-like shape, namely each carbon nano tube is formed by sequentially connecting more than 2 bamboo-like tube sections, the carbon nano tubes contain N elements, and one end of each carbon nano tube is wrapped with metal nano particles; the outer diameter of the carbon nano tube is 50-300 nm;
the preparation method of the carbon nano tube comprises the following steps,
(1) synthesis of metal organic framework: preparing a mixed solution of zinc salt and organic ligand 2-methylimidazole; reacting at 30-120 ℃, and then separating to obtain a metal organic framework;
(2) preparing a precursor: dissolving metal salt and an amino compound in a solvent, adding the metal organic framework prepared in the step (1), dispersing uniformly, and removing the solvent to obtain a precursor;
(3) preparing the carbon nano tube: carrying out heat treatment on the precursor obtained in the step (2) in an inert atmosphere to obtain a carbon nano tube with the tail end wrapped by metal nano particles;
the organic ligand in the step (1) is 2-methylimidazole;
wherein the amino compound in the step (2) is one or more than two of urea, dicyandiamide and melamine.
2. The method for producing carbon nanotubes according to claim 1, wherein: the N element exists in a form of one or more than two of pyridine N, pyrrole N, graphitized N and oxidized N, and the mass content of the nitrogen element is 2-8%.
3. The method for producing carbon nanotubes according to claim 1, wherein: the metal nano particles are iron and/or cobalt, and the diameter of the metal nano particles is 50-300 nm.
4. The method for producing carbon nanotubes according to claim 1, wherein: the metal nano-particles account for 1% -10% of the total mass of the carbon nano-tubes.
5. The method for producing carbon nanotubes according to claim 1, wherein: the outer diameter of the carbon nano tube is 300 nm; the diameter of the metal nano-particles is 300 nm.
6. The method for producing carbon nanotubes according to claim 1, wherein: in the step (1), the zinc salt is one or more of zinc nitrate, zinc chloride and zinc sulfate, and the concentration of zinc ions in the mixed solution is 0.0125-0.1 mol/L.
7. The method for producing carbon nanotubes according to claim 1, wherein: in the step (1), the concentration of the organic ligand 2-methylimidazole in the mixed solution is 0.1-0.8 mol/L.
8. The method for producing carbon nanotubes according to claim 1, wherein: the solvent in the mixed solution in the step (1) is one of methanol, ethanol, water and DMF.
9. The method for producing carbon nanotubes according to claim 1, wherein: in the step (2), the metal salt is one or more than two of cobalt or iron chloride, nitrate and acetate.
10. The method for producing carbon nanotubes according to claim 1, wherein: in the step (2), the solvent is one or a mixed solution of more than two of methanol, ethanol and water.
11. The method for producing carbon nanotubes according to claim 1, wherein: the mass ratio of the metal salt to the amino compound in the step (2) is 1:1-1: 5.
12. The method for producing carbon nanotubes according to claim 1, wherein: the method for removing the solvent in the step (2) is rotary evaporation and/or vacuum drying.
13. The method for producing carbon nanotubes according to claim 1, wherein: the heat treatment process in the step (3) is to heat up to 800-1100 ℃ and keep for 0.5-3h, and then cool down to room temperature; the heating rate of heating from room temperature to heat treatment temperature in the heating process is 2-5 ℃/min; the cooling rate is 1-10 ℃/min in the cooling process.
14. The method for producing carbon nanotubes according to claim 1, wherein: and (3) the inert atmosphere is one or a mixture of nitrogen and argon.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711339359.1A CN109956463B (en) | 2017-12-14 | 2017-12-14 | Carbon nano tube and preparation method thereof |
| PCT/CN2017/117054 WO2019113993A1 (en) | 2017-12-14 | 2017-12-19 | Carbon nanotube and method for fabrication thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711339359.1A CN109956463B (en) | 2017-12-14 | 2017-12-14 | Carbon nano tube and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109956463A CN109956463A (en) | 2019-07-02 |
| CN109956463B true CN109956463B (en) | 2022-07-05 |
Family
ID=66819878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711339359.1A Active CN109956463B (en) | 2017-12-14 | 2017-12-14 | Carbon nano tube and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109956463B (en) |
| WO (1) | WO2019113993A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683530A (en) * | 2019-08-26 | 2020-01-14 | 广西大学 | Method for in-situ synthesis of cobalt-nitrogen co-doped carbon nano tube |
| CN110813362B (en) * | 2019-12-03 | 2022-09-20 | 湘潭大学 | High-nitrogen-content carbon nanotube catalyst and preparation method and application thereof |
| CN111138367B (en) * | 2019-12-07 | 2021-07-27 | 北京科技大学 | Cobalt metal organic framework material and preparation method and application thereof |
| CN111193039B (en) * | 2020-01-08 | 2021-05-07 | 华中科技大学 | Method for preparing oxygen reduction catalyst from biomass and product |
| CN111489898A (en) * | 2020-04-16 | 2020-08-04 | 嘉兴学院 | Preparation method of low-cost ZnNCN material |
| CN112103518B (en) * | 2020-09-15 | 2022-07-29 | 上海理工大学 | Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material |
| CN112090441B (en) * | 2020-09-28 | 2023-04-25 | 浙江师范大学 | Preparation method, product and application of cobalt-based carbon nanomaterial |
| CN112331869A (en) * | 2020-11-06 | 2021-02-05 | 五邑大学 | Cobalt-nitrogen double-doped hybrid carbon material and preparation method thereof |
| CN112853378B (en) * | 2021-01-18 | 2023-10-10 | 南昌航空大学 | Preparation method of Bi-NC catalyst for carbon dioxide electroreduction |
| CN113036112A (en) * | 2021-03-04 | 2021-06-25 | 宁波晟默贸易有限公司 | Preparation method of lithium-sulfur battery electrode material with nitrogen-rich porous carbon framework |
| CN113788470A (en) * | 2021-09-29 | 2021-12-14 | 中北大学 | Preparation method of nitrogen-doped carbon nanotube with cup stack structure |
| CN113800509B (en) * | 2021-10-11 | 2024-02-06 | 安徽工业大学 | Method for preparing high-nitrogen-doped graphitized porous carbon material by metal nitrate catalytic carbonization method |
| CN114540868B (en) * | 2022-01-19 | 2022-11-08 | 苏州大学 | Preparation method and application of Co, N and S Co-doped carbon nano candida composite material |
| CN114751399B (en) * | 2022-04-29 | 2024-04-09 | 北京航空航天大学 | Carbon nanotube domain-limited metal nanowire material, and preparation method and application thereof |
| CN115215325B (en) * | 2022-07-08 | 2023-08-29 | 安徽大学 | Composite electromagnetic wave absorbing material and preparation method and application thereof |
| CN115475646A (en) * | 2022-09-20 | 2022-12-16 | 哈尔滨工业大学（深圳） | Carbon nanotube-based catalyst and preparation method and application thereof |
| CN116364907B (en) * | 2023-05-22 | 2023-08-29 | 天津巴莫科技有限责任公司 | Lithium-rich manganese-based layered cathode material, and preparation method and application thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1627933B1 (en) * | 2004-08-09 | 2007-03-14 | C.R.F. Società Consortile per Azioni | Method and device for adsorbing and/or desorbing hydrogen with the aid of shape memory materials |
| CN101450799A (en) * | 2007-11-29 | 2009-06-10 | 索尼株式会社 | Nitrogen doped carbon nanotube and preparation method thereof, and carbon nanotube element |
| KR101051402B1 (en) * | 2008-09-12 | 2011-07-22 | 재단법인서울대학교산학협력재단 | Composite of carbon nanotubes and inorganic-organic skeletal structures having high surface area, high hydrogen storage capacity and improved water safety and preparation method thereof |
| WO2014046107A1 (en) * | 2012-09-20 | 2014-03-27 | 国立大学法人京都大学 | Metal nanoparticle complex and method for producing same |
| CN104016328B (en) * | 2013-02-28 | 2015-12-23 | 中国科学院大连化学物理研究所 | A kind of preparation method of nitrogenous carbon nanotube |
| CN105618789A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Preparation method of nitrogen-doped carbon nano tube packaging cobalt nanoparticles |
| CN104745149B (en) * | 2015-03-05 | 2018-02-09 | 北京科技大学 | A kind of preparation method of carbonaceous material metal organic framework base composite phase-change material |
| CN104944410B (en) * | 2015-06-01 | 2017-06-16 | 北京理工大学 | A kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite |
| CN105084339B (en) * | 2015-06-25 | 2017-06-16 | 中国科学技术大学 | N doping multi-walled carbon nano-tubes and preparation method thereof |
| CN105413730B (en) * | 2015-11-25 | 2018-04-27 | 青岛大学 | A kind of preparation method of nitrogen-doped carbon nanometer pipe parcel cobalt electrocatalytic oxidation reducing material |
| CN105776181B (en) * | 2016-04-29 | 2018-12-21 | 大连理工大学 | A kind of preparation method of flake nano porous carbon and carbon nano tube compound material |
| CN106904596A (en) * | 2017-03-06 | 2017-06-30 | 武汉理工大学 | The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application |
-
2017
- 2017-12-14 CN CN201711339359.1A patent/CN109956463B/en active Active
- 2017-12-19 WO PCT/CN2017/117054 patent/WO2019113993A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN109956463A (en) | 2019-07-02 |
| WO2019113993A1 (en) | 2019-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109956463B (en) | Carbon nano tube and preparation method thereof | |
| CN109309214B (en) | Preparation method of carbon-coated nickel nano composite material | |
| CN106564875B (en) | A kind of preparation method of the nitrogen co-doped hollow carbon nano-particle of monodisperse cobalt | |
| CN108298518B (en) | Preparation method of monoatomic dispersed carbon material | |
| CN108689398B (en) | Preparation method of controllable nitrogen-doped carbon nanotube | |
| CN107032408B (en) | A kind of ferroso-ferric oxide/C classifying nano spherical structure composite materials of MnO doping and preparation method thereof | |
| CN109473651B (en) | Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material | |
| CN101704552A (en) | Molybdenum disulfide nano tube and preparation method thereof | |
| CN110148760B (en) | Porous carbon-carbon nanotube composite material and preparation method and application thereof | |
| CN112705235B (en) | Carbon-coated nickel carbide nanocomposite and preparation method and application thereof | |
| Meng et al. | High-purity helical carbon nanotubes by trace-water-assisted chemical vapor deposition: Large-scale synthesis and growth mechanism | |
| CN104016328A (en) | Method for preparing nitrogen-containing carbon nano tube | |
| CN112928388B (en) | Iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and preparation method and application thereof | |
| CN106829918A (en) | A kind of preparation method of the controllable micropore carbon nano rod of size | |
| CN108339562B (en) | Preparation method of iron ion doped carbon nitride nanotube and obtained product | |
| Wang et al. | Solution synthesis of ZnO nanotubes via a template-free hydrothermal route | |
| Wu et al. | One-step synthesis of hierarchical metal oxide nanosheet/carbon nanotube composites by chemical vapor deposition | |
| CN110841680A (en) | Preparation method of nitrogen and sulfur-doped graphene-CuS composite material | |
| CN114100648A (en) | Synthetic method of ZnMo-MOF-derived carbon-coated molybdenum carbide | |
| CN112978804B (en) | Preparation method of multilayer box-shaped ferrous sulfide @ nitrogen-doped carbon composite material | |
| Liu et al. | The green synthesis of PdO/Pd anchored on hierarchical ZnO microflowers with a synthetic effect for the efficient catalytic reduction of 4-nitrophenol | |
| CN110790267A (en) | Preparation method of nitrogen-doped graphene | |
| CN107224973B (en) | Cu2O/MWCNTs composite material, preparation method and catalytic application | |
| CN110040720A (en) | High-purity, narrow diameter distribution, minor diameter double-walled carbon nano-tube preparation method | |
| CN115475641A (en) | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |