CN118324123A - Nitrogen-doped carbon micro-tube and preparation method thereof - Google Patents
Nitrogen-doped carbon micro-tube and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- 238000010438 heat treatment Methods 0.000 claims description 55
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- 239000002041 carbon nanotube Substances 0.000 claims description 43
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- 229910052593 corundum Inorganic materials 0.000 claims description 37
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- 238000007740 vapor deposition Methods 0.000 claims description 27
- 239000012159 carrier gas Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
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- HPJKLCJJNFVOEM-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrochloride Chemical compound Cl.NC1=NC(N)=NC(N)=N1 HPJKLCJJNFVOEM-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention provides a nitrogen-doped carbon micro-tube and a preparation method thereof, belonging to the technical field of preparation of carbon micro-nano materials. The nitrogen-doped carbon micro-tube material is of a hollow tubular structure, the diameter of the tube is 1-2 mu m, the length of the tube is 5-15 mu m, and the thickness of the tube wall is 10-50nm. The preparation method comprises the following steps: firstly, thermal polycondensation of a nitrogen-containing compound to prepare a nitrogen-containing solid carbon source, then, thermal pyrolysis of the nitrogen-containing solid carbon source, and chemical vapor deposition catalytic growth of pyrolysis gas on the surface of a metal catalyst. The preparation method disclosed by the invention is simple in operation process, can be used for large-scale preparation, and the obtained nitrogen-doped carbon micro-tube has a unique micro-nano structure and high nitrogen content, and has a wide application prospect in the fields of electrochemical energy storage and the like.
Description
Technical Field
The invention relates to a nitrogen-doped carbon micro-tube and a preparation method thereof, belonging to the technical field of carbon micro-tube preparation.
Background
At present, carbon nanotubes have achieved remarkable achievements in various researches by virtue of excellent conductivity, excellent stability and the like, and related reports and researches are quite rare when the carbon nanotubes are used as micrometer-scale carbon tubes with similar structural properties as the carbon nanotubes. Due to the nano-scale reason, the carbon nanotubes have strong van der Waals force and pi-pi action, are easy to agglomerate, and are mutually entangled and difficult to disperse in a matrix. In addition, the smaller tube diameter of carbon nanotubes limits the entry of larger volume molecules into their cavities, both monodispersity and single operability of carbon nanotubes are often poor, and the hollow portions of carbon nanotubes are often partially or fully blocked by some products, making their molecular transport and mass transfer, etc., a series of problems. These disadvantages greatly reduce the practical application value of carbon nanotubes. Compared with the carbon nano tube, the carbon micro tube has remarkable tube diameter advantage, and has wide application prospect in the fields of micro-electronics, micro-mechanical devices, micro-nano reactors, drug delivery, micro-nano fluid and the like. However, since the catalyst activity decreases with increasing particle size, the conventional method for synthesizing carbon nanotubes is not suitable for synthesizing carbon nanotubes, and currently, high-efficiency and controllable synthesis of carbon nanotubes has a great challenge.
The existing method for synthesizing the carbon micro-tube generally has the defects of harsh conditions and poor controllability. The preparation method of the porous carbon micro-tube and the porous carbon micro-tube (application publication No. CN 110028066A) disclose a technology for preparing the carbon micro-tube with a porous structure by taking corn silk as a biomass precursor through carbonization and activation, but the controllable adjustment of the diameter of the carbon micro-tube cannot be realized, and the prepared carbon micro-tube belongs to a hard carbon material and cannot realize graphitization. A process for preparing the sustainable high-yield carbon-micrometer tube (authorized bulletin No. CN 103387220B) discloses a technology for synthesizing carbon-micrometer tube by high-temperature high-pressure method using urea and glycol as carbon source. However, the technology has the defect of high synthesis temperature and high synthesis pressure, and the synthesis conditions are very harsh, which is not beneficial to the large-scale synthesis of the carbon micro-tube. Therefore, it is necessary to provide a method for preparing carbon nanotubes with mild and controllable synthesis conditions, that is, to reduce the synthesis temperature of the carbon nanotubes, and synthesize the carbon nanotubes at normal pressure, and simultaneously, to realize accurate regulation and control of the diameter, crystallization degree and heteroatom doping of the carbon nanotubes, and finally, to realize controllable, large-scale and high-quality synthesis of the carbon nanotubes.
Disclosure of Invention
In order to solve the defects existing in the existing carbon micro-tube preparation technology, the invention provides a chemical vapor deposition catalytic controllable synthesis nitrogen-doped carbon micro-tube and a preparation method thereof, which can realize low-temperature, controllable and large-scale synthesis of the nitrogen-doped carbon micro-tube. The introduction of N atoms can alter the structure of the carbon matrix to create more electrochemical/catalytic active sites and can affect the charge distribution of the material to increase the conductivity of the carbon nanotubes. At the same time, the introduction of N atoms can also improve the wettability of the surface of the carbon micro-tube. In a word, nitrogen doping can endow the carbon micro-tube with more excellent physical and chemical properties, improve the application performance of the carbon micro-tube and greatly expand the application range of the carbon micro-tube.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The nitrogen-doped carbon micro-tube is of a hollow tubular structure, the diameter of the tube is 0.7-2 mu m, the length of the tube is 5-20 mu m, and the thickness of the tube wall is 10-80nm.
A preparation method of a nitrogen-doped carbon micro-tube comprises the steps of firstly, performing thermal condensation polymerization on a nitrogen-containing compound to prepare a nitrogen-containing solid carbon source. And secondly, respectively placing a nitrogen-containing solid carbon source and metal nickel powder in a pyrolysis zone and a vapor deposition reaction zone of heating equipment, carrying out pyrolysis on the nitrogen-containing solid carbon source, and carrying out chemical vapor deposition catalytic growth of carbon micro-tubes on the surface of the metal nickel powder by pyrolysis gas. And finally, taking out the sample after the reaction, adding hydrochloric acid solution, and performing post-treatment to obtain the nitrogen-doped carbon micro-tube material. The method specifically comprises the following steps:
firstly, preparing a nitrogen-containing solid carbon source:
Placing a nitrogen-containing compound into a corundum boat with a cover, transferring into a muffle furnace, heating to 400-600 ℃ from room temperature, reacting for 2-6h, and grinding the product to obtain a powdery nitrogen-containing solid carbon source;
Secondly, preparing the nitrogen-doped carbon micro-tube by a chemical vapor deposition method:
2.1 Placing the nitrogen-containing solid carbon source prepared in the first step into an open corundum boat container A; the metallic nickel powder is placed in an open corundum boat container B.
2.2 The container A and the container B are respectively arranged in a quartz tube, the quartz tube is arranged in a heating device, the container A is positioned in a pyrolysis zone of the heating device, and the container B is positioned in a vapor deposition reaction zone of the heating device.
2.3 Introducing carrier gas into the quartz tube, wherein the flow direction of the carrier gas is from the side of the container A to the side of the container B; and the pyrolysis zone and the vapor deposition reaction zone are heated to the final temperature for constant temperature reaction, wherein the final temperature of the pyrolysis zone is 650-900 ℃, the final temperature of the vapor deposition reaction zone is 700-1000 ℃, the constant temperature reaction time is 30-240min, and after the reaction is finished, the heating device is naturally cooled to the room temperature. In the reaction process of the step 2.3), the nitrogen-containing solid carbon source is pyrolyzed at high temperature to generate gaseous nitrogen-containing carbon small molecules, and the gaseous small molecules are contacted with the metal nickel powder, dissolved and gradually saturated under the action of carrier gas. And then the carbon atoms are connected and gradually diffused and deposited under the catalysis of high temperature and metallic nickel powder, and finally the nitrogen doped carbon micro-tube is grown.
Thirdly, taking out the sample in the container B, placing the sample in a beaker, and adding hydrochloric acid solution, wherein the mass ratio of the hydrochloric acid solution to the sample taken out from the container B is 100:1, reacting for 24-48h. And then carrying out suction filtration and water washing until the solution is neutral, and finally, carrying out freeze drying to obtain the nitrogen-doped carbon micro-tube material.
Further, in the first step, the nitrogen-containing compound is one or more of urea, thiourea, cyanamide, dicyandiamide, melamine and melamine chloride.
Further, in the step 2.1), the mass ratio of the nitrogen-containing solid carbon source to the metal nickel powder is 1:0.1-2. The particle size of the metal nickel powder is 100-300nm.
Further, in the step 2.3), the carrier gas is one of nitrogen, argon, helium, methane and ethylene.
Further, the temperature rising rate in the first step is 2-10 ℃/min. In the step 2.3), the pyrolysis zone and the vapor deposition reaction zone are heated to the final temperature at the heating rate of 1-10 ℃/min.
Further, the concentration of the hydrochloric acid solution in the third step is 2-8mol/L. The freeze drying temperature in the third step is-52 ℃ and the time is 24-72h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method realizes the preparation of the high-purity nitrogen-doped carbon micro-tube by a strategy of solid carbon source pyrolysis chemical vapor deposition.
(2) The structure of the nitrogen-doped carbon micro-tube is adjustable, and the morphology, the size and the nitrogen content of the hollow micro-tube structure can be regulated and controlled by adjusting the proportion of the nitrogen-containing solid carbon source, the particle size of the metal nickel powder, the reaction temperature, the constant temperature time and other factors.
(3) The method disclosed by the invention is simple to operate, easy to amplify, mild and controllable in reaction condition, wide in raw materials and wide in application prospect in the field of electrochemical energy storage.
Drawings
FIG. 1 is a scanning electron micrograph of a nitrogen-doped carbon nanotube obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of a nitrogen-doped carbon nanotube obtained in example 1 of the present invention;
FIG. 3 is a Raman spectrum of the nitrogen-doped carbon nanotube obtained in example 1 of the present invention;
FIG. 4 is an N1s chart of XPS spectrum of a nitrogen-doped carbon nanotube obtained in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the nitrogen-doped carbon nanotubes obtained in example 2 of the present invention;
FIG. 6 is a scanning electron microscope image of the nitrogen-doped carbon nanotubes obtained in example 3 of the present invention;
FIG. 7 is a scanning electron microscope image of the nitrogen-doped carbon nanotubes obtained in example 4 of the present invention;
FIG. 8 is a scanning electron microscope image of the nitrogen-doped carbon nanotube obtained in example 5 of the present invention.
Detailed Description
The invention is further illustrated in the following in connection with the specific embodiments, but the invention is not limited to the following examples.
Example 1:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) The preparation method of the nitrogen-containing solid carbon source comprises the following steps: and (3) weighing melamine, placing the melamine into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min, reacting for 4 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 0.2g of metal nickel powder with the specification of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 800 ℃ from room temperature at a speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 800 ℃ at a speed of 10 ℃/min, and carrying out constant-temperature reaction for 60min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 50mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The scanning electron microscope of the nitrogen-doped carbon micro-tube prepared by the embodiment is shown in fig. 1, and the scanning electron microscope shows that the prepared nitrogen-doped carbon micro-tube has a regular micro-nano structure, the diameter of the micro-tube is 1 μm, the length is about 10 μm, and the wall thickness is 60nm. XRD analysis was performed on the nitrogen-doped carbon nanotubes, as shown in FIG. 2, with distinct diffraction peaks characteristic of carbon, indicating successful conversion of the precursor to carbon material under the catalytic action of metallic nickel powder. The Raman analysis is performed on the nitrogen-doped carbon micro-tube, as shown in fig. 3, the Raman spectrum has two characteristic peaks of carbon, and the value of I D/IG is lower, which indicates that the nitrogen-doped micro-tube has higher graphitization degree.
Fig. 4 is an N1s plot of XPS spectra of nitrogen-doped carbon nanotubes prepared in this example, fitted with three characteristic peaks corresponding to pyridine nitrogen (398.7 eV), pyrrole nitrogen (399.7 eV) and graphite nitrogen (401.2 eV), which illustrates the presence of nitrogen atoms in the carbon nanotubes, successfully effecting nitrogen doping.
Example 2:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing melamine, placing the melamine into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min, reacting for 4 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 1.0g of metal nickel powder with the particle size of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 800 ℃ from room temperature at a speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 800 ℃ at a speed of 10 ℃/min, and carrying out constant-temperature reaction for 60min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 45mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The scanning electron microscope of the nitrogen-doped carbon micro-tube prepared by the embodiment is shown in fig. 5, and the scanning electron microscope shows that the prepared nitrogen-doped carbon micro-tube has a regular micro-nano structure, the diameter of the micro-tube is 1.5 μm, the length is about 9 μm, and the wall thickness is 60nm.
XRD analysis is carried out on the nitrogen-doped carbon micro-tube, and the carbon-doped carbon micro-tube has obvious characteristic diffraction peaks of carbon characterization, which indicate that the precursor is successfully converted into a carbon material under the catalysis of the metal nickel powder. And carrying out Raman analysis on the nitrogen-doped carbon micro-tube, wherein a Raman spectrogram has two characteristic peaks of carbon, and the I D/IG value is lower, so that the nitrogen-doped micro-tube has higher graphitization degree. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
Example 3:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing melamine, placing the melamine into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min, reacting for 4 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 2.0g of metal nickel powder with the grain diameter of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 800 ℃ from room temperature at a speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 800 ℃ at a speed of 10 ℃/min, and carrying out constant-temperature reaction for 60min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 40mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The scanning electron microscope of the nitrogen-doped carbon micro-tube prepared by the embodiment is shown in fig. 6, and the scanning electron microscope shows that the prepared nitrogen-doped carbon micro-tube has a regular micro-nano structure, the diameter of the micro-tube is 1.2 μm, the length is about 6 μm, and the wall thickness is about 60nm.
XRD analysis is carried out on the nitrogen-doped carbon micro-tube, and the carbon-doped carbon micro-tube has obvious characteristic diffraction peaks of carbon characterization, which indicate that the precursor is successfully converted into a carbon material under the catalysis of the metal nickel powder. And carrying out Raman analysis on the nitrogen-doped carbon micro-tube, wherein a Raman spectrogram has two characteristic peaks of carbon, and the I D/IG value is lower, so that the nitrogen-doped micro-tube has higher graphitization degree. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
Example 4:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing melamine, placing the melamine into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min, reacting for 4 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 0.2g of metal nickel powder with the particle size of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 700 ℃ from room temperature at a speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 700 ℃ at a speed of 10 ℃/min, and carrying out constant-temperature reaction for 60min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 50mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The scanning electron microscope of the nitrogen-doped carbon micro-tube prepared by the embodiment is shown in fig. 7, and the scanning electron microscope shows that the prepared nitrogen-doped carbon micro-tube has a regular micro-nano structure, the diameter of the micro-tube is 0.7 μm, the length is about 20 μm, and the wall thickness is about 50nm.
XRD analysis is carried out on the nitrogen-doped carbon micro-tube, obvious characteristic diffraction peaks exist for the carbon, raman analysis is carried out on the nitrogen-doped carbon micro-tube, two characteristic peaks of carbon exist in a Raman spectrogram, and the results show that the precursor is successfully converted into the carbon material under the action of nickel metal powder. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
Example 5:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing melamine, placing the melamine into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min, reacting for 4 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 0.2g of metal nickel powder with the particle size of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 900 ℃ from room temperature at the speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 900 ℃ at the speed of 10 ℃/min, and carrying out constant-temperature reaction for 60min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 50mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The scanning electron microscope of the nitrogen-doped carbon micro-tube prepared by the embodiment is shown in fig. 8, and the scanning electron microscope shows that the prepared nitrogen-doped carbon micro-tube has a regular micro-nano structure, the diameter of the micro-tube is 1 μm, the length is about 12 μm, and the wall thickness is about 70nm.
XRD analysis is carried out on the nitrogen-doped carbon micro-tube, and the carbon-doped carbon micro-tube has obvious characteristic diffraction peaks of carbon characterization, which indicate that the precursor is successfully converted into a carbon material under the action of a nickel metal catalyst. The Raman analysis is carried out on the nitrogen-doped carbon micro-tube, two characteristic peaks of carbon exist in a Raman spectrogram, and the I D/IG value is low, so that the nitrogen-doped carbon micro-tube has high graphitization degree, and the nitrogen-doped carbon micro-tube benefits from excellent catalysis of metal nickel powder at high temperature. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
Example 6:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing thiourea, placing the thiourea in a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min, reacting for 4 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 2.0g of metal nickel powder with the grain diameter of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 900 ℃ from room temperature at the speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 1000 ℃ at the speed of 10 ℃/min, and carrying out constant-temperature reaction for 100min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 50mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The nitrogen-doped carbon nanotubes prepared in this embodiment have a diameter of 1 μm, a length of about 10 μm and a wall thickness of about 80nm. XRD analysis is carried out on the nitrogen-doped carbon micro-tube, and the carbon-doped carbon micro-tube has obvious characteristic diffraction peaks of carbon characterization, which indicate that the precursor is successfully converted into a carbon material under the action of a nickel metal catalyst. And carrying out Raman analysis on the nitrogen-doped carbon micro-tube, wherein a Raman spectrogram has two characteristic peaks of carbon, and the I D/IG value is lower, so that the nitrogen-doped micro-tube has higher graphitization degree at a high vapor deposition temperature. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
Example 7:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing urea, placing the urea into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 400 ℃ at a speed of 10 ℃/min, reacting for 6 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 4.0g of metal nickel powder with the particle size of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 650 ℃ from room temperature at a speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 800 ℃ at a speed of 10 ℃/min, and carrying out constant-temperature reaction for 30min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 50mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The nitrogen-doped carbon nanotubes prepared in this embodiment have a diameter of 1 μm, a length of about 5 μm and a wall thickness of about 40nm. XRD analysis is carried out on the nitrogen-doped carbon micro-tube, obvious characteristic diffraction peaks exist for the carbon, raman analysis is carried out on the nitrogen-doped carbon micro-tube, two characteristic peaks of carbon exist in a Raman spectrogram, and the results show that the precursor is successfully converted into the carbon material under the action of nickel metal powder. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
Example 8:
the preparation method of the nitrogen-doped carbon micro-tube comprises the following steps:
(1) And (3) preparing a nitrogen-containing solid carbon source, namely weighing dicyandiamide, placing the dicyandiamide into a corundum boat with a cover, transferring the corundum boat into a muffle furnace, heating to 600 ℃ at a speed of 10 ℃/min, reacting for 2 hours, and grinding the product to obtain the powdery nitrogen-containing solid carbon source.
(2) 2.0G of nitrogen-containing solid carbon source powder is flatly paved at the bottom of a corundum boat container A, 0.5g of metal nickel powder with the particle size of 200nm is flatly paved at the bottom of a corundum boat container B, and the container A and the container B are placed into a quartz tube.
(3) Putting the quartz tube in the step (2) into a two-section heating furnace, so that an inner container A and an inner container B of the quartz tube are respectively positioned in a pyrolysis zone and a vapor deposition reaction zone; argon is introduced into the quartz tube, a container A containing nitrogen-containing solid carbon source powder is positioned at the upstream of the carrier gas, and a container B containing metal nickel powder is positioned at the downstream of the carrier gas.
(4) Heating the pyrolysis zone where the container A is positioned to 650 ℃ from room temperature at a speed of 10 ℃/min, heating the vapor deposition reaction zone where the container B is positioned to 800 ℃ at a speed of 10 ℃/min, and carrying out constant-temperature reaction for 240min; after the reaction is finished, the heating device is naturally cooled to room temperature.
(5) Taking out the sample in the container B, placing the sample in a beaker, adding 50mL of hydrochloric acid solution with the concentration of 2mol/L, and reacting for 48 hours to remove the metallic nickel powder. And (3) carrying out suction filtration and water washing on the sample from which the metal nickel powder is removed until the solution is neutral, and finally, carrying out freeze drying for 72 hours at the temperature of minus 52 ℃ to obtain the nitrogen-doped carbon micro-tube material.
The nitrogen-doped carbon nanotubes prepared in this embodiment had a diameter of 1.2 μm, a length of about 20 μm and a wall thickness of about 40nm. XRD analysis is carried out on the nitrogen-doped carbon micro-tube, obvious characteristic diffraction peaks exist for the carbon, raman analysis is carried out on the nitrogen-doped carbon micro-tube, two characteristic peaks of carbon exist in a Raman spectrogram, and the results show that the precursor is successfully converted into the carbon material under the action of nickel metal powder. XPS analysis was performed on nitrogen-doped carbon nanotubes, wherein the presence of an N1s diffraction peak indicates successful realization of nitrogen doping.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (8)
1. The preparation method of the nitrogen-doped carbon micro-tube is characterized in that firstly, a nitrogen-containing compound is subjected to thermal condensation to prepare a nitrogen-containing solid carbon source; secondly, respectively placing a nitrogen-containing solid carbon source and metal nickel powder in a pyrolysis zone and a vapor deposition reaction zone of heating equipment, and performing high-temperature pyrolysis on the nitrogen-containing solid carbon source, wherein pyrolysis gas is used for catalyzing and growing carbon micro-tubes on the surface of the metal nickel powder by chemical vapor deposition; and finally, adding the product obtained after the reaction into hydrochloric acid solution, and performing aftertreatment to obtain the nitrogen-doped carbon micro-tube material.
2. The method for preparing the nitrogen-doped carbon micro-tube according to claim 1, comprising the steps of:
firstly, preparing a nitrogen-containing solid carbon source:
Placing the nitrogen-containing compound in a muffle furnace, heating to 400-600 ℃ from room temperature, reacting for 2-6h, and grinding the product to obtain a powdery nitrogen-containing solid carbon source;
Secondly, preparing the nitrogen-doped carbon micro-tube by a chemical vapor deposition method:
2.1 Placing the nitrogen-containing solid carbon source prepared in the first step into an open corundum boat container A; placing metal nickel powder into an open corundum boat container B;
2.2 The container A and the container B are respectively arranged in a quartz tube, the quartz tube is arranged in a heating device, the container A is positioned in a pyrolysis zone of the heating device, and the container B is positioned in a vapor deposition reaction zone of the heating device;
2.3 Introducing carrier gas into the quartz tube, wherein the flow direction of the carrier gas is from the side of the container A to the side of the container B; the pyrolysis zone and the vapor deposition reaction zone are heated to a final temperature for constant temperature reaction, wherein the final temperature of the pyrolysis zone is 650-900 ℃, the final temperature of the vapor deposition reaction zone is 700-1000 ℃, the constant temperature reaction time is 30-240min, a nitrogen-containing solid carbon source is pyrolyzed at a high temperature in the reaction process to generate gaseous nitrogen-containing carbon micromolecules, the gaseous micromolecules are contacted with and dissolved in the presence of a carrier gas and gradually reach saturation with metal nickel powder, then carbon atoms are connected and gradually diffused and deposited under the catalysis of the high temperature and the metal nickel powder, and finally the nitrogen-doped carbon micro-tube is grown; after the reaction is finished, naturally cooling the heating device to room temperature;
And thirdly, adding the sample in the container B into hydrochloric acid solution for reaction, performing suction filtration, washing with water until the solution is neutral, and finally performing freeze drying to obtain the nitrogen-doped carbon micro-tube material.
3. The method for preparing a nitrogen-doped carbon nanotube according to claim 2, wherein the nitrogen-containing compound in the first step is one or more of urea, thiourea, cyanamide, dicyandiamide, melamine and melamine chloride.
4. The method for preparing a nitrogen-doped carbon nanotube according to claim 2, wherein in the step 2.1), the mass ratio of the nitrogen-containing solid carbon source to the metal nickel powder is 1:0.1-2; the particle size of the metal nickel powder is 100-300nm.
5. The method of claim 2, wherein in the step 2.3), the carrier gas is one of nitrogen, argon, helium, methane, and ethylene.
6. The method for preparing a nitrogen-doped carbon nanotube as claimed in claim 2, wherein the heating rate in the first step is 2-10 ℃/min; in the step 2.3), the pyrolysis zone and the vapor deposition reaction zone are heated to the final temperature at the heating rate of 1-10 ℃/min.
7. The method for preparing nitrogen-doped carbon nanotubes according to claim 2, wherein the concentration of the hydrochloric acid solution in the third step is 2-8mol/L; the freeze drying temperature in the third step is-52 ℃ and the time is 24-72h; in the third step, the mass ratio of the hydrochloric acid solution to the sample is 100:1, the reaction time is 24-48h.
8. The nitrogen-doped carbon micro-tube is characterized in that the nitrogen-doped carbon micro-tube is obtained by adopting the preparation method of any one of claims 1-7, the nitrogen-doped carbon micro-tube is of a hollow tubular structure, the diameter of the tube is 0.7-2 mu m, the length of the tube is 5-20 mu m, and the thickness of the tube wall is 10-80nm.
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