CN113511644A - Preparation method of nitrogen-doped carbon nano tube with ultrahigh nitrogen doping amount - Google Patents

Preparation method of nitrogen-doped carbon nano tube with ultrahigh nitrogen doping amount Download PDF

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CN113511644A
CN113511644A CN202111029502.3A CN202111029502A CN113511644A CN 113511644 A CN113511644 A CN 113511644A CN 202111029502 A CN202111029502 A CN 202111029502A CN 113511644 A CN113511644 A CN 113511644A
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王奇
赵晓倩
刘亚青
吴聪雅
韩孟杰
赵贵哲
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North University of China
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Abstract

The invention relates to the field of preparation of nitrogen-doped carbon nanotubes, in particular to a preparation method of an ultra-high nitrogen-doped carbon nanotube (NCNT), which comprises the following steps: based on the method of catalytic chemical vapor deposition, on the basis of providing a stable carbon-nitrogen source in a reactor, a carrier gas containing nitrogen atoms is provided, the carrier gas carries the carbon-nitrogen source to the surface of the metal-based catalyst, and the NCNT with ultrahigh nitrogen content is obtained by growing along the outer edge of the metal-based catalyst particles. The method can be carried out by a simple device, and has the advantages of simple process, economy, high efficiency, environmental protection and the like. The raw materials used by the method have the carbon source and the nitrogen source at the same time, and have the characteristics of simple operation, advanced process and high nitrogen doping amount. The prepared NCNT has ultrahigh nitrogen content and high yield. Has great competitiveness compared with the NCNT on the market at present. The catalyst used in the invention has mild reaction conditions and high efficiency.

Description

Preparation method of nitrogen-doped carbon nano tube with ultrahigh nitrogen doping amount
Technical Field
The invention relates to the field of preparation of nitrogen-doped carbon nanotubes, in particular to a method for preparing nitrogen-doped carbon nanotubes (NCNT) with ultrahigh nitrogen doping amount.
Background
Carbon Nanotubes (CNTs) have been widely studied in various fields such as conduction, electromagnetic shielding, microwave absorption, supercapacitors, electrode materials, catalysts, catalyst carriers, field emission displays, transparent conductive films, scanning probe tips, drug release, electronic devices, sensors, and drivers, due to their characteristics such as high aspect ratio, large specific surface area, and excellent mechanical properties. CNTs have become a current research hotspot and have great development potential, especially in the excellent properties after doping and compounding CNTs. At present, various heteroatoms such as boron, nitrogen, phosphorus, sulfur and the like are doped into the CNT, and the doping changes the outer electron number, electronegativity and atomic size of carbon atoms on the surface of the CNT, so that the CNT shows specific electronic characteristics and surface defects, has excellent mechanical, electrical and catalytic properties, and can be widely applied to the fields of photoelectronic devices, biochemical sensors, catalysts, super capacitors, lithium ion batteries, fuel batteries, solar batteries and the like. The controllable large-scale preparation of doped CNTs has also been a leading research topic. The current methods for preparing carbon nanotubes mainly include graphite arc method, floating catalysis method, laser vapor method, pyrolysis polymerization method and chemical vapor deposition. Among these methods, the chemical vapor deposition method is widely used as a method for preparing carbon nanotubes because it can adjust experimental conditions such as a carbon source, a catalyst, and a synthesis atmosphere. Nitrogen doping of CNTs is currently the most common and most widely studied subject of CNT doping, and we have studied nitrogen-doped carbon nanotubes (NCNTs) for controlled mass production.
Disclosure of Invention
The invention aims to provide a simple and green preparation method of carbon nano-tubes (NCNT) with ultrahigh nitrogen content and easy industrialization. By adopting the preparation method, NCNT with ultrahigh nitrogen content and high yield can be obtained. The method has simple process, economy and high efficiency, and solves the problem that the nitrogen doping amount of the nitrogen-doped carbon nano tube is generally not high at present.
The invention is realized by the following technical scheme: a simple, green and easily industrialized preparation method of a carbon nano tube doped with nitrogen with ultrahigh nitrogen content comprises the following steps: based on the method of catalytic chemical vapor deposition, on the basis of providing a stable carbon-nitrogen source in a reactor, a carrier gas containing nitrogen atoms is provided, the carrier gas carries the carbon-nitrogen source to the surface of the metal-based catalyst, and the NCNT with ultrahigh nitrogen content is obtained by growing along the outer edge of the metal-based catalyst particles.
As a further improvement of the technical scheme of the invention, the growth temperature of NCNT in the reactor is 300-1400 ℃.
As a further improvement of the technical scheme of the invention, the composition of the metal-based catalyst comprises but is not limited to one or more than two metal elements of Fe, Mo, Al, Co, Ni, Mg and Cu.
As a further improvement of the technical solution of the present invention, the preparation method of the metal-based catalyst includes, but is not limited to, a sol-gel method, a hydrothermal synthesis method, and a solution synthesis method.
As a further improvement of the technical scheme of the invention, the carbon-nitrogen source comprises a gaseous carbon-nitrogen source, a gasified solid carbon-nitrogen source or a gasified liquid carbon-nitrogen source.
As a further improvement of the technical scheme of the invention, the gaseous carbon-nitrogen source comprises but is not limited to ammonia gas, acetylene; the solid carbon and nitrogen source includes, but is not limited to, imidazole, nitrogen mustard, melamine, p-phenylenediamine, benzimidazole; the liquid carbon-nitrogen source includes, but is not limited to, hydrocyanic acid, ammonia, aniline, pyridine, ethylenediamine, acetonitrile.
As a further improvement of the technical solution of the present invention, the nitrogen atoms in the nitrogen atom-containing carrier gas include but are not limited to one or more of nitrogen, ammonia, nitric oxide, nitrogen dioxide, and dinitrogen trioxide.
As a further improvement of the technical scheme of the invention, the nitrogen doping amount of the NCNT is 0.1-50 at.%.
As a further improvement of the technical scheme of the invention, the yield of the NCNT is 1-2000% of the dosage of the metal-based catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1. the method can be carried out by a simple device, and has the advantages of simple process, economy, high efficiency, environmental protection and the like.
2. The raw materials used by the method have the carbon source and the nitrogen source at the same time, and have the characteristics of simple operation, advanced process and high nitrogen doping amount. The prepared NCNT has ultrahigh nitrogen content and high yield. Compared with the NCNT (the highest nitrogen content is about 3.5 at percent and the price is expensive, and the average price is about 100 yuan/g) on the market at present, the method has great competitiveness.
3. The catalyst used in the invention has mild reaction conditions and high efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XPS plot of the ultra-high nitrogen doped carbon nanotubes of example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a simple, green and easily industrialized preparation method of a carbon nano tube doped with nitrogen with ultrahigh nitrogen content, which comprises the following steps: based on the method of catalytic chemical vapor deposition, on the basis of providing a stable carbon-nitrogen source in a reactor, a carrier gas containing nitrogen atoms is provided, the carrier gas carries the carbon-nitrogen source to the surface of the metal-based catalyst, and the NCNT with ultrahigh nitrogen content is obtained by growing along the outer edge of the metal-based catalyst particles.
In the present invention, the nitrogen atom-containing carrier gas is used to further increase the nitrogen content in the NCNT.
In specific implementation, the growth temperature of NCNT in the reactor is 300-1400 ℃. In the present invention, the reactor is preferably a vessel, such as a quartz or metal vessel, with a heating device or capable of being heated. The growth temperature of the NCNT is preferably 500-1200 ℃, the specific growth time of the NCNT is 1-800 min, the preferred growth time is 10-100 min, and the more preferred growth time is 15-30 min.
Specifically, the composition of the metal-based catalyst includes, but is not limited to, one or more than two metal elements of Fe, Mo, Al, Co, Ni, Mg, and Cu.
When in specific application, the metal-based catalyst is Fe-Mo/Al2O3Catalyst or Co-Mo/Al2O3A catalyst.
Further, the present invention provides Fe-Mo/Al2O3Two preparation methods of the catalyst are as follows:
hydrothermal synthesis method: mixing Fe (NO)3)3·9H2O、Al(NO3)3·9H2O and (NH)4)6Mo7O24·4H2And dripping the O solution into the CTAB solution, continuously stirring uniformly, and adjusting the pH value of the solution to 8 by using ammonia water. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and held at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Fe-Mo/Al2O3A catalyst. In the presence of Fe-Mo/Al2O3In the preparation method of the catalyst, the molar ratio of Fe, Mo and Al is 8:3:10, and the molar ratio of Mo and CTAB is equal to 1: 13.
Sol-gel method: mixing Fe (NO)3)3·9H2O、 (NH4)6Mo7O24·4H2O、Al(NO3)3·9H2O and C6H8O7·H2Dissolving O in 50mL deionized water, continuously stirring in 80 ℃ water bath until a jelly is formed, transferring the formed jelly into a 110 ℃ oven for treatment for 2h, continuously roasting in air at 500 ℃ for 2h, collecting the product and grinding to obtain Fe-Mo/Al2O3Catalyst particles. In the presence of Fe-Mo/Al2O3In the method for preparing the catalyst, preferably, the ratio of Fe: mo: al: c6H8O7In a molar ratio of 8:1:9.2: 27.4.
experiments prove that when Fe-Mo/Al is adopted2O3When the catalyst is used as a metal-based catalyst, the NCNT prepared has a nitrogen content of 5.0at.% or more, specifically 15.0 at.% or more, and preferably 16.0 at.% or more.
Further, the present invention provides Co-Mo/Al2O3Two preparation methods of the catalyst are as follows:
hydrothermal synthesis method: mixing Co (NO)3)3·6H2O、Al(NO3)3·9H2O and (NH)4)6Mo7O24·4H2And dripping the O solution into the CTAB solution, continuously stirring uniformly, and adjusting the pH value of the solution to 8 by using ammonia water. Then, the precursor is transferred to a linerStainless steel autoclave with teflon and kept at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Co-Mo/Al2O3A catalyst.
In the presence of Co-Mo/Al2O3In the preparation method of the catalyst, the molar ratio of Co to Mo to Al is 8:3:10, and the molar ratio of Mo to CTAB is equal to 1:10.
Sol-gel method: mixing Co (NO)3)3·6H2O、 (NH4)6Mo7O24·4H2O、Al(NO3)3·9H2O and C6H8O7·H2Dissolving O in 50mL deionized water, continuously stirring in 80 ℃ water bath until a jelly is formed, transferring the formed jelly into a 110 ℃ oven for treatment for 2h, continuously roasting in air at 500 ℃ for 2h, collecting the product and grinding to obtain Fe-Mo/Al2O3Catalyst particles.
In the presence of Co-Mo/Al2O3In the method for preparing the catalyst, preferably, the Co: mo, Al, C6H8O7In a molar ratio of 8:1:9.2: 27.4.
Experiments show that when Co-Mo/Al is adopted2O3When the catalyst is used as a metal-based catalyst, the nitrogen content of the prepared NCNT is more than 5.0at.%, specifically more than 9.0 at.%.
Of course, the preparation method of the metal-based catalyst includes, but is not limited to, a sol-gel method, a hydrothermal synthesis method, a solution synthesis method. Fe-Mo/Al provided above2O3Catalyst and Co-Mo/Al2O3The preparation method of the catalyst belongs to a hydrothermal synthesis method and a sol-gel method. The invention can also adopt other preparation methods to prepare the metal-based catalyst capable of being used for growing the NCNT.
Specifically, in the preparation method of the present invention, the carbon-nitrogen source includes a gaseous carbon-nitrogen source, a gasified solid carbon-nitrogen source, or a gasified liquid carbon-nitrogen source. The gaseous carbon nitrogen source includes, but is not limited to, ammonia, acetylene; the solid carbon and nitrogen source includes, but is not limited to, imidazole, nitrogen mustard, melamine, p-phenylenediamine, benzimidazole; the liquid carbon-nitrogen source includes, but is not limited to, hydrocyanic acid, ammonia, aniline, pyridine, ethylenediamine, acetonitrile.
In specific application, the nitrogen atom in the nitrogen atom-containing carrier gas includes but is not limited to one or more of nitrogen, ammonia, nitric oxide, nitrogen dioxide and dinitrogen trioxide. In the carrier gas, the content of the nitrogen atom-containing component can be controlled according to the specific nitrogen doping amount in the NCNT, the content of the nitrogen atom-containing component can be different from 0.1 to 100 percent, and the content of the nitrogen atom-containing component is volume percent in the invention. Of course, the carrier gas contains an inert gas in addition to the nitrogen atom-containing gas.
In specific application, the nitrogen doping amount in the NCNT can be controlled by controlling the ratio of the carbon source and the nitrogen source in the carbon-nitrogen source and the content of nitrogen atom gas in the nitrogen atom-containing carrier gas, so that the NCNT with ultrahigh nitrogen doping amount can be obtained, and specifically, the nitrogen doping amount of the NCNT is 0.1-50 at.%.
In the specific application, the yield of the NCNT is 1-2000% of the dosage of the metal-based catalyst.
The technical solution of the present invention will be described in detail by the following specific examples.
Example 1
In this example, the method is as follows:
(1) preparation of Fe-Mo/Al by sol-gel method2O3Catalyst: mixing Fe (NO)3)3·9H2O、(NH4)6Mo7O24·4H2O、Al(NO3)3·9H2O and C6H8O7·H2O is mixed according to a molar ratio of Fe: mo: al: c6H8O7Dissolving the powder in deionized water in a ratio of =8:1:9.2:27.4, continuously stirring in a water bath at 80 ℃ until a jelly is formed, then transferring the formed jelly into an oven at 110 ℃ for treatment for 2 hours, continuously roasting in air at 500 ℃ for 2 hours, collecting the product and grinding to obtain Fe-Mo/Al2O3Catalyst particles.
(2) 5g of imidazole are prepared as carbonNitrogen source, 0.1g of Fe-Mo/Al prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 10% NH3The carrier gas flow rate is controlled to 100 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Fe-Mo/Al) in the reactor2O3Catalyst) surface, setting the growth temperature of NCNT at 700 ℃, the growth process lasts 15 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 16.3 at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 800% of the amount of metal-based catalyst used.
Example 2
In this example, the method is as follows:
(1) hydrothermal method for preparing Fe-Mo/Al2O3Catalyst: mixing Fe (NO)3)3·9H2O、Al(NO3)3·9H2O and (NH)4)6Mo7O24·4H2The O solution (molar ratio of Fe: Mo: Al 8:3:10) was added dropwise to the CTAB solution (molar ratio of Mo: CTAB equal to 1:10 with continuous stirring). The pH of the solution was adjusted to 8 using ammonia. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and held at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Fe-Mo/Al2O3A catalyst.
(2) 5g of imidazole as a carbon-nitrogen source was prepared and 0.1g of Fe-Mo/Al was prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing NH3Controlling the flow rate of carrier gas at 400 mL/min, carrying the gasified carbon-nitrogen source through a metal-based catalyst (Fe-Mo/Al) in the reactor2O3Catalyst) surface, setting the growth temperature of NCNT at 750 ℃, the growth process lasts 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 15.8 at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 1000% of the amount of metal-based catalyst used.
Example 3
In this example, the method is as follows:
(1) hydrothermal method for preparing Fe-Mo/Al2O3Catalyst: mixing Fe (NO)3)3·9H2O、Al(NO3)3·9H2O and (NH)4)6Mo7O24·4H2The O solution (molar ratio of Fe: Mo: Al 8:3:10) was added dropwise to the CTAB solution (molar ratio of Mo: CTAB equal to 1:14 with continuous stirring). The pH of the solution was adjusted to 8 using ammonia. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and held at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Fe-Mo/Al2O3A catalyst.
(2) 5g of imidazole are prepared and 0.1g of Fe-Mo/Al are prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing N2Controlling the flow rate of carrier gas at 500 mL/min, carrying the gasified carbon-nitrogen source through a metal-based catalyst (Fe-Mo/Al) in the reactor2O3Catalyst) surface, setting the growth temperature of NCNT at 750 ℃, the growth process lasts 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 15.6 at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 1100% of the amount of metal-based catalyst used.
Example 4
In this example, the method is as follows:
(1) hydrothermal method for preparing Co-Mo/Al2O3Catalyst: mixing Co (NO)3)3·6H2O、Al(NO3)3·9H2O and (NH)4)6Mo7O24·4H2The O solution (molar ratio of Co: Mo: Al 8:3:10) was added dropwise to the CTAB solution (molar ratio of Mo: CTAB equal to 1:10 with continuous stirring). The pH of the solution was adjusted to 8 using ammonia. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and at 130 deg.CAnd keeping for 24 hours. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Co-Mo/Al2O3A catalyst.
(2) 5g of imidazole are prepared and 0.1g of Co-Mo/Al are prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 30% NH3The carrier gas flow rate is controlled to 500 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Co-Mo/Al) in the reactor2O3Catalyst) surface, setting the growth temperature of NCNT at 800 ℃, the growth process lasts 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 9.2 at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 1600% of the amount of metal-based catalyst used.
Example 5
In this example, the method is as follows:
(1) hydrothermal method for preparing Co-Mo/Al2O3Catalyst: mixing Co (NO)3)3·6H2O、Al(NO3)3·9H2O and (NH)4)6Mo7O24·4H2The O solution (molar ratio of Co: Mo: Al 8:3:10) was added dropwise to the CTAB solution (molar ratio of Mo: CTAB equal to 1:15 with continuous stirring). The pH of the solution was adjusted to 8 using ammonia. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and held at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Co-Mo/Al2O3A catalyst.
(2) 5g of imidazole are prepared and 0.1g of Co-Mo/Al are prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 10% NH3The carrier gas flow rate is controlled to 500 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Co-Mo/Al) in the reactor2O3Catalyst) surface, setting the growth temperature of NCNT at 800 ℃, and the growth processLasting for 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 9.0 at.% as determined by X-ray photoelectron spectroscopy (XPS) and a yield of NCNT of 1200% of the amount of metal-based catalyst used.
Example 6
In this example, the method is as follows:
(1) preparation of Co-Mo/Al by sol-gel method2O3Catalyst: mixing Co (NO)3)3·6H2O、(NH4)6Mo7O24·4H2O、Al(NO3)3·9H2O and C6H8O7·H2O is mixed according to the mol ratio of Co, Mo, Al and C6H8O7Dissolving the powder in 50mL of deionized water in a ratio of =9:1:10.2:27.4, continuously stirring in a water bath at 80 ℃ until a jelly is formed, then transferring the formed jelly into a drying oven at 110 ℃ for treating for 2 hours, continuously roasting in air at 500 ℃ for 2 hours, collecting the product and grinding to obtain Co-Mo/Al2O3Catalyst particles.
(2) 5g of imidazole is prepared as a carbon-nitrogen source, and 0.1g of Co-Mo/Al is prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 30% NH3The carrier gas flow rate was controlled at 300 mL/min by/Ar carrying a vaporized carbon-nitrogen source over a metal-based catalyst (Fe-Mo/Al) in the reactor2O3Catalyst) surface, the growth temperature of NCNT was set at 850 ℃, the growth process lasted for 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 9at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 1600% of the amount of metal-based catalyst.
Example 7
In this example, the method is as follows:
(1) hydrothermal method for preparing Fe-Mo2O3Catalyst: mixing Fe (NO)3)3·9H2O and (NH)4)6Mo7O24·4H2The O solution (molar ratio of Fe: Mo is 8:3) is dropped into the CTAB solution (Mo: CTAB under continuous stirring)Is equal to 1: 10). The pH of the solution was adjusted to 8 using ammonia. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and held at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Fe-Mo2O3A catalyst.
(2) 4g of imidazole are prepared and 0.1g of Fe-Mo/Al are prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 10% NH3The carrier gas flow rate is controlled to be 500 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Fe-Mo) in the reactor2O3Catalyst) surface, setting the growth temperature of NCNT at 1000 ℃, the growth process lasts 20 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 6.0 at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 700% of the amount of metal-based catalyst used.
Example 8
In this example, the method is as follows:
(1) sol-gel method for preparing Co-Mo2O3Catalyst: mixing Co (NO)3)3·6H2O、 (NH4)6Mo7O24·4H2O and C6H8O7·H2O is mixed according to the molar ratio of Co to Mo to C6H8O7Dissolving the powder in 50mL of deionized water at a ratio of 8:1:17.4, continuously stirring in a water bath at 80 ℃ until a jelly is formed, transferring the formed jelly into a drying oven at 110 ℃ for 2 hours, continuously roasting in air at 500 ℃ for 2 hours, collecting the product, and grinding to obtain Co-Mo2O3Catalyst particles.
(2) Preparing 4g of imidazole as a carbon-nitrogen source, and preparing 0.1g of Co-Mo2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 30% NH3The flow rate of carrier gas is controlled to 300 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Co-Mo) in the reactor2O3Catalyst) surface, the growth temperature of NCNT was set at 850 ℃, the growth process lasted for 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 9.7 at.% as determined by X-ray photoelectron spectroscopy (XPS) and a yield of NCNT of 880% of the amount of metal-based catalyst used.
Example 9
In this example, the method is as follows:
(1) hydrothermal method for preparing Fe2O3Catalyst: mixing Fe (NO)3)3·9H2The O solution was added dropwise to the CTAB solution (Fe: CTAB molar ratio equal to 1:10 with continuous stirring). The pH of the solution was adjusted to 8 using ammonia. The precursor was then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and held at 130 ℃ for 24 h. After separation, the precipitate was washed with distilled water and ethanol, then dried at 60 ℃ overnight, and then calcined at 500 ℃ for 2h to obtain Fe2O3A catalyst.
(2) 4.5g of imidazole are prepared and 0.1g of Fe is preformed2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 15% NH3The carrier gas flow rate is controlled to 500 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Fe) in the reactor2O3Catalyst) surface, the growth temperature of NCNT was set at 1200 ℃, the growth process lasted 20 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 7.9at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 1050% of the amount of metal-based catalyst used.
Example 10
In this example, the method is as follows:
(1) preparation of Fe by sol-gel method2O3Catalyst: mixing Fe (NO)3)3·9H2O and C6H8O7·H2O is added according to the mol ratio of Fe to C6H8O7Dissolve in 50mL of deionized water, then continue stirring in a water bath at 80 ℃ until a gum is formed, after which the gum formed is transferred to 1Treating in a 10 ℃ oven for 2h, continuously roasting in air at 500 ℃ for 2h, collecting the product and grinding to obtain Fe2O3Catalyst particles.
(2) 4.5g of imidazole as a carbon-nitrogen source are prepared, and 0.1g of Fe is prepared2O3The catalyst is placed in the reactor.
(3) Gasifying imidazole and introducing 30% NH3The carrier gas flow rate is controlled to 300 mL/min by/Ar, and the gasified carbon-nitrogen source is carried through the metal-based catalyst (Fe) in the reactor2O3Catalyst) surface, the growth temperature of NCNT was set at 850 ℃, the growth process lasted for 30 min.
(4) The product was collected and the prepared NCNT had a nitrogen content of 9.1 at.% as determined by X-ray photoelectron spectroscopy (XPS) and the yield of NCNT was 980% of the amount of metal-based catalyst used.
The results of the examples show that the invention provides a preparation method of high-nitrogen-doping-amount NCNT, which has easily controlled reaction temperature and can meet the requirements of large-scale and large-scale production processes.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. The preparation method of the simple, green and easily industrialized carbon nanotube with ultrahigh nitrogen doping amount is characterized by comprising the following steps: based on the method of catalytic chemical vapor deposition, on the basis of providing a stable carbon-nitrogen source in a reactor, a carrier gas containing nitrogen atoms is provided, the carrier gas carries the carbon-nitrogen source to the surface of the metal-based catalyst, and the NCNT with ultrahigh nitrogen content is obtained by growing along the outer edge of the metal-based catalyst particles.
2. The method for preparing simple, green and easily industrialized carbon nanotubes with ultra-high nitrogen content according to claim 1, wherein the growth temperature of NCNT in the reactor is 300-1400 ℃.
3. The method for preparing the simple, green and easily industrialized carbon nanotube with ultrahigh nitrogen content according to claim 1, wherein the composition of the metal-based catalyst comprises one or more than two metal elements selected from Fe, Mo, Al, Co, Ni, Mg and Cu.
4. The method of claim 1, wherein the method of preparing the metal-based catalyst comprises sol-gel method, hydrothermal synthesis method, and solution synthesis method.
5. The method for preparing the simple, green and easily industrialized carbon nanotube with ultra-high nitrogen doping content according to claim 1, wherein the carbon-nitrogen source comprises a gaseous carbon-nitrogen source, a gasified solid carbon-nitrogen source or a gasified liquid carbon-nitrogen source.
6. The method for preparing the simple, green and easily industrialized carbon nano tube with the ultra-high nitrogen doping content according to the claim 5, wherein the gaseous carbon-nitrogen source comprises ammonia gas and acetylene; the solid carbon-nitrogen source comprises imidazole, nitrogen mustard, melamine, p-phenylenediamine and benzimidazole; the liquid carbon-nitrogen source comprises hydrocyanic acid, ammonia water, aniline, pyridine, ethylenediamine and acetonitrile.
7. The method for preparing simple, green and easily industrialized carbon nanotubes with ultra-high nitrogen content according to claim 1, wherein the nitrogen atom in the nitrogen atom-containing carrier gas is derived from one or more of nitrogen, ammonia, nitric oxide, nitrogen dioxide and dinitrogen trioxide.
8. The method of claim 1, wherein the NCNT has a nitrogen content of 0.1-50 at.%.
9. The method for preparing simple, green and easily industrialized carbon nanotubes with ultra-high nitrogen content according to claim 1, wherein the yield of NCNT is 1-2000% of the amount of metal-based catalyst.
CN202111029502.3A 2021-09-03 2021-09-03 Preparation method of nitrogen-doped carbon nano tube with ultrahigh nitrogen doping amount Pending CN113511644A (en)

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