CN109607513A - A kind of single-walled carbon nanotube method of growth promoter controllable preparation not sulfur-containing impurities - Google Patents
A kind of single-walled carbon nanotube method of growth promoter controllable preparation not sulfur-containing impurities Download PDFInfo
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- CN109607513A CN109607513A CN201811445735.XA CN201811445735A CN109607513A CN 109607513 A CN109607513 A CN 109607513A CN 201811445735 A CN201811445735 A CN 201811445735A CN 109607513 A CN109607513 A CN 109607513A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/158—Carbon nanotubes
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- C01B32/162—Preparation characterised by catalysts
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
Abstract
The present invention relates to low catalyst levels, the controllable preparation field of the not high quality single-walled carbon nanotube of sulfur-containing impurities, the single-walled carbon nanotube method of specially a kind of growth promoter controllable preparation not sulfur-containing impurities.Using selenophen as growth promoter presoma, ferrocene is dissolved in toluene solvant as catalyst precursor, and by the two, converts the solutions into aerosol by ultrasonic spray nozzle, high-temperature region is brought by carrier gas again, catalysis ethylene decomposition forming core grows high quality, high-purity (IG/IDUp to 180, catalyst content < 4.5wt.%), the single-walled carbon nanotubes of not sulfur-containing impurities.The present invention using seleno for sulphur as growth promoter, realization prepares the high quality single-walled carbon nanotube of low catalyst remnants, not sulfur-containing impurities；Meanwhile avoid in the tail gas of growth carbon nanotube containing being difficult to isolated hydrogen sulfide gas, convenient for tail gas processing and recycle, realize that magnanimity prepares the high quality single-walled carbon nanotube of low catalyst levels.
Description
Technical field
The present invention relates to the high quality of not sulfur-containing impurities, the controllable preparation field of high-purity single-walled carbon, specially
With a kind of method of novel growth promoter selenium controllable preparation low catalyst levels single-walled carbon nanotube, high quality, height are being prepared
The single-walled carbon nanotube of purity, not sulfur-containing impurities simultaneously, realize tail gas in do not contain hydrogen sulfide gas, be conducive to vent gas treatment and
It recycles.
Background technique
Carbon nanotube has chiral conductive properties relied on, ballistic transport characteristic, excellent mechanical property, excellent flexible
Property and lower density etc., therefore be expected to be widely applied in the high-grade, precision and advanced technical field such as nanometer electronic device, Aeronautics and Astronautics.Carbon
The preparation of nanotube be unable to do without catalyst, but remaining catalyst can bring many negative effects in carbon nanotube-sample.Example
Such as, the intrinsic performances such as thermal stability, the chemical stability of carbon nanotube are influenced, metal nanoparticle and biology in biologic applications
Body is incompatible, and catalyst residue influences light transmission etc. in transparent conductive film application.And general pickling removes carbon nanotube
The method of middle catalyst can destroy the structure of carbon nanotube, influence its physical and chemical performance, also bring along problem of environmental pollution.Cause
This, control preparation high quality, the carbon nanotube of low catalyst remnants are of great significance.
Currently, floating catalytic agent chemical vapour deposition technique be prepare high quality, high-purity single-walled carbon it is most effective
One of method.Using this method preparation carbon nanotube in addition to necessary catalyst, it is also necessary to which otherwise the auxiliary of growth promoter is given birth to
Long efficiency is extremely low, most common growth promoter be sulphur (one: A.H.Windle et al.Faraday Discuss. of document,
2014,173,47-65；Two: Lili Zhang et al.J.Phys.Chem.Lett.2014,5,8,1427-1432 of document).
Growth promoter of sulfur is added and will lead in prepared single-walled carbon nanotube sample and contains sulphur impurity, these sulphur impurities will cause
Nanocatalyst poisoning and deactivation (document three: Bartholomew, the C.H.Applied Catalysis supported in carbon nanotube
A:General, 2001,212 (1-2), 17-60), or the stability of catalyst is reduced, and release sulphur in acid condition
Change hydrogen.So application of the presence limitation carbon nanotube of sulphur impurity in catalytic field.In addition, traditional growth promoter of sulfur
Hydrogen sulfide gas easily is formed with the hydrogen in reaction atmosphere, is polluted the environment if hydrogen sulfide gas is discharged into atmosphere, if following
Ring is then removed hydrogen sulfide higher cost using tail gas and is difficult to completely remove.On the other hand, floating current catalyst chemical gaseous phase
The temperature of sedimentation growth high quality single-walled carbon nanotube is generally greater than 1100 DEG C, this is very high to the material requirement of reaction boiler tube,
Increase prepare with scale difficulty.
Thus, current critical issue urgently to be solved is: how high quality, high-purity is realized in the case where not using sulphur
It is prepared by the magnanimity of single-walled carbon nanotube.
Summary of the invention
The object of the present invention is to provide a kind of novel growth promoter controllable preparation high-purities, high quality, not sulfur-containing impurities
Single-walled carbon nanotube method make selenium and iron in chemical vapor deposition stove that is, using the selenium of the same clan with sulphur as growth promoter
High-temperature region forms the iron selenium compound of low melting point, efficient catalytic single-walled carbon nanotube growth, to prepare high-purity, high-quality
The single-walled carbon nanotube of amount, not sulfur-containing impurities.First technical problem that the present invention solves is to realize that iron selenium compound is efficiently urged
The long carbon nanotube of metaplasia prepares the high quality single-walled carbon nanotube of high-purity, not sulfur-containing impurities；Solve second of the present invention
Technical problem is realized and is floated lower than iron sulfide molten point (1194 DEG C) this intrinsic physical property using (965 DEG C) of molten point of ferrous selenide
Catalyst chemical gas phase deposition method grows high quality single-walled carbon nanotube at a lower temperature；The third technology that the present invention solves
Problem is to overcome existing floating catalytic agent chemical vapour deposition technique to prepare single-walled carbon nanotube tail gas to contain the vulcanization for being difficult to remove
The problem of hydrogen.
The technical scheme is that
A kind of single-walled carbon nanotube method of growth promoter controllable preparation not sulfur-containing impurities, is made with seleno for traditional sulphur
Using ferrocene as catalyst precursor, and the two is dissolved for growth promoter using selenophen as growth promoter presoma
Solution is formed in phase carbon source, aerosol is converted the solutions by ultrasonic atomizing device, then by carrier gas together with gas phase carbon source
Bring the high-temperature region of chemical vapor deposition stove into together, selenophen decomposites selenium atom in high-temperature region, and forms low melting point iron selenium with iron
Compound promotes carbon source decomposing shape nucleus growth single-walled carbon nanotube, to prepare low catalyst levels, not sulfur-containing impurities
High quality single-walled carbon nanotube.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, is added minimal amount of selenium
Pheno: 0.01~0.09g selenophen/10g phase carbon source realizes the efficient growth of carbon nanotube.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, thermogravimetric analysis single wall carbon are received
The content of catalyst impurities is less than 4.5wt.% in mitron, and reducing single-walled carbon nanotube, catalyst residue is brought in practical applications
Negative effect；The concentration oxidation resistance temperature of sample is higher than 780 DEG C, the I of single-walled carbon nanotubeG/IDValue is greater than 150, illustrates that carbon is received
The crystallinity of mitron is high.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, in single-walled carbon nanotube not
Sulfur-containing impurities widen the practical ranges of single-walled carbon nanotube.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, diameter of single-wall carbon nano tube
It is distributed in 1.9~2.3nm close limit, average diameter 2.1nm.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, without being difficult to point in tail gas
From hydrogen sulfide gas, be conducive to vent gas treatment and recycle.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, the life of single-walled carbon nanotube
Long temperature is 900~1100 DEG C, temperature needed for reducing floating catalytic agent chemical vapour deposition technique growing single-wall carbon nano tube, drop
Low energy consumption.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, utilizes syringe pump and ultrasound
The solution of phase carbon source, catalyst precursor and growth promoter presoma is introduced chemical vapor deposition stove, liquid by atomising device
The mass ratio of phase carbon source, catalyst precursor and growth promoter presoma is (9~11g): (0.2~0.4g): (0.01~
0.09g), chemical vapor deposition stove is injected with 0.1 ml/hour~0.5 ml/hour of speed.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, phase carbon source conduct simultaneously
The solvent of catalyst precursor and growth promoter presoma specifically uses toluene, and gas phase carbon source uses ethylene, and carrier gas is hydrogen
Gas, argon gas or nitrogen.
The single-walled carbon nanotube method of the growth promoter controllable preparation not sulfur-containing impurities, the flow of carrier gas are 2000
~8000 ml/mins, the flow of gas phase carbon source are 2~15 ml/mins；Chemical vapor deposition carries out under a shielding gas,
The flow of protective gas is 100~300 ml/mins.
Design philosophy of the invention is:
Present invention firstly provides using selenium as growth promoter, magnanimity prepare high quality, high-purity, not sulfur-containing impurities single wall
Carbon nanotube is free of for tail gas and is difficult to separate and the preparation of the single-walled carbon nanotube of the hydrogen sulfide gas of severe toxicity provides new method.
Replace sulphur as the growth promoter of floating catalytic agent chemical vapour deposition technique growing single-wall carbon nano tube using with selenium, solves sulphur
Impurity remained in carbon nanotube-sample and tail gas in containing being difficult to isolated hydrogen sulfide gas and floating catalytic agent chemical gaseous phase
Sedimentation is difficult to this two big science of low-temperature epitaxy high quality single-walled carbon nanotube and technical problem.In turn, a kind of cleaning, nothing are proposed
High-purity, the magnanimity preparation method of high quality single-walled carbon nanotube of pollution.
The invention has the advantages and beneficial effects that:
1, the present invention replaces sulphur as growth promoter using seleno, realizes the magnanimity of not sulfur-containing impurities single-walled carbon nanotube for the first time
Preparation solves usually there is this pass of sulphur impurity in the single-walled carbon nanotube sample of floating catalytic agent chemical vapour deposition technique preparation
Key problem, to widen single-walled carbon nanotube in the application range in the fields such as catalysis.
2, the method for the present invention avoid there are problems that being difficult in tail gas separating and the hydrogen sulfide gas of severe toxicity this, be conducive to
It the processing of tail gas and recycles.
3, the method for the present invention reduces the preference temperature of floating catalytic agent chemical vapour deposition technique growing single-wall carbon nano tube
To 900~1100 DEG C, the energy consumption in single-walled carbon nanotube preparation process is greatly reduced, the floating of single-walled carbon nanotube is urged
Agent chemical vapour deposition technique magnanimity prepare with scale is significant.
4, the present invention by using selenium be used as growth promoter, that is, realize high quality, high-purity single-walled carbon can
It controls standby, and avoids using sulphur impurity, hydrogen sulfide emission brought by growth promoter of sulfur etc. one being problem, to pushing and promote
The practical application of single-walled carbon nanotube is of great significance.
Detailed description of the invention
The preparation system schematic diagram of Fig. 1 single-walled carbon nanotube.In figure, 1 argon bottle；2 ethylene bottles；3 hydrogen cylinders；4 chemical gas
Phase cvd furnace；5 ultrasonic spray nozzles；6 precise injections pump.
Fig. 2 .1# sample Raman Characterization result: (a), (b), (c) be respectively that 532nm, 633nm, 785nm laser swash
The Raman spectrum of hair breathes mould；It (d) is G mould and D mould (633nm laser), by the way that I is calculatedG/ID=180；In figure, abscissa
Raman Shift is Raman shift (cm-1), ordinate Intensity is relative intensity (a.u.).
The stereoscan photograph of Fig. 3 .1# sample: (a) and (b) be respectively sample high power and low power stereoscan photograph.
Fig. 4 .1# sample transmission Electronic Speculum characterization result: (a) and (b) is respectively that the high power of sample and low power transmission electron microscope shine
Piece；It (c) is the diameter distribution results of 100 carbon nanotubes of statistics.
The thermogravimetric analysis characterization result of Fig. 5 .1# sample.In figure, right side ordinate DSC represents the power for flowing to every gram of sample
(mW/mg)。
Fig. 6 (a) and (b) are respectively the X-ray electron spectrum characterization result of 1# and 2# sample.
Specific embodiment
As shown in Figure 1, the preparation system of single-walled carbon nanotube includes: argon bottle 1, ethylene bottle 2, hydrogen cylinder 3, chemical gaseous phase
Cvd furnace 4, ultrasonic spray nozzle 5, precise injection pump 6 etc., specific structure is as follows: argon bottle 1, ethylene bottle 2, in hydrogen cylinder 3 respectively
Equipped with argon gas, ethylene, hydrogen, the outlet of argon bottle 1, ethylene bottle 2, hydrogen cylinder 3 is collected to ultrasonic spray nozzle 5 by pipeline, essence
The output pipe of close syringe pump 6 is collected to ultrasonic spray nozzle 5, and the outlet of ultrasonic spray nozzle 5 is communicated with chemical vapor deposition stove 4,
After toluene, selenophen, ferrocene in precise injection pump 6 are mixed with hydrogen, ethylene, chemical vapor deposition is sprayed by ultrasonic spray nozzle 5
In product furnace 4, growing single-wall carbon nano tube.
In the specific implementation process, the present invention is prepared high-quality using injection floating catalytic agent chemical vapour deposition technique
The single-walled carbon nanotube of amount, low catalyst levels.Using volatile metallo-organic compound ferrocene as catalyst precursor, contain
The organic matter selenophen of selenium be growth promoter presoma, hydrocarbon ethylene and toluene be carbon source, hydrogen is carrier gas, 900
Growing single-wall carbon nano tube at~1100 DEG C.
Specific step is as follows for this method:
(1) under protection of argon gas, chemical vapor deposition stove temperature is first risen into carbon pipe growth temperature (such as 1100 DEG C), will contained
There is the syringe of toluene solution to connect with ultrasonic atomizing device (ultrasonic spray nozzle), then is passed through carrier gas hydrogen and carbon source ethylene；
(2) solution of syringe pump supply is (comprising before auxiliary carbon source toluene, catalyst precursor ferrocene and growth promoter
Drive body selenophen) be atomized into aerosol after, carrier gas carrying under enter high-temperature region；Ferrocene and selenophen crack to form catalyst particles
Grain, under the action of high mild catalyst, ethylene and toluene decomposite carbon atom and on the catalyst particles forming core, growing single-wall
Carbon nanotube；
(3) carbon nanotube generated flows to reactor tail end with carrier gas, and the porous membrane for being ultimately placed to tail end is collected
Form carbon nano-tube film.
(4) at the end of preparing, the cooling of chemical vapor deposition stove natural cooling stops supply solution, hydrogen and ethylene, and leads to
Enter argon gas as protective gas.
Wherein, the argon flow for preparing front and back is all 200 ml/mins, and the hydrogen flowing quantity in preparation is 2000~8000
Ml/min, ethene flow are 2~15 ml/mins, and the feed speed of solution is 0.1~0.5 ml/hour, solution formula
For toluene: ferrocene: selenophen=(9~11g): (0.2~0.4g): (0.01~0.09g).
Using in product obtained by the method for the present invention, single-walled carbon nanotube passes through Raman spectrum, scanning electron microscope, transmission electricity
The characterization methods such as mirror, thermogravimetric analysis analyze its structure feature.
In the following, the present invention is described in further detail by embodiment and attached drawing.
Embodiment 1.
In the present embodiment, under the argon gas protection of 200 ml/mins, chemical vapor deposition stove temperature is first risen to 1100
DEG C, then it is passed through the hydrogen of 5000 ml/mins and the ethylene of 5 ml/mins, promote containing catalyst precursor ferrocene and growth
Toluene solution into agent presoma selenophen is entered in ultrasonic spray nozzle with 0.2 ml/hour of speed injection, the carbon nanotube of growth
With air flow direction pipe tail, carbon nano-tube film is finally formed on the porous membrane for be placed in tail end.
Raman spectrum, scanning electron microscope, transmission electricity are carried out to the single wall carbon nano-tube film sample (being denoted as 1#) of above-mentioned preparation
The characterization such as mirror, thermogravimetric analysis.
As shown in Fig. 2 (a, b, c), the Raman spectrum breathing mould peak type of single wall carbon nano-tube film is concentrated, and shows single wall carbon
The diameter narrowly distributing of nanotube.As shown in Fig. 2 (d), single-walled carbon nanotube has the G mould and extremely low intensive D mould of very high strength
(IG/IDIt is 180, usual I reported in the literatureG/IDCrystallinity less than the single-walled carbon nanotube 50), illustrated in film is very high；
As shown in figure 3, scanning electron microscopic observation discovery carbon nano tube surface is very clean, few catalyst residues.Such as Fig. 4 (a, b) institute
Show, high power transmission electron microscope photo shows that resulting materials are single-walled carbon nanotube and are in bundle-shaped, and macrograph shows carbon nanometer
Few catalyst attachments on pipe.As shown in Fig. 4 (c), by counting the diameter of 100 single-walled carbon nanotubes, its diameter is found
Integrated distribution is between 1.9~2.3nm, and average diameter is about 2.1nm.As shown in figure 5, thermogravimetric analysis shows the sample
Concentrating oxidation resistance temperature is about 780 DEG C, and the residual volume of catalyst is obtained by calculation less than 4.5%, illustrates the knot of carbon nanotube
Crystalline substance is good, with high purity.As shown in Fig. 6 (a), x-ray photoelectron spectroscopy (XPS) analyzes the peak that sulphur is not observed, and shows that carbon is received
Not sulfur-containing impurities in mitron sample.
Embodiment 2.
In the present embodiment, under the argon gas protection of 200 ml/mins, chemical vapor deposition stove temperature is first risen to 900
DEG C, then it is passed through the hydrogen of 2000 ml/mins and the ethylene of 15 ml/mins, contain catalyst precursor ferrocene and growth
The toluene solution of promotor presoma selenophen is entered in ultrasonic spray nozzle with 0.5 ml/hour of speed injection, the carbon nanometer of growth
Pipe finally forms carbon nano-tube film with air flow direction pipe tail on the porous membrane for be placed in tail end.
The Raman spectrum breathing mould peak shape of single wall carbon nano-tube film sharply shows the diameter narrowly distributing of single-walled carbon nanotube,
IG/IDIt is 170, illustrates that the crystallinity of the single-walled carbon nanotube in film is very high；The table of scanning electron microscopic observation discovery carbon nanotube
Face is very clean, and catalyst residue is seldom.High power transmission electron microscope photo shows that resulting materials are single-walled carbon nanotubes and are in pipe
Pencil, macrograph show few catalyst attachments in carbon nanotube.By counting the diameter of 100 single-walled carbon nanotubes,
It was found that its diameter integrated distribution is between 1.8~2.2nm, average diameter is about 2.0nm.Thermogravimetric analysis shows the concentration of the sample
Oxidation resistance temperature is about 760 DEG C, and catalyst residue amount is less than 4.2wt.%, illustrates that the crystallinity of carbon nanotube is high, with high purity.Such as
Shown in Fig. 6 (a), the peak of sulphur is not observed in x-ray photoelectron spectroscopy (XPS) analysis, shows to be free of in carbon nanotube-sample
Sulphur impurity.
Comparative example
In this comparative example, under the argon gas protection of 200 ml/mins, chemical vapor deposition stove temperature is first risen to 1100
DEG C, then it is passed through the hydrogen of 5000 ml/mins and the ethylene of 5 ml/mins, selenophen used in example is substituted for equal substances
The thiophene of amount is dissolved in toluene solution, then the toluene solution containing ferrocene and thiophene is entered with 0.2 ml/hour of speed injection
In ultrasonic spray nozzle.The carbon nanotube of growth forms carbon with air flow direction pipe tail, finally on the porous membrane for be placed in tail end and receives
Mitron film is denoted as 2# to above-mentioned single wall carbon nano-tube film sample.
The Raman spectrum breathing mould peak type of single wall carbon nano-tube film is sharp, shows the diameter distribution of single-walled carbon nanotube
It is narrow, IG/IDIt is 170, illustrates that the crystallinity of the single-walled carbon nanotube in film is very high；Scanning electron microscopic observation finds carbon nanotube
Surface it is very clean, catalyst residue is seldom.High power transmission electron microscope photo show resulting materials be single-walled carbon nanotube and
In bundle-shaped, macrograph shows few catalyst attachments in carbon nanotube.It is straight by 100 single-walled carbon nanotubes of statistics
Diameter finds its diameter integrated distribution between 1.7~2.3nm, and average diameter is about 2.0nm.Thermogravimetric analysis shows the sample
Concentration oxidation resistance temperature be about 780 DEG C, catalyst residue amount is less than 5.0wt.%, illustrates that the crystallinity of carbon nanotube is high, pure
Degree is high.As shown in Fig. 6 (b), in X-ray photoelectron spectroscopic analysis, detects the peak 2p of sulphur, show to contain sulphur in carbon nanotube
Impurity.
Embodiment and comparative example the result shows that, by select with sulphur selenium of the same clan be used as growth promoter, realization lower
At a temperature of (900~1100 DEG C) magnanimity growth high quality, high-purity single-walled carbon nanotube, and not sulfur-bearing in carbon nanotube-sample
Impurity is remaining, in chemical vapor deposition tail gas without containing being difficult to remove and the hydrogen sulfide gas of severe toxicity, this using floating for being urged
Agent chemical vapour deposition technique prepare with scale single-walled carbon nanotube and its application are of great significance.
Claims (10)
1. a kind of single-walled carbon nanotube method of growth promoter controllable preparation not sulfur-containing impurities, which is characterized in that replaced with seleno
Traditional sulphur is as growth promoter, using selenophen as growth promoter presoma, using ferrocene as catalyst precursor, and
The two is dissolved in phase carbon source and forms solution, aerosol is converted the solutions by ultrasonic atomizing device, then connected by carrier gas
Bring the high-temperature region of chemical vapor deposition stove into together with gas phase carbon source, selenophen decomposites selenium atom in high-temperature region, and is formed with iron
Low melting point iron selenium compound promotes carbon source decomposing shape nucleus growth single-walled carbon nanotube, to prepare low catalyst levels, be free of
The high quality single-walled carbon nanotube of sulphur impurity.
2. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is that minimal amount of selenophen is added: 0.01~0.09g selenophen/10g phase carbon source realizes the efficient growth of carbon nanotube.
3. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is that the content of catalyst impurities is less than 4.5wt.% in thermogravimetric analysis single-walled carbon nanotube, reduces single-walled carbon nanotube and exists
Catalyst residue bring negatively affects in practical application；The concentration oxidation resistance temperature of sample is higher than 780 DEG C, single-walled carbon nanotube
IG/IDValue is greater than 150, illustrates that the crystallinity of carbon nanotube is high.
4. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is, not sulfur-containing impurities in single-walled carbon nanotube widen the practical ranges of single-walled carbon nanotube.
5. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is that diameter of single-wall carbon nano tube is distributed in 1.9~2.3nm close limit, average diameter 2.1nm.
6. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is, without isolated hydrogen sulfide gas is difficult in tail gas, is conducive to vent gas treatment and recycles.
7. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is that the growth temperature of single-walled carbon nanotube is 900~1100 DEG C, and it is single to reduce the growth of floating catalytic agent chemical vapour deposition technique
Temperature needed for wall carbon nano tube reduces energy consumption.
8. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is, using syringe pump and ultrasonic atomizing device by the molten of phase carbon source, catalyst precursor and growth promoter presoma
Liquid introduces chemical vapor deposition stove, the mass ratio of phase carbon source, catalyst precursor and growth promoter presoma be (9~
11g): (0.2~0.4g): (0.01~0.09g) injects chemical gaseous phase with 0.1 ml/hour~0.5 ml/hour of speed
Cvd furnace.
9. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is that phase carbon source is used as the solvent of catalyst precursor and growth promoter presoma simultaneously, specifically uses toluene, gas phase
Carbon source uses ethylene, and carrier gas is hydrogen, argon gas or nitrogen.
10. the single-walled carbon nanotube method of growth promoter controllable preparation described in accordance with the claim 1 not sulfur-containing impurities, special
Sign is that the flow of carrier gas is 2000~8000 ml/mins, and the flow of gas phase carbon source is 2~15 ml/mins；Chemical gas
Mutually deposition carries out under a shielding gas, and the flow of protective gas is 100~300 ml/mins.
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| CN112250060A (en) * | 2020-09-22 | 2021-01-22 | 江西铜业技术研究院有限公司 | Device and method for continuously preparing single-walled carbon nanotubes |
| CN114174220A (en) * | 2019-08-09 | 2022-03-11 | 学校法人早稻田大学 | Apparatus and method for manufacturing carbon nanotubes |
| CN114538416A (en) * | 2022-01-19 | 2022-05-27 | 北京大学 | Preparation method of carbon nanotube film |
| CN115739126A (en) * | 2022-11-29 | 2023-03-07 | 湖北大学 | Application of (ZnS) mIn2S3 photocatalyst in photocatalytic degradation of ethylene and storage and preservation of fruits and vegetables |
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