CN113860283A - Preparation method and application of metal monoatomic and nitrogen double-doped carbon microtube - Google Patents
Preparation method and application of metal monoatomic and nitrogen double-doped carbon microtube Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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 the technical field of carbon micron tube preparation, and particularly discloses a preparation method and application of a metal monoatomic and nitrogen double-doped carbon micron tube. The method comprises the following steps: (1) an organic solvent containing 1,3, 5-tris (4-aminophenyl) benzene and a metal salt is provided for use. (2) And (3) adding the acid liquor into the organic solvent obtained in the step (1) to carry out polymerization reaction, thereby obtaining a carbon nanotube precursor. (3) And calcining the carbon micron tube precursor in an inert atmosphere to obtain the carbon micron tube precursor. Compared with some traditional carbon tube synthesis methods, the method utilizes the characteristic that 1,3, 5-tri (4-aminophenyl) benzene and metal salt can generate in-situ polymerization reaction in an acid solution to synthesize the hollow carbon microtubes doped with metal single atoms and nitrogen in one step, and the method has the advantages of simple and convenient operation, controllable shape and size, more uniform dispersion of doped hetero atoms and effective reduction of the preparation cost of materials.
Description
Technical Field
The invention relates to the technical field of carbon micron tube preparation, in particular to a preparation method and application of a metal monoatomic and nitrogen double-doped carbon micron tube.
Background
The information in this background section is disclosed to enhance understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms part of the prior art already known to a person of ordinary skill in the art.
Since the discovery of carbon nanotubes by Iijima in japan in 1991, carbon nanotubes have been widely noticed as a research hotspot, and are commonly called buckytubes (buckytubes), which are seamless nanoscale tubes formed by rolling single-layer or multi-layer graphite sheets, and have unique properties of cavity structure, hexagonal carbon atom configuration, electronic and mechanical properties, and thus, have unique electrochemical, optical, magnetomechanical properties, and the like. The material is often preferred for electrode materials, catalysts, microelectronic elements, fuel cells, etc., and particularly, it is commercially valuable to use it as a catalyst carrier for fuel cells.
In recent years, with the development of carbon nanotubes, carbon nanotubes have been receiving more and more attention because of their similar structure and physicochemical properties to those of nanotubes. Because the carbon nano tube has a small tube diameter, crystals are easy to separate out in a high-temperature or electrochemical process to block the tube body, and the application value of the carbon nano tube in the directions of catalysis, micro-nano reactors, micro-nano fluid transmission, ion batteries and the like can be reduced. The carbon micron tube has a large tube diameter, so that the catalytic products can be better transferred and accelerated to be discharged in the processes of catalysis and the like. On the other hand, the relatively large pipe diameter of the pipe is not easy to cause the doped elements to agglomerate in the doping process, thereby being beneficial to the uniform distribution of the doped elements.
At present, the preparation method of the carbon micron tube mainly comprises a template method, a hydrothermal method and the like. The template method comprises the steps of firstly preparing a micron tube or micron fiber, then preparing a surface carbon layer by high-temperature catalytic deposition or liquid phase deposition in combination with pyrolysis, and finally obtaining the carbon micron tube by acid etching. The hydrothermal method is characterized in that absolute ethyl alcohol, ethylene glycol, toluene, hexabromobenzene and the like are used as carbon sources, a proper amount of catalyst is added, and the catalyst is prepared at high temperature and high pressure. The carbon micron tube prepared by the method is further applied to the fields of catalysis, ion batteries and the like, and element doping is required to be carried out by methods such as dipping or high-temperature evaporation. The doping processes have the defects of non-uniform doping elements, easy agglomeration and untight combination with the carbon nanotube substrate. As can be seen from the above, the conditions for preparing and doping modification of the carbon nanotube are harsh at present, and a mild and simple preparation and doping method is urgently needed.
Disclosure of Invention
The invention aims to solve the problems that the existing method for synthesizing and doping the modified carbon nanotube is complex, the process requirement is high, and the variety and distribution of doping elements are uncontrollable. Therefore, the invention provides a preparation method of the metal monoatomic and nitrogen double-doped carbon nanotube, the preparation process of the method is simple, easy to operate and controllable, and finally the doped carbon nanotube with metal elements in a monoatomic dispersion state is obtained. In order to achieve the purpose, the invention discloses the following technical scheme:
in a first aspect of the present invention, a method for preparing a carbon nanotube doped with a metal single atom and nitrogen includes the steps of:
(1) an organic solvent containing 1,3, 5-tris (4-aminophenyl) benzene and a metal salt is provided for use.
(2) And (3) adding the acid liquor into the organic solvent obtained in the step (1) to carry out polymerization reaction, thereby obtaining a carbon nanotube precursor.
(3) And calcining the carbon micron tube precursor in an inert atmosphere to obtain the carbon micron tube precursor.
Further, in the step (1), the organic solvent includes at least one of acetonitrile, ethylene glycol, N-dimethylformamide, and the like.
Further, in the step (1), the ratio of the metal ions in the 1,3, 5-tris (4-aminophenyl) benzene and the metal salt is 700: 3-70: 3.
further, the metal elements corresponding to the metal salt include: any one of iron, manganese, cobalt, nickel, platinum, palladium, and the like.
Further, the solution of the metal salt includes at least one of a nitrate solution, a sulfate solution, a hydrochloride solution, an acetate solution, etc. of metal ions, such as ferric nitrate, manganese sulfate, cobalt chloride, nickel acetate, platinum chloride, palladium nitrate, etc.
Further, in the step (2), the acid solution comprises: at least one of dilute nitric acid, dilute hydrochloric acid, dilute sulfuric acid, acetic acid, perchloric acid, phosphoric acid, chloroplatinic acid, citric acid, and the like.
Further, in the step (2), the pH of the acid solution is = 2-5. Under an acidic environment, the 1,3, 5-tri (4-aminophenyl) benzene and metal salt ions are subjected to polymerization reaction to form a micron tubular structure. The shape and size of the finally obtained carbon micron tube can be controlled by changing the pH value of the acid solution.
Further, a solid product in the reaction liquid in the step (2) can be separated by means of filtration, centrifugation and the like, and then the solid product is washed and dried to obtain the precursor.
Further, in the step (3), the calcining manner comprises: the temperature is kept at 500-650 ℃ for 2-4 hours, and then the heating is continued until the temperature is 700-1100 ℃ and the temperature is kept for 1.5-2.5 hours. The temperature is set at 500-650 ℃ for preliminary decomposition and maintaining the morphology, and the subsequent temperature rise is for improving the graphitization degree and promoting the bonding between the metal and the carbon skeleton.
Further, in the step (3), the calcination under the inert atmosphere is to ensure the formation of the carbon nanotube.
In a second aspect of the invention, the application of the metal monoatomic and nitrogen double-doped carbon nanotube in the fields of organic catalysis, low-temperature fuel cells, super capacitor electrodes, ion batteries and the like is provided. The carbon micron tube has thin wall, uniform shape, excellent oxygen reduction performance and catalytic activity, is beneficial to promoting organic catalytic reaction, and improves the electrochemical performance of low-temperature fuel cells, super capacitor electrodes and the like.
The synthesis principle of the invention is as follows: in a certain pH value range, 1,3, 5-tri (4-aminophenyl) benzene and metal salt are subjected to in-situ polymerization reaction in an acid solution and then calcined at a proper temperature, so that the metal and nitrogen double-doped hollow carbon nanotube is synthesized in one step.
Compared with the prior art, the invention has the following beneficial and unique effects:
(1) compared with the traditional template method, the hydrothermal method and the like, the method utilizes the characteristic that 1,3, 5-tri (4-aminophenyl) benzene and metal salt can directly generate in-situ polymerization reaction in an acid solution, and synthesizes the metal and nitrogen double-doped hollow carbon nanotube in one step, and the method is simple and convenient to operate.
(2) Compared with the traditional impregnation method, the problem that the doping is only on the surface is solved, in the process of preparing the carbon micron tube precursor, the metal elements can be combined with the 1,3, 5-tri (4-aminophenyl) benzene, so that the metal elements are uniformly dispersed in the whole micron tube and are tightly combined.
(3) Compared with the traditional impregnation method, the method has the advantages that the doping elements are easy to agglomerate, in-situ doping can be carried out through the combination reaction of metal and polymer, the in-situ doped hetero atoms are dispersed more uniformly and combined with a carbon skeleton more tightly, the utilization rate of the doping elements (such as noble metal elements of platinum, palladium and the like) is increased, and more active sites are provided for the performances of catalysis, batteries and the like of the prepared material.
(4) The invention can fully improve the dispersibility of the doping elements, simultaneously increases the performances of the prepared material such as catalysis and the like, and when the invention is used in the fields of catalysis or batteries and the like, under the condition of the same catalytic activity or battery capacity, the amount of the doping elements used in the invention is less, the dispersion is more uniform, and the invention can effectively reduce the preparation cost of the material, especially in the aspect of preparing the noble metal doped carbon material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a scanning electron microscope image of a monatomic iron and nitrogen double-doped carbon nanotube prepared in the first example.
Fig. 2 is a transmission electron microscope image of the monatomic iron and nitrogen double-doped carbon nanotube prepared in the first example.
FIG. 3 is an SEM image of spherical aberration correction of the monatomic Fe-and N-double-doped carbon nanotube prepared in the first example.
Fig. 4 is an X-ray diffraction pattern of the monatomic iron and nitrogen double-doped carbon nanotube prepared in the first example.
Fig. 5 is a cyclic voltammogram of a commercial platinum carbon, a monoatomic iron and nitrogen double-doped carbon nanotube prepared in the first example.
Fig. 6 is a polarization graph of a commercial platinum-carbon, monoatomic iron-and nitrogen-double-doped carbon nanotube prepared in the first example.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this invention are exemplary only. The invention will now be further described with reference to the drawings and specific examples in the specification.
First embodiment
A preparation method of a metal monoatomic and nitrogen double-doped carbon nanotube comprises the following steps:
(1) 10 mg of 1,3, 5-tris (4-aminophenyl) benzene and 0.15 mg of ferric nitrate were weighed and dissolved in 5 ml of acetonitrile at ordinary temperature to obtain solution A.
(2) Dissolving 10 mu L of nitric acid solution in 4 ml of acetonitrile to obtain a dilute nitric acid solution with pH = 4.6.
(3) And (2) dropwise adding the diluted nitric acid solution into the solution A obtained in the step (1) completely, keeping the solution in a continuously stirred state, and fully performing polymerization reaction on the 1,3, 5-tri (4-aminophenyl) benzene and ferric nitrate in the diluted nitric acid solution.
(4) And (4) taking out the solution reacted in the step (3), putting the solution into a centrifuge tube, putting the centrifuge tube into a centrifuge for centrifugation, wherein the centrifugation speed is 3000 rpm, the centrifugation time is 3 min, and washing the obtained solid product with acetonitrile for 3 times.
(5) And (3) putting the obtained solid product into a blast type drying oven to be dried for 6 hours at the temperature of 60 ℃ to obtain the carbon micron tube precursor.
(6) And (3) putting the precursor in the step (5) into a porcelain boat, transferring the precursor into a tube furnace, heating the tube furnace to 600 ℃ at the speed of 2 ℃/min under the protection of argon atmosphere, preserving heat for 3 hours, heating to 900 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, and finally collecting a product in the porcelain boat to obtain a target product: a hollow carbon micron tube with double doping of single atom iron and nitrogen.
Second embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the acetonitrile of the steps (1) and (2) with ethylene glycol.
Third embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (3) replacing the acetonitrile obtained in the step (1) and the step (2) by N, N-dimethylformamide.
Fourth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: dilute nitric acid at pH =4.6 of step (2) was replaced with dilute sulfuric acid at pH = 2.
Fifth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the dilute nitric acid of pH =4.6 of step (2) with dilute hydrochloric acid of pH = 5.
Sixth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the nitric acid in the step (2) with chloroplatinic acid with the same pH.
Seventh embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (3) replacing the nitric acid in the step (2) with acetic acid with the same pH.
Eighth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the nitric acid of the step (2) with perchloric acid with the same pH.
Ninth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the nitric acid of the step (2) with phosphoric acid with the same pH.
Tenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the nitric acid of step (2) with citric acid of the same pH.
Eleventh embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the ferric nitrate in the step (1) with cobalt chloride.
Twelfth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (3) replacing the ferric nitrate in the step (1) with manganese sulfate.
Thirteenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the ferric nitrate in the step (1) with nickel acetate.
Fourteenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the ferric nitrate in the step (1) with platinum chloride.
Fifteenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: replacing the ferric nitrate in the step (1) with palladium nitrate.
Sixteenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (4) replacing the heat preservation at 600 ℃ for 3 hours in the step (6) with the heat preservation at 500 ℃ for 4 hours.
Seventeenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (3) replacing the heat preservation at 600 ℃ for 3 hours in the step (6) with the heat preservation at 650 ℃ for 2 hours.
Eighteenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (4) replacing the temperature preservation at 900 ℃ for 2 hours in the step (6) with the temperature preservation at 1100 ℃ for 1.5 hours.
Nineteenth embodiment
A method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen, which is similar to the first embodiment, except that: and (4) replacing the temperature preservation at 900 ℃ for 2 hours in the step (6) with the temperature preservation at 700 ℃ for 2.5 hours.
Performance testing
1. The target product prepared in the first example was observed by scanning electron microscopy and transmission electron microscopy, and the results are shown in fig. 1 and fig. 2, respectively. As can be seen from fig. 1: the target product prepared in this example was a fiber rod structure. As can be further seen from FIG. 2, the tube diameter of the target product prepared in this example is about 1.3 microns, and the wall thickness is about 130nm, which indicates that the hollow tubular product with micron scale is successfully prepared in this example.
2. XRD testing was performed on the target product prepared in the first example, and the results are shown in fig. 4, where it can be seen that: the target product is carbon, the prepared microtube is a carbon material which can be seen by XRD, no diffraction peak related to metal is found, and the isolated iron monoatomic atoms dispersed on the carbon matrix in combination with the graph of FIG. 3 shows that the metal state in the prepared microtube is relatively dispersed. The test results shown in fig. 1 and fig. 2 are combined to demonstrate that the carbon nanotube doped with metal monoatomic atoms and nitrogen is successfully prepared in the first embodiment.
3. Oxygen reduction catalytic activity test: taking the hollow carbon micron tube prepared in the first embodiment, placing the tube in a mortar for grinding, taking 4mg of the tube to be placed in a centrifuge tube, adding 1ml of ethanol and 0.1ml of perfluorosulfonic acid-polytetrafluoroethylene copolymer, placing the tube in an ultrasonic cleaning machine for constant temperature ultrasound for 3 hours to obtain catalyst slurry, dripping the catalyst slurry on a rotating disc electrode by a liquid-transferring gun with the capacity of 5ul each time, baking a bearing sample under an infrared lamp, and repeating the operation for 2-3 times. AgCl is used as a reference electrode, a platinum net is used as a counter electrode, 0.1M KOH is dissolved in 100ml of water to prepare electrolyte to carry out oxygen reduction test on the carbon micron tube, and O is introduced2And connecting the three-electrode test system. The oxygen reduction catalytic activity of commercial platinum carbon (E-TEK) was tested in the same manner. As shown in fig. 5 and 6, it can be seen that the prepared carbon nanotube has a significant reduction peak in an oxygen atmosphere, the reduction peak position is close to that of commercial platinum carbon, the initial potential and the half-slope potential are comparable to those of platinum carbon, and the carbon nanotube has good oxygen reduction performance.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a metal monoatomic and nitrogen double-doped carbon nanotube comprises the following steps:
(1) providing an organic solvent containing 1,3, 5-tri (4-aminophenyl) benzene and a metal salt for later use;
(2) adding acid liquor into the organic solvent obtained in the step (1) for polymerization reaction to obtain a carbon nanotube precursor;
(3) and calcining the carbon micron tube precursor in an inert atmosphere to obtain the carbon micron tube precursor.
2. The method of claim 1, wherein the organic solvent comprises at least one of acetonitrile, ethylene glycol, and N, N-dimethylformamide.
3. The method for preparing a metal monatomic and nitrogen-double-doped carbon nanotube according to claim 1, wherein in the step (1), the ratio of the 1,3, 5-tris (4-aminophenyl) benzene to the metal salt ion is 700: 3-70: 3.
4. the method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen according to claim 3, wherein the metal element includes any one of iron, manganese, cobalt, nickel, platinum, palladium, etc.;
preferably, the solution of the metal salt includes at least one of a nitrate solution, a sulfate solution, a hydrochloride solution, and an acetate solution of metal ions, such as iron nitrate, manganese sulfate, cobalt chloride, nickel acetate, platinum chloride, palladium nitrate, and the like.
5. The method for preparing a metal monatomic and nitrogen-double-doped carbon nanotube according to claim 1, wherein in the step (2), the acid solution comprises: at least one of dilute nitric acid, dilute hydrochloric acid, dilute sulfuric acid, acetic acid, perchloric acid, phosphoric acid, chloroplatinic acid and citric acid.
6. The method for preparing a metal monatomic and nitrogen-double-doped carbon nanotube according to claim 1, wherein in the step (2), the acid solution has a pH of =2 to 5.
7. The method for preparing the metal monatomic and nitrogen double-doped carbon nanotube according to claim 1, wherein the precursor is obtained by separating a solid product in the reaction solution of the step (2) by a filtration or centrifugation method, and then washing and drying the solid product.
8. The method for preparing a metal monatomic and nitrogen-double-doped carbon nanotube according to any one of claims 1 to 7, wherein in the step (3), the calcination is carried out in a manner comprising: the heat preservation is carried out for 2-4 hours at 500-650 ℃, then the heating is continued to 700-1100 ℃, the heat preservation is carried out for 1.5-2.5 hours, the constant temperature of 500-650 ℃ is used for preliminary decomposition and keeping the appearance, and the later temperature rise is used for improving the graphitization degree and promoting the bonding between the metal and the carbon skeleton.
9. The method for preparing a carbon nanotube doped with metal monoatomic atoms and nitrogen according to any one of claims 1 to 7, wherein the inert atmosphere calcination in the step (3) is performed to ensure the formation of the carbon nanotube.
10. The application of the carbon micro-tube obtained by the preparation method of any one of claims 1 to 9 and double-doped with metal monoatomic atoms and nitrogen comprises the following application fields: organic catalysis, low-temperature fuel cells, supercapacitor electrodes, and ion batteries.
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| US20080292530A1 (en) * | 2007-05-11 | 2008-11-27 | The Government Of Us, As Represented By The Secretary Of The Navy | Calcination of carbon nanotube compositions |
| US20110104040A1 (en) * | 2009-10-29 | 2011-05-05 | Songmin Shang | Simple, effective and scalable process for making carbon nanotubes |
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| US20080292530A1 (en) * | 2007-05-11 | 2008-11-27 | The Government Of Us, As Represented By The Secretary Of The Navy | Calcination of carbon nanotube compositions |
| US20110104040A1 (en) * | 2009-10-29 | 2011-05-05 | Songmin Shang | Simple, effective and scalable process for making carbon nanotubes |
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| XUN CUI等: "\"Simultaneously Crafting Single-Atomic Fe Sites and Graphitic Layer-Wrapped Fe3C Nanoparticles Encapsulated within Mesoporous Carbon Tubes for Oxygen Reduction\"", 《ADVANCED FUNCTIONAL MATERIALS》 * |
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