CN109607513B - Method for preparing single-walled carbon nanotube without sulfur impurities by controllable growth promoter - Google Patents
Method for preparing single-walled carbon nanotube without sulfur impurities by controllable growth promoter Download PDFInfo
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- CN109607513B CN109607513B CN201811445735.XA CN201811445735A CN109607513B CN 109607513 B CN109607513 B CN 109607513B CN 201811445735 A CN201811445735 A CN 201811445735A CN 109607513 B CN109607513 B CN 109607513B
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Abstract
The invention relates to the field of controllable preparation of high-quality single-walled carbon nanotubes with low catalyst content and no sulfur impurities, in particular to a method for controllably preparing single-walled carbon nanotubes without sulfur impurities by using a growth promoter. Selenophen is used as a precursor of a growth promoter, ferrocene is used as a precursor of a catalyst, the selenophen and the ferrocene are dissolved in a toluene solvent, the solution is converted into aerosol through an ultrasonic spray head, and the aerosol is carried into a high-temperature zone through a carrier gas to catalyze ethylene decomposition nucleation growth with high quality and high purity (I)G/IDUp to 180, catalyst content<4.5 wt.%), sulfur-free impurities. The invention uses selenium to replace sulfur as a growth promoter to realize the preparation of the high-quality single-walled carbon nanotube with low catalyst residue and no sulfur impurity; meanwhile, the tail gas for growing the carbon nano tube is prevented from containing hydrogen sulfide gas which is difficult to separate, the treatment and the cyclic utilization of the tail gas are convenient, and the macro preparation of the high-quality single-walled carbon nano tube with low catalyst content is realized.
Description
Technical Field
The invention relates to the field of controllable preparation of high-quality and high-purity single-walled carbon nanotubes without sulfur impurities, in particular to a method for controllably preparing low-catalyst-content single-walled carbon nanotubes by using a novel growth promoter selenium, which realizes that tail gas does not contain hydrogen sulfide gas while preparing the high-quality and high-purity single-walled carbon nanotubes without sulfur impurities, and is beneficial to tail gas treatment and recycling.
Background
The carbon nano tube has chirality-dependent conductive property, ballistic transport property, excellent mechanical property, excellent flexibility, lower density and the like, so that the carbon nano tube is expected to be widely applied to the high-precision technical fields of nano electronic devices, aviation, aerospace and the like. The carbon nanotubes can be prepared without separation of the catalyst, but the catalyst remaining in the carbon nanotube sample has many negative effects. For example, intrinsic properties such as thermal stability and chemical stability of the carbon nanotube are affected, metal nanoparticles are not compatible with organisms in biological applications, catalyst residues affect light transmission properties in transparent conductive thin film applications, and the like. However, the general method of removing the catalyst in the carbon nanotube by acid washing can destroy the structure of the carbon nanotube, affect the physical and chemical properties thereof, and bring about the problem of environmental pollution. Therefore, the control of the preparation of the carbon nano tube with high quality and low catalyst residue is of great significance.
At present, the floating catalyst chemical vapor deposition method is one of the most effective methods for preparing high-quality and high-purity single-walled carbon nanotubes. The carbon nano tube prepared by the method needs the assistance of a growth promoter besides a necessary catalyst, otherwise, the growth efficiency is extremely low, and the most commonly used growth promoter is sulfur (A.H.Window et al.Faraday Discuss, 2014,173, 47-65; and II: Lili Zhang et al.J.Phys.chem.Lett.2014,5,8, 1427-. The addition of sulfur growth promoters resulted in samples of single-walled carbon nanotubes containing sulfur impurities that caused poisoning and deactivation of the nanocatalyst loaded on the carbon nanotubes (document three: Bartholomew, c.h. applied Catalysis a: General,2001,212(1-2),17-60), or reduced catalyst stability, as well as the evolution of hydrogen sulfide gas under acidic conditions. Therefore, the presence of sulfur impurities limits the application of carbon nanotubes in the field of catalysis. In addition, conventional sulfur growth promoters tend to form hydrogen sulfide gas with hydrogen in the reaction atmosphere, which can pollute the environment if the hydrogen sulfide gas is discharged into the atmosphere, and which is costly and difficult to remove completely if the tail gas is recycled. On the other hand, the temperature for growing the high-quality single-walled carbon nanotube by the existing floating catalyst chemical vapor deposition method is generally higher than 1100 ℃, which has high requirements on the material of a reaction furnace tube and increases the difficulty of large-scale preparation.
Therefore, the key problems to be solved urgently at present are: how to achieve the macroscopic preparation of high-quality, high-purity single-walled carbon nanotubes without using sulfur.
Disclosure of Invention
The invention aims to provide a method for preparing a single-walled carbon nanotube with high purity, high quality and no sulfur impurity by using a novel growth promoter in a controllable way, namely selenium in the same family with sulfur is used as the growth promoter, so that selenium and iron form an iron selenium compound with a low melting point in a high-temperature region of a chemical vapor deposition furnace, and the growth of the single-walled carbon nanotube is catalyzed with high efficiency, thereby preparing the single-walled carbon nanotube with high purity, high quality and no sulfur impurity. The invention solves the first technical problem of realizing the high-efficiency catalytic growth of the carbon nano tube by the iron selenium compound and preparing the high-quality single-wall carbon nano tube with high purity and no sulfur impurity; the invention solves the second technical problem that the floating catalyst chemical vapor deposition method is realized to grow the high-quality single-walled carbon nanotube at lower temperature by utilizing the intrinsic property that the melting point (965 ℃) of the iron selenide is lower than the melting point (1194 ℃) of the iron sulfide; the third technical problem solved by the invention is to overcome the problem that the tail gas generated in the preparation of the single-walled carbon nanotube by the existing floating catalyst chemical vapor deposition method contains hydrogen sulfide gas which is difficult to remove.
The technical scheme of the invention is as follows:
a method for preparing a single-walled carbon nanotube without sulfur impurities by using a growth promoter in a controllable manner comprises the steps of replacing traditional sulfur with selenium as the growth promoter, using selenophene as a growth promoter precursor, using ferrocene as a catalyst precursor, dissolving the selenophene and the ferrocene in a liquid-phase carbon source to form a solution, converting the solution into aerosol through an ultrasonic atomization device, bringing the aerosol into a high-temperature region of a chemical vapor deposition furnace together with a gas-phase carbon source through carrier gas, decomposing selenium atoms by the selenophene at the high-temperature region, forming a low-melting-point iron selenium compound with iron, and promoting the carbon source to decompose and nucleate to grow the single-walled carbon nanotube, thereby preparing the high-quality single-walled carbon nanotube with low catalyst content and without sulfur impurities.
The method for preparing the single-walled carbon nanotube without sulfur impurities by the controllable growth promoter comprises the following steps of adding a very small amount of selenophen: 0.01-0.09 g of selenophene/10 g of liquid-phase carbon source, and realizing the high-efficiency growth of the carbon nano tube.
The method for preparing the single-walled carbon nanotube without sulfur impurities by controlling the growth promoter is used for thermogravimetric analysis of catalyst impurities in the single-walled carbon nanotubeThe content is less than 4.5 wt.%, so that the negative influence caused by catalyst residue in the practical application of the single-walled carbon nanotube is reduced; the concentrated oxidation resistance temperature of the sample is higher than 780 ℃, and the temperature of the single-walled carbon nanotube IG/IDValues greater than 150 indicate high crystallinity of the carbon nanotubes.
The method for preparing the single-walled carbon nanotube without sulfur impurities by using the growth promoter in a controllable way has the advantages that the single-walled carbon nanotube does not contain sulfur impurities, and the actual application range of the single-walled carbon nanotube is widened.
The method for preparing the single-walled carbon nanotube without sulfur impurities by using the growth promoter in a controllable manner has the advantages that the diameter of the single-walled carbon nanotube is distributed in a narrow range of 1.9-2.3 nm, and the average diameter is 2.1 nm.
The method for preparing the single-walled carbon nanotube without sulfur impurities by using the growth promoter in a controllable manner has the advantages that tail gas does not contain hydrogen sulfide gas which is difficult to separate, and the tail gas treatment and the recycling are facilitated.
The growth promoter can control the preparation method of the single-walled carbon nanotube without sulfur impurities, the growth temperature of the single-walled carbon nanotube is 900-1100 ℃, the temperature required by the floating catalyst chemical vapor deposition method for growing the single-walled carbon nanotube is reduced, and the energy consumption is reduced.
The method for preparing the single-walled carbon nanotube without sulfur impurities under the control of the growth promoter comprises the steps of introducing a liquid-phase carbon source, a catalyst precursor and a growth promoter precursor solution into a chemical vapor deposition furnace by using an injection pump and an ultrasonic atomization device, wherein the mass ratio of the liquid-phase carbon source, the catalyst precursor and the growth promoter precursor is (9-11 g): (0.2-0.4 g): 0.01-0.09 g), and the liquid-phase carbon source, the catalyst precursor and the growth promoter precursor solution are injected into the chemical vapor deposition furnace at the speed of 0.1 ml/h-0.5 ml/h.
The method for preparing the single-walled carbon nanotube without sulfur impurities under the control of the growth promoter comprises the steps of simultaneously using a liquid-phase carbon source as a solvent for a catalyst precursor and a growth promoter precursor, specifically using toluene, using ethylene as a gas-phase carbon source, and using hydrogen, argon or nitrogen as carrier gas.
The method for preparing the single-walled carbon nanotube without sulfur impurities by using the growth promoter in a controllable manner has the advantages that the flow of carrier gas is 2000-8000 ml/min, and the flow of a gas-phase carbon source is 2-15 ml/min; the chemical vapor deposition is carried out under the protective gas, and the flow rate of the protective gas is 100-300 ml/min.
The design idea of the invention is as follows:
the invention firstly provides a method for massively preparing the single-walled carbon nanotube with high quality, high purity and no sulfur impurity by using selenium as a growth promoter, and provides a new method for preparing the single-walled carbon nanotube with tail gas containing no hydrogen sulfide gas which is difficult to separate and highly toxic. The method utilizes selenium to replace sulfur as a growth promoter for growing the single-walled carbon nanotube by a floating catalyst chemical vapor deposition method, and solves two scientific and technical problems that sulfur impurities are remained in a carbon nanotube sample, tail gas contains hydrogen sulfide gas which is difficult to separate, and the floating catalyst chemical vapor deposition method is difficult to grow the high-quality single-walled carbon nanotube at low temperature. Furthermore, a clean, pollution-free, high-purity and high-quality mass preparation method of the single-walled carbon nanotube is provided.
The invention has the advantages and beneficial effects that:
1. according to the invention, selenium is used for replacing sulfur as a growth promoter, the macroscopic preparation of the single-walled carbon nanotube without sulfur impurities is realized for the first time, and the key problem that sulfur impurities usually exist in a single-walled carbon nanotube sample prepared by a floating catalyst chemical vapor deposition method is solved, so that the application range of the single-walled carbon nanotube in the fields of catalysis and the like is widened.
2. The method of the invention avoids the problem that the hydrogen sulfide gas which is difficult to separate and highly toxic exists in the tail gas, and is beneficial to the treatment and the cyclic utilization of the tail gas.
3. The method reduces the appropriate temperature for growing the single-walled carbon nanotube by the floating catalyst chemical vapor deposition method to 900-1100 ℃, greatly reduces the energy consumption in the preparation process of the single-walled carbon nanotube, and has great significance for the macro-scale preparation of the single-walled carbon nanotube by the floating catalyst chemical vapor deposition method.
4. The invention adopts selenium as the growth promoter, thereby realizing the controllable preparation of the single-walled carbon nano-tube with high quality and high purity, avoiding the problems of sulfur impurity, hydrogen sulfide emission and the like caused by using the sulfur growth promoter, and having important significance for promoting and popularizing the practical application of the single-walled carbon nano-tube.
Drawings
FIG. 1 is a schematic diagram of a system for preparing single-walled carbon nanotubes. In the figure, 1 argon bottle; 2, a vinyl bottle; 3 hydrogen gas cylinders; 4, a chemical vapor deposition furnace; 5, an ultrasonic spray head; 6 precision syringe pump.
Fig. 2.1# sample raman spectrum characterization results: (a) the (b) and (c) are respectively Raman spectrum breathing modes excited by 532nm, 633nm and 785nm lasers; (d) for G mode and D mode (633nm laser), I is obtained by calculationG/I D180; in the figure, the abscissa Raman Shift is Raman Shift (cm)-1) The ordinate Intensity is the relative Intensity (a.u.).
Scanning electron micrograph of sample # 3.1: (a) and (b) high and low power scanning electron micrographs of the sample, respectively.
FIG. 4.1# sample transmission electron microscopy characterization results: (a) and (b) high power and low power transmission electron micrographs of the sample, respectively; (c) the diameter distribution results of 100 carbon nanotubes are counted.
FIG. 5.1# sample thermogravimetric analysis characterization results. In the figure, the right ordinate DSC represents the power flow per gram of sample (mW/mg).
Fig. 6(a) and (b) are X-ray electron spectrum characterization results of sample # 1 and sample # 2, respectively.
Detailed Description
As shown in fig. 1, the system for preparing single-walled carbon nanotubes comprises: argon bottle 1, ethylene bottle 2, hydrogen bottle 3, chemical vapor deposition furnace 4, ultrasonic shower nozzle 5, accurate syringe pump 6 etc. and the concrete structure is as follows: argon gas, ethylene and hydrogen are respectively filled in an argon gas bottle 1, a ethylene bottle 2 and a hydrogen bottle 3, the outlets of the argon gas bottle 1, the ethylene bottle 2 and the hydrogen bottle 3 are converged to an ultrasonic spray head 5 through pipelines, the output pipeline of a precise injection pump 6 is converged to the ultrasonic spray head 5, the outlet of the ultrasonic spray head 5 is communicated with a chemical vapor deposition furnace 4, and toluene, selenophen and ferrocene in the precise injection pump 6 are mixed with hydrogen and ethylene and then sprayed into the chemical vapor deposition furnace 4 through the ultrasonic spray head 5 to grow a single-walled carbon nano tube.
In the specific implementation process, the invention adopts an injection floating catalyst chemical vapor deposition method to control and prepare the single-walled carbon nanotube with high quality and low catalyst content. The method comprises the steps of taking volatile metal organic compound ferrocene as a catalyst precursor, taking selenium-containing organic selenophene as a growth promoter precursor, taking hydrocarbon ethylene and methylbenzene as carbon sources, and taking hydrogen as carrier gas, and growing the single-walled carbon nanotube at 900-1100 ℃.
The method comprises the following specific steps:
(1) under the protection of argon, the temperature of a chemical vapor deposition furnace is firstly raised to the growth temperature (such as 1100 ℃) of a carbon tube, an injector containing a toluene solution is connected with an ultrasonic atomization device (an ultrasonic spray head), and then carrier gas hydrogen and carbon source ethylene are introduced;
(2) atomizing a solution (containing an auxiliary carbon source toluene, a catalyst precursor ferrocene and a growth promoter precursor selenophene) supplied by an injection pump into aerosol, and then carrying the aerosol into a high-temperature region; cracking ferrocene and selenophen to form catalyst particles, decomposing ethylene and toluene into carbon atoms under the action of a catalyst at high temperature, nucleating on the catalyst particles and growing single-walled carbon nanotubes;
(3) the generated carbon nano-tube flows to the tail end of the reactor along with the carrier gas, and is finally collected by a porous filter membrane arranged at the tail end to form a carbon nano-tube film.
(4) And when the preparation is finished, naturally cooling the chemical vapor deposition furnace, stopping supplying the solution, the hydrogen and the ethylene, and introducing argon as protective gas.
Wherein, the argon flow before and after preparation is 200 ml/min, the hydrogen flow during preparation is 2000-8000 ml/min, the ethylene flow is 2-15 ml/min, the supply speed of the solution is 0.1-0.5 ml/h, and the formula of the solution is toluene: ferrocene: selenophene (9-11 g), (0.2-0.4 g) and (0.01-0.09 g).
In the product obtained by the method, the structural characteristics of the single-walled carbon nanotube are analyzed by the characterization means such as Raman spectrum, scanning electron microscope, transmission electron microscope, thermogravimetric analysis and the like.
The present invention will be described in more detail below with reference to examples and the accompanying drawings.
Example 1.
In this embodiment, under the protection of argon gas at 200 ml/min, the temperature of the chemical vapor deposition furnace is first raised to 1100 ℃, then 5000 ml/min of hydrogen and 5 ml/min of ethylene are introduced, a toluene solution containing ferrocene as a catalyst precursor and selenophene as a growth promoter precursor is injected into the ultrasonic nozzle at a speed of 0.2 ml/h, the grown carbon nanotubes flow to the tail of the tube along with the gas flow, and finally a carbon nanotube film is formed on the porous filter membrane arranged at the tail end.
And (3) performing characterization such as Raman spectrum, scanning electron microscope, transmission electron microscope, thermogravimetric analysis and the like on the prepared single-walled carbon nanotube film sample (marked as 1 #).
As shown in fig. 2(a, b, c), the raman spectrum of the single-walled carbon nanotube film has a concentrated peak pattern, indicating a narrow diameter distribution of the single-walled carbon nanotubes. As shown in FIG. 2(D), the single-walled carbon nanotube has a G mode with extremely high strength and a D mode (I) with extremely low strengthG/IDIs 180, generally reported in the literature as IG/IDLess than 50), indicating that the crystallinity of the single-walled carbon nanotubes in the film is very high; as shown in fig. 3, the surface of the carbon nanotube was very clean and there was little catalyst residue observed by scanning electron microscopy. As shown in fig. 4(a, b), the high power transmission electron micrograph shows that the resulting material is single-walled carbon nanotubes and is in the shape of a tube bundle, and the low power micrograph shows that few catalysts are attached to the carbon nanotubes. As shown in FIG. 4(c), the diameters of 100 single-walled carbon nanotubes were counted, and the diameters were found to be distributed in a concentrated manner between 1.9 and 2.3nm, and the average diameter was about 2.1 nm. As shown in fig. 5, thermogravimetric analysis shows that the concentrated oxidation resistance temperature of the sample is about 780 ℃, and the residual amount of the catalyst obtained by calculation is less than 4.5%, which indicates that the carbon nanotube has good crystallinity and high purity. As shown in fig. 6(a), no peak of sulfur was observed by X-ray photoelectron spectroscopy (XPS) analysis, indicating that the carbon nanotube sample contained no sulfur impurities.
Example 2.
In this embodiment, under the protection of argon gas at 200 ml/min, the temperature of the chemical vapor deposition furnace is first raised to 900 ℃, 2000 ml/min hydrogen and 15 ml/min ethylene are then introduced, a toluene solution containing ferrocene as a catalyst precursor and selenophene as a growth promoter precursor is injected into the ultrasonic nozzle at a speed of 0.5 ml/h, the grown carbon nanotubes flow to the tail of the tube along with the gas flow, and finally a carbon nanotube film is formed on a porous filter membrane disposed at the tail end.
The sharp Raman spectrum breathing mode peak shape of the single-walled carbon nanotube film indicates that the diameter distribution of the single-walled carbon nanotube is narrow, IG/ID170, indicating that the single-walled carbon nanotubes in the film had very high crystallinity; the observation of a scanning electron microscope shows that the surface of the carbon nano tube is very clean, and the catalyst residue is little. The high power transmission electron micrograph shows that the obtained material is a single-walled carbon nanotube and is in a tube bundle shape, and the low power micrograph shows that the carbon nanotube is rarely adhered with a catalyst. The diameters of 100 single-walled carbon nanotubes are counted, and the diameters are intensively distributed between 1.8-2.2 nm, and the average diameter is about 2.0 nm. Thermogravimetric analysis shows that the concentrated oxidation resistance temperature of the sample is about 760 ℃, and the residual amount of the catalyst is less than 4.2 wt.%, which indicates that the carbon nano tube has high crystallinity and high purity. As shown in fig. 6(a), no peak of sulfur was observed in X-ray photoelectron spectroscopy (XPS) analysis, indicating that the carbon nanotube sample contained no sulfur impurities.
Comparative example.
In this comparative example, the temperature of the cvd furnace was first raised to 1100 ℃ under the protection of 200 ml/min of argon, 5000 ml/min of hydrogen and 5 ml/min of ethylene were introduced, selenophene used in the examples was replaced with thiophene of equal mass and dissolved in toluene solution, and the toluene solution containing ferrocene and thiophene was injected into the ultrasonic nozzle at a rate of 0.2 ml/h. The grown carbon nanotubes flow to the tail of the tube along with the airflow, and finally a carbon nanotube film is formed on the porous filter membrane arranged at the tail end, and the sample of the single-walled carbon nanotube film is marked as # 2.
The Raman spectrum of the single-walled carbon nanotube film has sharp breathing mode peak, which shows that the diameter distribution of the single-walled carbon nanotube is narrow, IG/ID170, indicating that the single-walled carbon nanotubes in the film had very high crystallinity; the observation of a scanning electron microscope shows that the surface of the carbon nano tube is very clean, and the catalyst residue is little. The high-power transmission electron micrograph shows that the obtained material is a single-walled carbon nanotube and is in a tube bundle shape, and the low-power micrographIndicating that there is little catalyst attachment to the carbon nanotubes. The diameters of 100 single-walled carbon nanotubes are counted, and the diameters of the single-walled carbon nanotubes are intensively distributed between 1.7 and 2.3nm, and the average diameter of the single-walled carbon nanotubes is about 2.0 nm. Thermogravimetric analysis shows that the sample has a concentrated oxidation resistance temperature of about 780 ℃ and a catalyst residue content of less than 5.0 wt.%, which indicates that the carbon nanotube has high crystallinity and high purity. As shown in fig. 6(b), the 2p peak of sulfur was detected by X-ray photoelectron spectroscopy, indicating that the carbon nanotubes contained sulfur impurities.
The results of the embodiment and the comparative example show that the selenium in the same family with sulfur is selected as the growth promoter, so that the high-quality and high-purity single-walled carbon nanotube can be massively grown at a lower temperature (900-1100 ℃), a carbon nanotube sample does not contain sulfur impurity residues, and chemical vapor deposition tail gas does not contain hydrogen sulfide gas which is difficult to remove and is extremely toxic, so that the method has important significance for the modeling preparation and the application of the single-walled carbon nanotube by adopting a floating catalyst chemical vapor deposition method.
Claims (7)
1. A method for preparing a single-walled carbon nanotube without sulfur impurities by using a growth promoter in a controllable manner is characterized in that selenium is used for replacing traditional sulfur as the growth promoter, selenophene is used as a precursor of the growth promoter, ferrocene is used as a precursor of a catalyst, the selenophene and the ferrocene are dissolved in a liquid-phase carbon source to form a solution, the solution is converted into aerosol through an ultrasonic atomization device, carrier gas and a gas-phase carbon source are brought into a high-temperature area of a chemical vapor deposition furnace together, selenium atoms are separated by the selenophene at the high-temperature area, a low-melting-point iron selenium compound is formed by the selenophene and iron, the carbon source is promoted to be decomposed to form nuclei for growing the single-walled carbon nanotube, and thus the high-quality single-walled carbon nanotube with low catalyst content and without sulfur impurities is prepared;
addition of very small amounts of selenophene: 0.01-0.09 g of selenophene/10 g of liquid-phase carbon source to realize the high-efficiency growth of the carbon nano tube;
the diameter of the single-walled carbon nanotube is distributed in a narrow range of 1.9-2.3 nm, and the average diameter is 2.1 nm;
the growth temperature of the single-walled carbon nanotube is 900-1100 ℃, the temperature required by the floating catalyst chemical vapor deposition method for growing the single-walled carbon nanotube is reduced, and the energy consumption is reduced.
2. The method for controllably preparing the single-walled carbon nanotube without the sulfur impurity by the growth promoter according to claim 1, wherein the content of the catalyst impurity in the single-walled carbon nanotube is less than 4.5 wt.% by thermogravimetric analysis, so that the negative effect caused by the catalyst residue in the practical application of the single-walled carbon nanotube is reduced; the concentrated oxidation resistance temperature of the sample is higher than 780 ℃, and the temperature of the single-walled carbon nano tube is IG/IDValues greater than 150 indicate high crystallinity of the carbon nanotubes.
3. The method for controllably preparing single-walled carbon nanotubes free of sulfur impurities with the growth promoter as claimed in claim 1, wherein the single-walled carbon nanotubes are free of sulfur impurities, thereby widening the practical application range of the single-walled carbon nanotubes.
4. The method for controllably preparing the single-walled carbon nanotube free of sulfur impurities by using the growth promoter as claimed in claim 1, wherein the tail gas does not contain hydrogen sulfide gas which is difficult to separate, thereby facilitating the treatment and recycling of the tail gas.
5. The method for preparing the single-walled carbon nanotube without sulfur impurities by controlling the growth promoter according to claim 1, wherein the solution of the liquid-phase carbon source, the catalyst precursor and the growth promoter precursor is introduced into the chemical vapor deposition furnace by using an injection pump and an ultrasonic atomization device, and the liquid-phase carbon source, the catalyst precursor and the growth promoter precursor are injected into the chemical vapor deposition furnace at a rate of 0.1 ml/h to 0.5 ml/h, wherein the mass ratio of the liquid-phase carbon source, the catalyst precursor and the growth promoter precursor is (9-11 g): 0.2-0.4 g): 0.01-0.09 g.
6. The method for preparing single-walled carbon nanotubes free of sulfur impurities under control of growth promoter as claimed in claim 1, wherein liquid carbon source is used as solvent for both catalyst precursor and growth promoter precursor, specifically toluene, gas carbon source is ethylene, and carrier gas is hydrogen, argon or nitrogen.
7. The method for controllably preparing the single-walled carbon nanotube free of sulfur impurities by using the growth promoter as claimed in claim 1, wherein the flow rate of the carrier gas is 2000-8000 ml/min, and the flow rate of the gas-phase carbon source is 2-15 ml/min; the chemical vapor deposition is carried out under the protective gas, and the flow rate of the protective gas is 100-300 ml/min.
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| JP7158646B2 (en) * | 2019-08-09 | 2022-10-24 | 学校法人早稲田大学 | CARBON NANOTUBE MANUFACTURING APPARATUS AND MANUFACTURING METHOD |
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| CN114538416B (en) * | 2022-01-19 | 2023-06-02 | 北京大学 | Preparation method of carbon nano tube film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101683976A (en) * | 2008-09-27 | 2010-03-31 | 索尼株式会社 | Carbon nano tube, preparation method thereof and carbon nano tube element |
| US20120088039A1 (en) * | 2010-10-11 | 2012-04-12 | University Of Houston System | Fabrication of single-crystalline graphene arrays |
| CN106660799A (en) * | 2014-06-09 | 2017-05-10 | 卡纳图有限公司 | Catalyst particle and method for producing thereof |
| CN107196020A (en) * | 2017-06-03 | 2017-09-22 | 太原理工大学 | The preparation method of nitrogen-doped carbon nanometer pipe array/carbon fibre material air electrode |
| CN108479712A (en) * | 2018-03-28 | 2018-09-04 | 中山大学 | A kind of the modified carbon nano-tube thin-film material and its application process of adsorbable degrading tetrabromobisphenol A |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100745736B1 (en) * | 2006-02-23 | 2007-08-02 | 삼성에스디아이 주식회사 | Carbon nanotube, a supported catalyst comprising the same, and fuel cell using the same |
| CN104677879B (en) * | 2015-02-11 | 2017-06-20 | 中国科学院金属研究所 | A kind of flexible, transparent gas sensor based on semi-conductive single-walled carbon nanotubes |
-
2018
- 2018-11-29 CN CN201811445735.XA patent/CN109607513B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101683976A (en) * | 2008-09-27 | 2010-03-31 | 索尼株式会社 | Carbon nano tube, preparation method thereof and carbon nano tube element |
| US20120088039A1 (en) * | 2010-10-11 | 2012-04-12 | University Of Houston System | Fabrication of single-crystalline graphene arrays |
| CN106660799A (en) * | 2014-06-09 | 2017-05-10 | 卡纳图有限公司 | Catalyst particle and method for producing thereof |
| CN107196020A (en) * | 2017-06-03 | 2017-09-22 | 太原理工大学 | The preparation method of nitrogen-doped carbon nanometer pipe array/carbon fibre material air electrode |
| CN108479712A (en) * | 2018-03-28 | 2018-09-04 | 中山大学 | A kind of the modified carbon nano-tube thin-film material and its application process of adsorbable degrading tetrabromobisphenol A |
Non-Patent Citations (3)
| Title |
|---|
| Carbon nanotube fibers with martensite and austenite Fe residual catalyst:room temperature ferromagnetism and implications for CVD growth;Aleman,B;《Journal of materials chemistry C》;20170515;第5卷(第22期);第5544-5550页 * |
| Group 16 elements control the synthesis of continuous fibers of;B.Aleman;《CARBON》;20160210;第101卷;第458-464页 * |
| 碳纳米管有序增强体及其复合材料研究进展;李敏等;《航空学报》;20141025;全文 * |
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